CN102516575A - Method for preparing bipolar membrane modified by heavy metal ion loaded carbon nao tube - Google Patents
Method for preparing bipolar membrane modified by heavy metal ion loaded carbon nao tube Download PDFInfo
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- CN102516575A CN102516575A CN2012100079052A CN201210007905A CN102516575A CN 102516575 A CN102516575 A CN 102516575A CN 2012100079052 A CN2012100079052 A CN 2012100079052A CN 201210007905 A CN201210007905 A CN 201210007905A CN 102516575 A CN102516575 A CN 102516575A
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Abstract
The invention relates to a method for preparing a bipolar membrane modified by a heavy metal ion loaded carbon nao tube. According to the method, the heavy metal ion loaded carbon nao tube is added into a cation exchange membrane to modify the bipolar membrane. The method comprises the following steps of: 1) weighing the heavy metal ion loaded carbon nao tube, adding into absolute ethanol, and performing ultra-sonic oscillation to ensure that the carbon nano tube can be dispersed uniformly in the absolute ethanol; and 2) mixing the absolute ethanol containing the carbon nano tube and the prepared cation membrane solution, and preparing the bipolar membrane by a curtain coating or hot-pressing method. The bipolar membrane prepared by the method has the characteristics of high hydrolytic dissociation efficiency, low membrane impedance, low cell voltage, and high compatibility of two membrane layers, and the like.
Description
Technical field
The present invention relates to a kind of PREPARATIOM OF BIPOLAR MEMBRANE method, is loaded with heavy metals ionic carbon nano-tube modification PREPARATIOM OF BIPOLAR MEMBRANE method specifically.
Background technology
(Bipolar Membrane BPM), is made up of anion-exchange membrane and cationic exchange membrane Bipolar Membrane.Under the DC electric field effect, the water in the Bipolar Membrane intermediate layer will be dissociated into H
+And OH
-, its theoretical voltage is 0.828V.Compare with common electrolysis, bipolar membrane electrodialysis has many advantages, therefore has very widely at aspects such as foodstuffs industry, chemical industry, life science and pollution control, resource recovery, organic acid separation and preparations and uses.Therefore Bipolar Membrane becomes the extremely important branch in film field.The resistance drop that Bipolar Membrane intermediate layer water decomposition efficient directly influences Bipolar Membrane (is a film
IRFall) and the size of bath voltage.Bipolar Membrane yin, yang two retes are carried out modification, with promotion intermediate layer water decomposition, thereby the reduction Bipolar Membrane
IRFall and bath voltage, cut down the consumption of energy, the generation that reduces the side reaction of electric groove electrochemistry has become the focus of current Bipolar Membrane research.
Since Iijima found carbon nanotube (CNTs) in 1991, because its big specific surface area and unique electricity, machinery and structural performance have caused scientific worker's extensive interest and concern.According to the difference of himself structure, carbon nanotube can be divided into SWCN (SWCNTs) and multi-walled carbon nano-tubes (MWCNTs).Although carbon nanotube has these meliority, because its bad dispersibility in the aqueous solution, so its application is restricted.In order to improve its dispersiveness, can introduce some hydrophilic functional group on its surface through appropriate means, for example: hydroxyl, carboxyl, amino, tensio-active agent and hydrophilic polymers etc.
The present invention utilizes loaded with heavy metals ionic carbon nano-tube modification Bipolar Membrane, and with the water decomposition efficient of raising Bipolar Membrane, thereby the IR that reduces Bipolar Membrane falls and bath voltage, reduces the loss of heavy metal ion, improves the mechanical property and the thermostability of Bipolar Membrane.
Summary of the invention
The object of the present invention is to provide that a kind of doping loaded with heavy metals ionic carbon nanotube is with the method for modification Bipolar Membrane in cationic exchange membrane, prepared Bipolar Membrane has low membrane impedance and premium properties such as high mechanical property and thermostability.
