CN101624449B - Organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane as well as preparation and application - Google Patents
Organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane as well as preparation and application Download PDFInfo
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Abstract
The invention relates to an organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane as well as a preparation and an application. The hybrid membrane is prepared by taking tetrabutyl titanate, glycol, organic phosphoric acid and chitosan as raw materials according to the following matching: the mole ratio of tetrabutyl titanate and glycol is 1:30-1:60 to prepare titanium dioxide micrballon, the mass volume ratio of titanium dioxide micrballon and organic phosphoric acid is 1:4-6, the mass ratio of titanium dioxide micrballon and chitosan is 0.05-0.2:1. The preparation method is as follows: the mixed solution of tetrabutyl titanate and glycol are precipitated in acetone water solution, washed and dried to obtain titanium dioxide micrballon which is put into organic phosphoric acid water solution for standing, the micrballon is put into glacial acetic acid water solution for ultrasound dispersion and is added with chitosan to obtain casting solution which subjects to casting on a substrate (glass plate) and is dried to form a membrane for crosslinking in sulphuric acid water solution, then washing and vacuum drying. The titanium dioxide micrballon and the membrane of the invention have rich source of raw materials, low cost and simple operation, and the prepared hybrid membrane has lower methanol permeability and higher proton conductivity, and can be used as direct methanol fuel cell membrane.
Description
Technical field
The present invention relates to a kind of organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane and preparation and application of leading the proton ability that have.More specifically, the present invention is a kind of organic phosphoric acid (Amino Trimethylene Phosphonic Acid and hydroxy ethylene diphosphonic acid) phosphorylation titanium dioxide microballoon sphere that utilizes, with comprise organic phosphorylated titanium dioxide micrballon, and to methanol permeability reduces, proton conductivity improves and thermostability is improved chitosan hybrid membrane.
Background technology
Fuel cell replaces nonrenewable resources to produce the energy with renewable resources, is acknowledged as one of major technique of future source of energy.Fuel cell is without burning, directly changes the chemical energy of fuel the efficient generating apparatus of electric energy in the mode of electrochemical reaction, have not to be subjected to carnot's working cycle restriction, energy efficiency advantages of higher, and be a kind of eco-friendly new chemical energy.In fuel cell, direct methanol fuel cell (DMFC) is directly to be fuel with the methanol aqueous solution, proton exchange membrane is electrolytical fuel cell, it is except that the advantage with general fuel cell, but also have normal temperature startup fast, high-energy-density, the cheap outstanding advantages such as easily storage, battery structure is simple, cost is low of enriching of fuel, this is particularly useful for portable power source, becomes 21st century fuel cell technology development focus.
Among the DMFC, business-like proton exchange membrane is mainly perfluoro sulfonic acid membrane, as the Nafion series membranes of Dupond company at present.This class film is applied to DMFC, has higher proton conductivity, chemical stability, thermostability and mechanical stability, yet but exists serious methanol permeability, studies show that, when methanol concentration was 1mol/L, the methanol crossover amount can be up to 40%.The methyl alcohol penetrate proton exchange membrane arrives negative electrode and oxygen reacts, reduce fuel availability on the one hand, cause cathod catalyst to poison on the other hand, form mixed current potential at negative electrode, reduce cathode performance, thereby make the degradation of battery and shorten work-ing life of battery greatly.In addition, the perfluoro sulfonic acid membrane (600～1200$/m that costs an arm and a leg
2), so DMFC technology popularization is subjected to the restriction of aspects such as the methanol permeability, proton conduction, cost of proton exchange membrane.Therefore, preparation features good methanol diffusion resistance, proton conductivity be higher, proton exchange membrane material cheaply, is the important step that DMFC technology popularization is used.Hybrid organic-inorganic film has the methanol crossover of inhibition and improves advantages such as film machinery and thermostability thereof because of it, in numerous direct methanol fuel cell films clear superiority is arranged.CN101259382 proposes multiple zeolite is filled in the chitosan film, obviously improved the alcohol-rejecting ability of film, yet the proton conductivity of film also has decline.Be filled into and both can have hindered the proton conductivity that alcohol can also improve simultaneously film in the film so will have the inorganic particle of leading the proton ability, CN1869011 proposes the titanate of sulfonic acid modified is filled in the polymeric film, has increased the proton-conducting of film.Be used for the DMFC film for the titanium dioxide microballoon sphere of organophosphorus acidifying and the chitosan hybrid membrane that comprises it and yet there are no report.
Summary of the invention
The invention provides a kind of organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane and preparation and application.It comprises organic phosphorylated titanium dioxide micrballon and has lower methanol permeability and higher proton conductivity, can be used as the chitosan hybrid membrane of direct methanol fuel cell.
A kind of organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane provided by the invention is to be that raw material is made with butyl (tetra) titanate, ethylene glycol, organic phosphoric acid and chitosan, proportioning: the mol ratio of butyl (tetra) titanate, ethylene glycol is to make titanium dioxide microballoon sphere in 1: 30～1: 60, the mass volume ratio of titanium dioxide microballoon sphere and organic phosphoric acid: 1: 4-6, the mass ratio of titanium dioxide microballoon sphere and chitosan: 0.05-0.5: 1, concrete technology:
Butyl (tetra) titanate and ethylene glycol mixing solutions are added to and carry out precipitin reaction in the aqueous acetone solution, throw out water and washing with alcohol, drying obtains titanium dioxide microballoon sphere, titanium dioxide microballoon sphere is put into the organic phosphoric acid aqueous solution to be stirred, leave standstill, take out microballoon and be placed on ultra-sonic dispersion in the glacial acetic acid aqueous solution through washes clean, add chitosan and obtain film-casting liquid, the filtering and standing deaeration is gone up curtain coating, drying and forming-film with film-casting liquid at substrate (sheet glass), in aqueous sulfuric acid, carry out crosslinked then, cross linking membrane is washed to neutrality, and vacuum-drying promptly obtains organic phosphorylated titanium dioxide micrballon-chitosan hybrid membrane.The mean diameter of described organic phosphorylated titanium dioxide micrballon is about 200-850nm.The thickness of film is between 55-70 μ m.
The step that the preparation method of a kind of organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane provided by the invention comprises:
1) under room temperature and nitrogen protection respectively with butyl (tetra) titanate and ethylene glycol stir process 8～24h, then by measuring at 15～50 ℃ of following mixing solutionss, be poured in the aqueous acetone solution of the moisture 0.2～0.5wt% of being, control butyl (tetra) titanate concentration in acetone is 0.005～0.1M, stirs 0.5～1h, still aging 0.5～1h, produce white precipitate, this precipitation is spent ionized water and ethanol repetitive scrubbing respectively 5 times, and 50～80 ℃ dry down, obtains titanium dioxide microballoon sphere;
2) under the room temperature, the titanium dioxide microballoon sphere of 0.2～1.0g is joined in the organic phosphoric acid aqueous solution of 3～25wt%, stir 3～12h, taking out the microballoon water washing be neutral, centrifugal to pH, and 50～80 ℃ of dryings down obtain organic phosphorylated titanium dioxide micrballon;
3) will contain 5～20% organic phosphorylated titanium dioxide micrballon and place 2wt% glacial acetic acid aqueous solution ultra-sonic dispersion 1～3h, 60～80 ℃ add 2wt% chitosan 2wt% glacial acetic acid aqueous solution down and mix, and stir 1～2h, obtain film-casting liquid.
4) filter under the room temperature, leave standstill 1～2h deaeration, film-casting liquid is gone up curtain coating at substrate (sheet glass), drying and forming-film is put into 2mol/L H
2SO
4Carry out crosslinkedly in the aqueous solution, crosslinked back is washed till neutrality with deionized water, obtains the crosslinked organic phosphorylated titanium dioxide micrballon-chitosan hybrid membrane of sulfuric acid;
5) under the room temperature, the sulfuric acid cross linking membrane vacuum-drying 24h with the step gained obtains organic phosphorylated titanium dioxide micrballon and chitosan hybrid membrane.
Chitosan-the hybridized film that comprises organic phosphorylated titanium dioxide micrballon that the present invention makes is as the direct methanol fuel cell film.