The objective of the invention is to realize through following scheme:
1, the preparation of loaded with heavy metals ionic carbon nano-tube modification cationic exchange rete
Accurately take by weighing Xylo-Mucine (CMC) or sodium-alginate (SA), be mixed with massfraction and be 1～10% the CMC aqueous solution or the SA aqueous solution; Other gets Z 150PH (PVA), with the dissolving of zero(ppm) water heated and stirred, joins in the CMC aqueous solution or the SA aqueous solution of above-mentioned preparation, stirs, and gets the PVA-SA aqueous solution or the PVA-CMC aqueous solution.The carbon nanotube of purchasing (CNTs) through pre-treatment, is made heavy metal ion in its load.Accurately take by weighing carbon nanotube then, add in the ethanol, use ultra-sonic oscillation through heavy metal ion in the pretreated load; It is uniformly dispersed, joins in the PVA-SA aqueous solution or the PVA-CMC aqueous solution of above-mentioned preparation, stir; Vacuum deaerator obtains thickness film liquid.Thickness film flow is prolonged in smooth sheet glass, at room temperature air-dry film forming, the use massfraction is 1～10% FeCl earlier
3Crosslinked 10～30 min of solution soaking, the back is clean with distilled water flushing, and natural air drying promptly gets PVA
-CMC-CNTs cationic exchange membrane or SA-CMC-CNTs cationic exchange membrane.
Described PVAC polyvinylalcohol is 0.5～1:1 with the massfraction ratio of CMC or SA.
Described carbon nanotube is 1～100:1000 with the massfraction ratio of CMC or SA.
Described carbon nanotube (CNTs) through pretreated process is: a certain amount of carbon nanotube was put into the concentrated nitric acid reflux 6 hours; Cooling after scouring carbon nanotube; To be that 5% heavy metal nitrate salt joins in the finely dispersed carbon nanotube alcohol suspending liquid of ultra-sonic oscillation with respect to the carbon nanotube mol ratio then; Induction stirring is heated to 100 ℃ of evaporations, promptly gets the nano composite material of carbon nanotube loaded heavy metal ion after the oven dry.
Described loaded with heavy metals ionic carbon nanotube, its heavy metal ion is: Fe
3+, Ni
2+, Cu
2+, Cd
3+, Sn
4+
2, the preparation of chitosan cavity block liquid
Take by weighing certain amount of chitosan (CS); Using massfraction is 1% acetic acid aqueous solution stirring and dissolving, is mixed with 1～10% chitosan acetic acid aqueous solution, slowly drips volume(tric)fraction while stirring and be 2.5% glutaraldehyde solution; Vacuum deaerator can obtain heavy-gravity CS cavity block liquid.
Chitosan acetic acid aqueous solution and glutaraldehyde solution volume ratio are 1000:2～8.
3, PREPARATIOM OF BIPOLAR MEMBRANE
Adopt curtain coating, superimposed, bonding or hot pressed method is with CS cavity block liquid system film and be fixed on the prepared PVA of step 1
-On the anode membrane layer of CMC-CNTs cationic exchange membrane or SA-CMC-CNTs cationic exchange membrane, at room temperature air-dry, promptly get PVA
-CMC-CNTs/CS Bipolar Membrane or SA-CMC-CNTs/CS Bipolar Membrane.
The invention has the advantages that:
Characteristics such as what the present invention relates to utilizes loaded with heavy metals ionic carbon nano-tube modification anode membrane layer, and it is high to make Bipolar Membrane have water decomposition efficient, and membrane impedance is little, and bath voltage is low, and two rete consistencies are good.
Table 1 is a mechanical properties data of utilizing the Bipolar Membrane sample of CMT6104 type microcomputer control electronics universal testing machine survey.
The mechanical property of the different Bipolar Membrane of table 1
| Bipolar Membrane | Maximum load/N | Tensile strength/MPa | Elongation at break/% | Young's modulus/MPa |
| PVA-CMC/CS | 64.70 | 44.46 | 53.82 | 243.78 |
| PVA-CMC-CNTs-Fe/CS | 126.73 | 63.79 | 73.34 | 383.62 |
Can know that from table 1 behind the interpolation CNTs-Fe, elongation at break increases in the PVA-CMC/CS Bipolar Membrane.This is owing to after adding CNTs-Fe, weakened molecule or intermolecular ydrogen bonding effect on the CMC macromolecular chain, and CMC macromolecular chain kindliness is strengthened.In addition, behind the interpolation CNTs-Fe, form hybrid organic-inorganic film, tensile strength, overall loading and the Young's modulus of Bipolar Membrane are all obviously improved, mechanical property obviously strengthens.
Description of drawings
Can know that from table 1 behind the interpolation CNTs-Fe, elongation at break increases in the PVA-CMC/CS Bipolar Membrane.This is owing to after adding CNTs-Fe, weakened molecule or intermolecular ydrogen bonding effect on the CMC macromolecular chain, and CMC macromolecular chain kindliness is strengthened.In addition, behind the interpolation CNTs-Fe, form hybrid organic-inorganic film, tensile strength, overall loading and the Young's modulus of Bipolar Membrane are all obviously improved, mechanical property obviously strengthens.