The invention has the advantages that: the organic phosphorylated titanium dioxide micrballon preparation process is simple, the particle good dispersity, and uniform particle diameter is controlled.The chitosan hybrid membrane preparation process that comprises organic phosphorylated titanium dioxide micrballon is simple, and controllability is strong.Raw material sources are abundant, and are cheap, and system film cost is low.The prepared chitosan hybrid membrane that comprises organic phosphorylated titanium dioxide micrballon has lower methanol permeability as the direct methanol fuel cell film in intermediate concentration methanol aqueous solution (12mol/L), and higher proton conductivity, can be used as the direct methanol fuel cell film.
Description of drawings
Fig. 1 is profile scanning electron microscope (SEM) photo of hybridized film of the organic phosphorylated titanium dioxide micrballon-filled chitosan of embodiment 2 preparation.
Fig. 2 is profile scanning electron microscope (SEM) photo of hybridized film of the organic phosphorylated titanium dioxide micrballon-filled chitosan of embodiment 4 preparation.
Embodiment
Embodiment 1
Under the room temperature, the 6.81g butyl (tetra) titanate is joined 107g ethylene glycol, under nitrogen protection, stir 8h after, with above-mentioned butyl (tetra) titanate and ethylene glycol mixing solutions, be poured into moisture in the aqueous acetone solution of 0.3wt%, control butyl (tetra) titanate concentration in acetone is 0.01M, stirs 1h, still aging 0.5h, produce white precipitate, this precipitation is spent ionized water and ethanol repetitive scrubbing respectively 5 times, and 80 ℃ dry down, obtains titanium dioxide microballoon sphere; Under the room temperature, 0.5g titanium microballoon is joined in 10wt% Amino Trimethylene Phosphonic Acid (ATMP) aqueous solution of 30mL mechanical stirring 12h, use deionized water wash then, until supernatant liquor Ph is neutral, and 80 ℃ dry down, obtains organic phosphorylated titanium dioxide micrballon (ball 1).The diameter of ball 1 is about 250nm.
The 1.0g Glacial acetic acid is dissolved in the 50mL water, is mixed with the aqueous acetic acid of 2wt%, the aqueous acetic acid of 50mL is divided into two parts: a 35mL, add the 1g chitosan therein, in 80 ℃ of waters bath with thermostatic control, stir 1h, dissolving fully obtains the film-casting liquid of chitosan; Another part 15mL adds the ball 1 of 0.15g, ultra-sonic dispersion 2h therein.Then above-mentioned two portions solution is mixed, obtain chitosan 2wt%, behind 80 ℃ of following restir 2h, obtain leaving standstill 1h after film-casting liquid filters and carry out deaeration, obtain evenly still film-casting liquid.With film-casting liquid curtain coating on sheet glass, film forming under the room temperature.Then with diaphragm at 2mol/L H
2SO
4Crosslinked 24h in the aqueous solution, be washed till neutrality with deionized water after, with drying at room temperature 24h in the film vacuum drying oven, make the chitosan hybrid membrane (film 1) that comprises organic phosphorylated titanium dioxide micrballon.The thickness of film 1 is about 70 μ m.
When not specifying in the embodiment of the invention, the concentration of use is mass percent concentration.
Embodiment 2
Under the room temperature, the 6.81g butyl (tetra) titanate is joined 107g ethylene glycol, under nitrogen protection, stir 8h after, with above-mentioned butyl (tetra) titanate and ethylene glycol mixing solutions, be poured into moisture in the aqueous acetone solution of 0.3wt%, control butyl (tetra) titanate concentration in acetone is 0.03M, stirs 1h, still aging 0.5h, produce white precipitate, this precipitation is spent ionized water and ethanol repetitive scrubbing respectively 5 times, and 80 ℃ dry down, obtains titanium dioxide microballoon sphere; Under the room temperature, 0.5g titanium microballoon is joined in 10wt% Amino Trimethylene Phosphonic Acid (ATMP) aqueous solution of 30mL mechanical stirring 12h, use deionized water wash then, until supernatant liquor Ph is neutral, and 80 ℃ dry down, obtains organic phosphorylated titanium dioxide micrballon (ball 2).The diameter of ball 2 is about 370nm.
The 1.0g Glacial acetic acid is dissolved in the 50mL water, is mixed with the aqueous acetic acid of 2wt%, the aqueous acetic acid of 50mL is divided into two parts: a 35mL, add the 1g chitosan therein, in 80 ℃ of waters bath with thermostatic control, stir 1h, dissolving fully obtains the film-casting liquid of chitosan; Another part 15mL adds the ball 2 of 0.15g, ultra-sonic dispersion 2h therein.Then above-mentioned two portions solution is mixed, obtain chitosan 2wt%, behind 80 ℃ of following restir 2h, obtain leaving standstill 1h after film-casting liquid filters and carry out deaeration, obtain evenly still film-casting liquid.With film-casting liquid curtain coating on sheet glass, film forming under the room temperature.Then with diaphragm at 2mol/L H
2SO
4Crosslinked 24h in the aqueous solution, be washed till neutrality with deionized water after, with drying at room temperature 24h in the film vacuum drying oven, make the chitosan hybrid membrane (film 2) that comprises organic phosphorylated titanium dioxide micrballon.The thickness of film 2 is about 55 μ m.
Embodiment 3
Under the room temperature, the 6.81g butyl (tetra) titanate is joined 107g ethylene glycol, under nitrogen protection, stir 8h after, with above-mentioned butyl (tetra) titanate and ethylene glycol mixing solutions, be poured into moisture in the aqueous acetone solution of 0.3wt%, control butyl (tetra) titanate concentration in acetone is 0.05M, stirs 1h, still aging 0.5h, produce white precipitate, this precipitation is spent ionized water and ethanol repetitive scrubbing respectively 5 times, and 80 ℃ dry down, obtains titanium dioxide microballoon sphere; Under the room temperature, 0.5g titanium microballoon is joined in 10wt% Amino Trimethylene Phosphonic Acid (ATMP) aqueous solution of 30mL mechanical stirring 12h, use deionized water wash then, until supernatant liquor Ph is neutral, and 80 ℃ dry down, obtains organic phosphorylated titanium dioxide micrballon (ball 3).The diameter of ball 3 is about 510nm.
The 1.0g Glacial acetic acid is dissolved in the 50mL water, is mixed with the aqueous acetic acid of 2wt%, the aqueous acetic acid of 50mL is divided into two parts: a 35mL, add the 1g chitosan therein, in 80 ℃ of waters bath with thermostatic control, stir 1h, dissolving fully obtains the film-casting liquid of chitosan; Another part 15mL adds the ball 3 of 0.15g, ultra-sonic dispersion 2h therein.Then above-mentioned two portions solution is mixed, obtain chitosan 2wt%, behind 80 ℃ of following restir 2h, obtain leaving standstill 1h after film-casting liquid filters and carry out deaeration, obtain evenly still film-casting liquid.With film-casting liquid curtain coating on sheet glass, film forming under the room temperature.Then with diaphragm at 2mol/L H
2SO
4Crosslinked 24h in the aqueous solution, be washed till neutrality with deionized water after, with drying at room temperature 24h in the film vacuum drying oven, make the chitosan hybrid membrane (film 3) that comprises organic phosphorylated titanium dioxide micrballon.The thickness of film 3 is about 70 μ m.
Embodiment 4
Under the room temperature, the 6.81g butyl (tetra) titanate is joined 107g ethylene glycol, under nitrogen protection, stir 8h after, with above-mentioned butyl (tetra) titanate and ethylene glycol mixing solutions, be poured into moisture in the aqueous acetone solution of 0.3wt%, control butyl (tetra) titanate concentration in acetone is 0.07M, stirs 1h, still aging 0.5h, produce white precipitate, this precipitation is spent ionized water and ethanol repetitive scrubbing respectively 5 times, and 80 ℃ dry down, obtains titanium dioxide microballoon sphere; Under the room temperature, 0.5g titanium microballoon is joined in 10wt% Amino Trimethylene Phosphonic Acid (ATMP) aqueous solution of 30mL mechanical stirring 12h, use deionized water wash then, until supernatant liquor Ph is neutral, and 80 ℃ dry down, obtains organic phosphorylated titanium dioxide micrballon (ball 4).The diameter of ball 4 is about 800nm.