Description of drawings
Fig. 1 is the prepared PVA of the embodiment of the invention 1
-CMC-CNTs-Fe/CS Bipolar Membrane structural representation.
Fig. 2 is the prepared PVA of the embodiment of the invention 1
-CMC-CNTs-Fe/CS Bipolar Membrane cross section Electronic Speculum figure.
Fig. 3 is with PVA
-Bath voltage was with the change curve of current density when the CMC-CNTs-Fe/CS Bipolar Membrane was electric groove barrier film.
Embodiment
Among Fig. 1, the 1st, load Fe
3+The carbon nano-tube modification cationic exchange membrane; The 2nd, intermediate layer; 3 anion-exchange membranes.Below in conjunction with embodiment the present invention is described in more detail.
Embodiment 1
Load Fe is used in preparation
3+The PVA of carbon nano-tube modification anode membrane layer
-The concrete steps of CMC-CNTs-Fe/CS Bipolar Membrane are following:
1, load Fe
3+The preparation of carbon nano-tube modification cationic exchange membrane
Accurately take by weighing the CMC of 100 grams, be dissolved in the zero(ppm) water, be mixed with massfraction and be 10% the CMC aqueous solution.Other gets PVA, with the dissolving of zero(ppm) water heated and stirred, joins in the CMC aqueous solution of above-mentioned preparation, stirs, and vacuum deaerator obtains thickness film liquid, and PVA is 1:1 with the massfraction ratio of CMC in the step.
A certain amount of carbon nanotube being put into the concentrated nitric acid reflux 6 hours, cool off the after scouring carbon nanotube, will be 5% Fe (NO then with respect to the carbon nanotube mol ratio
3)
3Join in the finely dispersed carbon nanotube alcohol suspending liquid of ultra-sonic oscillation, induction stirring is heated to 100 ℃ of evaporations, promptly gets carbon nanotube loaded iron (CNTs-Fe) nano composite material after the oven dry.Accurately take by weighing load Fe
3+Carbon nanotube 0.1g, add in the 80mL ethanol, use ultra-sonic oscillation, it is uniformly dispersed, join in the PVA-CMC aqueous solution of above-mentioned preparation, stir, vacuum deaerator obtains thickness film liquid.Thickness film flow is prolonged in smooth sheet glass at room temperature air-dry film forming.Elder generation's use massfraction is 8% FeCl after the air-dry film forming
3Crosslinked 10 min of solution soaking, the back is clean with distilled water flushing, and natural air drying promptly gets PVA
-The CMC-CNTs-Fe cationic exchange membrane.
2, the preparation of chitosan cavity block liquid
Take by weighing the CS of 50 grams; Using massfraction is 1% acetic acid aqueous solution stirring and dissolving, is mixed with massfraction and is 5% chitosan acetic acid aqueous solution 1000mL, slowly drips the 3mL volume(tric)fraction while stirring and be 2.5% glutaraldehyde solution; Vacuum deaerator can obtain thickness CS cavity block liquid.
3, PVA
-The CMC-CNTs-Fe/CS PREPARATIOM OF BIPOLAR MEMBRANE
CS cavity block flow is prolonged in the PVA of preparation
-On the CMC-CNTs-Fe cationic exchange membrane, at room temperature air-dry, promptly get PVA
-The CMC-CNTs-Fe/CS Bipolar Membrane, its structural representation is as shown in Figure 1.
Fig. 2 is the PVA for preparing with environmental scanning electronic microscope observation present embodiment
-CMC-CNTs-Fe/CS Bipolar Membrane cross section shape appearance figure.Lower floor is a PVA-CMC-CNTs-Fe cationic exchange rete among the figure, and thickness is about 87.8 μ m, is evenly distributed, and the upper strata is the CS anion exchange membrane facing, and thickness is about 65.7 μ m.The anode membrane layer combines closely with the cavity block layer, and no tiny bubble and hole are found between rete, and film intermediate interface layer thickness is in nanometer scale.
PVA with the present embodiment preparation
-The CMC-CNTs-Fe/CS Bipolar Membrane is injected 1mol/L Na as the barrier film between cathode compartment and the anolyte compartment respectively in chamber, yin, yang the two poles of the earth
2SO
4Solution 250mL is that (the electrode apparent area is 2 cm at yin, yang the two poles of the earth with lead
2), measure the variation relation of yin, yang two interpolar bath voltages with current density, as shown in Figure 3.Under the same conditions, measure chamber, yin, yang the two poles of the earth and do not have bath voltage and current density relation curve under the barrier film situation.Under certain current density, the difference that has or not yin, yang two interpolar bath voltages under the barrier film situation that records is Bipolar Membrane
IRFall.