The 1.0g Glacial acetic acid is dissolved in the 50mL water, is mixed with the aqueous acetic acid of 2wt%, the aqueous acetic acid of 50mL is divided into two parts: a 35mL, add the 1g chitosan therein, in 80 ℃ of waters bath with thermostatic control, stir 1h, dissolving fully obtains the film-casting liquid of chitosan; Another part 15mL adds the ball 4 of 0.15g, ultra-sonic dispersion 2h therein.Then above-mentioned two portions solution is mixed, obtain chitosan 2wt%, behind 80 ℃ of following restir 2h, obtain leaving standstill 1h after film-casting liquid filters and carry out deaeration, obtain evenly still film-casting liquid.With film-casting liquid curtain coating on sheet glass, film forming under the room temperature.Then with diaphragm at 2mol/L H
2SO
4Crosslinked 24h in the aqueous solution, be washed till neutrality with deionized water after, with drying at room temperature 24h in the film vacuum drying oven, make the chitosan hybrid membrane (film 4) that comprises organic phosphorylated titanium dioxide micrballon.The thickness of film 4 is about 65 μ m.
Embodiment 5
Under the room temperature, the 6.81g butyl (tetra) titanate is joined 107g ethylene glycol, under nitrogen protection, stir 8h after, with above-mentioned butyl (tetra) titanate and ethylene glycol mixing solutions, be poured into moisture in the aqueous acetone solution of 0.3wt%, control butyl (tetra) titanate concentration in acetone is 0.05M, stirs 1h, still aging 0.5h, produce white precipitate, this precipitation is spent ionized water and ethanol repetitive scrubbing respectively 5 times, and 80 ℃ dry down, obtains titanium dioxide microballoon sphere; Under the room temperature, 0.5g titanium microballoon is joined in 10wt% Amino Trimethylene Phosphonic Acid (ATMP) aqueous solution of 30mL mechanical stirring 12h, use deionized water wash then, until supernatant liquor Ph is neutral, and 80 ℃ dry down, obtains organic phosphorylated titanium dioxide micrballon (ball 3).
The 1.0g Glacial acetic acid is dissolved in the 50mL water, is mixed with the aqueous acetic acid of 2wt%, the aqueous acetic acid of 50mL is divided into two parts: a 35mL, add the 1g chitosan therein, in 80 ℃ of waters bath with thermostatic control, stir 1h, dissolving fully obtains the film-casting liquid of chitosan; Another part 15mL adds the ball 3 of 0.05g, ultra-sonic dispersion 2h therein.Then above-mentioned two portions solution is mixed, obtain chitosan 2wt%, behind 80 ℃ of following restir 2h, obtain leaving standstill 1h after film-casting liquid filters and carry out deaeration, obtain evenly still film-casting liquid.With film-casting liquid curtain coating on sheet glass, film forming under the room temperature.Then with diaphragm at 2mol/L H
2SO
4Crosslinked 24h in the aqueous solution, be washed till neutrality with deionized water after, with drying at room temperature 24h in the film vacuum drying oven, make the chitosan hybrid membrane (film 5) that comprises organic phosphorylated titanium dioxide micrballon.The thickness of film 5 is about 70 μ m.
Embodiment 6
Under the room temperature, the 6.81g butyl (tetra) titanate is joined 107g ethylene glycol, under nitrogen protection, stir 8h after, with above-mentioned butyl (tetra) titanate and ethylene glycol mixing solutions, be poured into moisture in the aqueous acetone solution of 0.3wt%, control butyl (tetra) titanate concentration in acetone is 0.05M, stirs 1h, still aging 0.5h, produce white precipitate, this precipitation is spent ionized water and ethanol repetitive scrubbing respectively 5 times, and 80 ℃ dry down, obtains titanium dioxide microballoon sphere; Under the room temperature, 0.5g titanium microballoon is joined in 10wt% Amino Trimethylene Phosphonic Acid (ATMP) aqueous solution of 30mL mechanical stirring 12h, use deionized water wash then, until supernatant liquor Ph is neutral, and 80 ℃ dry down, obtains organic phosphorylated titanium dioxide micrballon (ball 3).
The 1.0g Glacial acetic acid is dissolved in the 50mL water, is mixed with the aqueous acetic acid of 2wt%, the aqueous acetic acid of 50mL is divided into two parts: a 35mL, add the 1g chitosan therein, in 80 ℃ of waters bath with thermostatic control, stir 1h, dissolving fully obtains the film-casting liquid of chitosan; Another part 15mL adds the ball 3 of 0.10g, ultra-sonic dispersion 2h therein.Then above-mentioned two portions solution is mixed, obtain chitosan 2wt%, behind 80 ℃ of following restir 2h, obtain leaving standstill 1h after film-casting liquid filters and carry out deaeration, obtain evenly still film-casting liquid.With film-casting liquid curtain coating on sheet glass, film forming under the room temperature.Then with diaphragm at 2mol/L H
2SO
4Crosslinked 24h in the aqueous solution, be washed till neutrality with deionized water after, with drying at room temperature 24h in the film vacuum drying oven, make the chitosan hybrid membrane (film 6) that comprises organic phosphorylated titanium dioxide micrballon.The thickness of film 6 is about 60 μ m.
Embodiment 7
Under the room temperature, the 6.81g butyl (tetra) titanate is joined 107g ethylene glycol, under nitrogen protection, stir 8h after, with above-mentioned butyl (tetra) titanate and ethylene glycol mixing solutions, be poured into moisture in the aqueous acetone solution of 0.3wt%, control butyl (tetra) titanate concentration in acetone is 0.05M, stirs 1h, still aging 0.5h, produce white precipitate, this precipitation is spent ionized water and ethanol repetitive scrubbing respectively 5 times, and 80 ℃ dry down, obtains titanium dioxide microballoon sphere; Under the room temperature, 0.5g titanium microballoon is joined in 10wt% Amino Trimethylene Phosphonic Acid (ATMP) aqueous solution of 30mL mechanical stirring 12h, use deionized water wash then, until supernatant liquor Ph is neutral, and 80 ℃ dry down, obtains organic phosphorylated titanium dioxide micrballon (ball 3).
The 1.0g Glacial acetic acid is dissolved in the 50mL water, is mixed with the aqueous acetic acid of 2wt%, the aqueous acetic acid of 50mL is divided into two parts: a 35mL, add the 1g chitosan therein, in 80 ℃ of waters bath with thermostatic control, stir 1h, dissolving fully obtains the film-casting liquid of chitosan; Another part 15mL adds the ball 3 of 0.20g, ultra-sonic dispersion 2h therein.Then above-mentioned two portions solution is mixed, obtain chitosan 2wt%, behind 80 ℃ of following restir 2h, obtain leaving standstill 1h after film-casting liquid filters and carry out deaeration, obtain evenly still film-casting liquid.With film-casting liquid curtain coating on sheet glass, film forming under the room temperature.Then with diaphragm at 2mol/L H
2SO
4Crosslinked 24h in the aqueous solution, be washed till neutrality with deionized water after, with drying at room temperature 24h in the film vacuum drying oven, make the chitosan hybrid membrane (film 7) that comprises organic phosphorylated titanium dioxide micrballon.The thickness of film 7 is about 55 μ m.
Embodiment 8
Under the room temperature, the 6.81g butyl (tetra) titanate is joined 107g ethylene glycol, under nitrogen protection, stir 8h after, with above-mentioned butyl (tetra) titanate and ethylene glycol mixing solutions, be poured into moisture in the aqueous acetone solution of 0.3wt%, control butyl (tetra) titanate concentration in acetone is 0.07M, stirs 1h, still aging 0.5h, produce white precipitate, this precipitation is spent ionized water and ethanol repetitive scrubbing respectively 5 times, and 80 ℃ dry down, obtains titanium dioxide microballoon sphere; Under the room temperature, 0.5g titanium microballoon is joined in 10wt% hydroxy ethylene diphosphonic acid (HEDP) aqueous solution of 30mL mechanical stirring 12h, use deionized water wash then, until supernatant liquor Ph is neutral, and 80 ℃ dry down, obtains organic phosphorylated titanium dioxide micrballon (ball 5).The diameter of ball 5 is about 800nm.。
The 1.0g Glacial acetic acid is dissolved in the 50mL water, is mixed with the aqueous acetic acid of 2wt%, the aqueous acetic acid of 50mL is divided into two parts: a 35mL, add the 1g chitosan therein, in 80 ℃ of waters bath with thermostatic control, stir 1h, dissolving fully obtains the film-casting liquid of chitosan; Another part 15mL adds the ball 5 of 0.20g, ultra-sonic dispersion 2h therein.Then above-mentioned two portions solution is mixed, obtain chitosan 2wt%, behind 80 ℃ of following restir 2h, obtain leaving standstill 1h after film-casting liquid filters and carry out deaeration, obtain evenly still film-casting liquid.With film-casting liquid curtain coating on sheet glass, film forming under the room temperature.Then with diaphragm at 2mol/L H
2SO
4Crosslinked 24h in the aqueous solution, be washed till neutrality with deionized water after, with drying at room temperature 24h in the film vacuum drying oven, make the chitosan hybrid membrane (film 8) that comprises organic phosphorylated titanium dioxide micrballon.The thickness of film 8 is about 60 μ m.
Comparative Examples 1
The 1.0g Glacial acetic acid is dissolved in the 50mL water, is mixed with the aqueous acetic acid of 2wt%, add the 1g chitosan therein, in 80 ℃ of waters bath with thermostatic control, stir 1h, dissolve fully, obtain the film-casting liquid of chitosan 2wt%, to obtain leaving standstill 1h after film-casting liquid filters and carry out deaeration, obtain evenly still film-casting liquid.With film-casting liquid curtain coating on sheet glass, film forming under the room temperature.Then with diaphragm at 2mol/L H
2SO
4Crosslinked 24h in the aqueous solution, be washed till neutrality with deionized water after, with drying at room temperature 24h in the film vacuum drying oven, make pure chistosan film (film 9).The thickness of film 9 is about 58 μ m.
Table 1 is depicted as the prepared film 1 of embodiment, film 2, film 3, film 4, film 5, film 6, film 7, the methanol permeability and the proton conductivity result of film 8 and Comparative Examples 1 prepared film 9.
Table 1:
By in the table 1 shown in the result, the chitosan hybrid membrane of having filled organic phosphorylated titanium dioxide micrballon all increases than the pure chistosan film alcohol-rejecting ability, and this is because inserting of inorganic particle prolonged the evolving path of methyl alcohol, suppresses methanol crossover; Along with the particle diameter increase of organic phosphorylated titanium dioxide micrballon, the methanol crossover coefficient reduces gradually, and this is that what particle diameter was big provides longer the evolving path to methanol molecules because with respect to the titanium dioxide microballoon sphere than small particle size; By the increase along with loading level, the methanol crossover coefficient also is to reduce gradually.Owing on titanium dioxide microballoon sphere, introduced organic phosphoric acid, increased the proton transfer avtive spot, so having filled the chitosan hybrid membrane of organic phosphorylated titanium dioxide micrballon all increases than the pure chistosan film proton conductivity, increase along with loading level, the proton conduction of film takes the lead in rising, and the back descends, may be owing to filled 20% o'clock, reunion to a certain degree appears in ball 3 in film, phosphate group can not be given full play to lead proton-effect; The particle diameter of ball is little to the proton conductivity influence.
Claims (5)
1. organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane, it is characterized in that it is is that raw material is made with butyl (tetra) titanate, ethylene glycol, organic phosphoric acid and chitosan, by proportioning: the mol ratio of butyl (tetra) titanate, ethylene glycol is to make titanium dioxide microballoon sphere in 1: 30～1: 60, the mass volume ratio of titanium dioxide microballoon sphere and organic phosphoric acid: 1: 4～6, the mass ratio of titanium dioxide microballoon sphere and chitosan: 0.05～0.2: 1, concrete technology:
Butyl (tetra) titanate and ethylene glycol mixing solutions are added to and carry out precipitin reaction in the aqueous acetone solution, throw out water and washing with alcohol, drying obtains titanium dioxide microballoon sphere, titanium dioxide microballoon sphere is put into the organic phosphoric acid aqueous solution to be stirred, leave standstill, take out microballoon and be placed on ultra-sonic dispersion in the glacial acetic acid aqueous solution through washes clean, add chitosan and obtain film-casting liquid, the filtering and standing deaeration is with film-casting liquid curtain coating on substrate, drying and forming-film, in aqueous sulfuric acid, carry out crosslinked then, cross linking membrane is washed to neutrality, and vacuum-drying promptly obtains organic phosphorylated titanium dioxide micrballon-chitosan hybrid membrane; Described organic phosphoric acid is Amino Trimethylene Phosphonic Acid or hydroxy ethylene diphosphonic acid.
2. according to the described hybridized film of claim 1, it is characterized in that: the mean diameter of described organic phosphorylated titanium dioxide micrballon is 200-850nm.
3. according to the described hybridized film of claim 1, it is characterized in that: the thickness of film is 55-70 μ m.
4. the preparation method of the described organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane of claim 1 is characterized in that the step that comprises:
1) under room temperature and nitrogen protection respectively with butyl (tetra) titanate and ethylene glycol stir process 8～24h, then by measuring at 15～50 ℃ of following mixing solutionss, be poured in the aqueous acetone solution of the moisture 0.2～0.5wt% of being, control butyl (tetra) titanate concentration in acetone is 0.005～0.1M, stirs 0.5～1h, still aging 0.5～1h, produce white precipitate, this precipitation is spent ionized water and ethanol repetitive scrubbing respectively 5 times, and 50～80 ℃ dry down, obtains titanium dioxide microballoon sphere;
2) under the room temperature, the titanium dioxide microballoon sphere of 0.2～1.0g is joined in the organic phosphoric acid aqueous solution of 3～25wt%, stir 3～12h, taking out the microballoon water washing be neutral, centrifugal to pH, and 50～80 ℃ of dryings down obtain organic phosphorylated titanium dioxide micrballon;
3) will contain 5～20% organic phosphorylated titanium dioxide micrballon and place 2wt% glacial acetic acid aqueous solution ultra-sonic dispersion 1～3h, 60～80 ℃ add the 2wt% glacial acetic acid aqueous solution that contain the 2wt% chitosan down and mix, and stir 1～2h, obtain film-casting liquid;
4) filter under the room temperature, leave standstill 1～2h deaeration, film-casting liquid curtain coating on sheet glass, drying and forming-film, put into the 2mol/L H2SO4 aqueous solution then and carry out crosslinkedly, crosslinked back is washed till neutrality with deionized water, obtains the crosslinked organic phosphorylated titanium dioxide micrballon-chitosan hybrid membrane of sulfuric acid;
5) under the room temperature, the sulfuric acid cross linking membrane vacuum-drying 24h with the step 4) gained obtains organic phosphorylated titanium dioxide micrballon and chitosan hybrid membrane.
5. the application of the described organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane of claim 1 is characterized in that it is used as the methanol fuel cell film.
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| CN101798403B (en) * | 2010-03-30 | 2012-02-01 | 东华大学 | Method for preparing chitosan/polyving alcohol/polylactic acid blended dense membrane |
| CN102949744B (en) * | 2011-08-26 | 2015-06-17 | 中国科学院沈阳应用生态研究所 | Biological nano-deodorant and preparation method thereof |
| CN102974230B (en) * | 2012-12-04 | 2014-10-29 | 天津大学 | Chitosan/titanium dioxide ultrathin hybrid film, and preparation method and application thereof |
| CN103897221A (en) * | 2014-03-13 | 2014-07-02 | 天津大学 | Chitosan/phosphorylated silicon dioxide particle hybrid film as well as preparation and application thereof |
| CN105175960B (en) * | 2015-10-08 | 2017-10-24 | 天津大学 | Nafion/ phytic acid modifies hollow dopamine composite membrane and preparation and application |
| CN108155406B (en) * | 2017-12-26 | 2021-04-06 | 中国科学院青岛生物能源与过程研究所 | Phosphosilicate glass doped chitosan intermediate-temperature proton exchange membrane and preparation method thereof |
| CN108511664B (en) * | 2018-03-30 | 2021-05-18 | 吉林师范大学 | Lithium-sulfur battery diaphragm and preparation method thereof |
| CN109569323B (en) * | 2018-11-27 | 2021-09-03 | 华南理工大学 | Organic phosphoric acid modified TiO2Preparation method of/PVC (polyvinyl chloride) blended cation exchange membrane and application of cation exchange membrane in electrodialysis |
| CN112479392B (en) * | 2020-11-23 | 2021-08-27 | 纳琦绿能工程有限公司 | Composite sewage treatment agent and preparation method and application thereof |
| CN115418256B (en) * | 2022-09-22 | 2024-04-12 | 天津大学 | Fuel microsphere, preparation method thereof and propellant |
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