By visible among Fig. 3, through load Fe
3+Carbon nano-tube modification anode membrane layer after, under identical current density, bath voltage obviously descends.This is because Fe
3+With carbon nanotube the water decomposition of Bipolar Membrane is had synergistic effect, promote dissociating of intermediate layer water greatly, thereby the IR that reduces Bipolar Membrane falls.The decline of bath voltage helps reducing the generation of electric groove electrochemistry side reaction, cuts down the consumption of energy.
Preparation is through load Ni
2+The PVA of carbon nano-tube modification cationic exchange rete
-The concrete steps of SA-CNTs-Ni/CS Bipolar Membrane are following:
1, load Ni
2+The preparation of carbon nano-tube modification cationic exchange membrane
Accurately take by weighing the SA of 80 grams, be dissolved in the zero(ppm) water, be mixed with massfraction and be 8% the SA aqueous solution.Other gets PVA (PVA is 1:1 with the massfraction ratio of CMC), with the dissolving of zero(ppm) water heated and stirred, joins in the SA aqueous solution of above-mentioned preparation, stirs, and vacuum deaerator obtains thickness film liquid.
A certain amount of carbon nanotube being put into the concentrated nitric acid reflux 6 hours, cool off the after scouring carbon nanotube, will be 5% Ni (NO then with respect to the carbon nanotube mol ratio
3)
2Join in the finely dispersed carbon nanotube alcohol suspending liquid of ultra-sonic oscillation, induction stirring is heated to 100 ℃ of evaporations, promptly gets carbon nanotube loaded nickel (CNTs-Ni) nano composite material after the oven dry.Accurately take by weighing load Ni
2+Carbon nanotube 0.2g, add in the 100mL ethanol, use ultra-sonic oscillation, it is uniformly dispersed.Join in the SA-PVA aqueous solution of above-mentioned preparation, stir, vacuum deaerator obtains thickness film liquid.Thickness film flow is prolonged in smooth sheet glass at room temperature air-dry film forming.The use massfraction is 8% FeCl earlier
3Crosslinked 10 min of solution soaking, the back is clean with distilled water flushing, natural air drying, i.e. PVA
-The CMC-CNTs-Ni cationic exchange membrane.
2, the preparation of chitosan cavity block liquid
Take by weighing the CS of 50 grams; The use massfraction is 1% acetic acid aqueous solution stirring and dissolving, and being mixed with massfraction is 5% chitosan acetic acid aqueous solution 1000mL, and slow while stirring Dropwise 5 mL volume(tric)fraction is 2.5% glutaraldehyde solution; Vacuum deaerator can obtain thickness CS cavity block liquid.Thickness film flow is prolonged in smooth petridish at room temperature air-dry CS anion-exchange membrane.
3, PVA
-The SA-CNTs-Ni/CS PREPARATIOM OF BIPOLAR MEMBRANE
Preparation used load Ni
2+Cationic exchange rete and the CS anion exchange membrane facing of carbon nano-tube modification at 250 ℃
Following hot pressing 10h promptly gets PVA
-The SA-CNTs-Ni/CS Bipolar Membrane.
Loaded Cu is used in preparation
2+The PVA of carbon nano-tube modification anode membrane layer
-The concrete steps of CMC-CNTs-Cu/CS Bipolar Membrane are following:
1, loaded Cu
2+The preparation of carbon nano-tube modification cationic exchange membrane
Accurately take by weighing the CMC of 100 grams, be dissolved in the zero(ppm) water, be mixed with massfraction and be 10% the CMC aqueous solution.Other gets PVA (PVA is 0.6:1 with the massfraction ratio of CMC), with the dissolving of zero(ppm) water heated and stirred, joins in the CMC aqueous solution of above-mentioned preparation, stirs, and vacuum deaerator obtains thickness film liquid.
A certain amount of carbon nanotube being put into the concentrated nitric acid reflux 12 hours, cool off the after scouring carbon nanotube, will be 5% Cu (NO then with respect to the carbon nanotube mol ratio
3)
2Join in the finely dispersed carbon nanotube alcohol suspending liquid of ultra-sonic oscillation, induction stirring is heated to 100 ℃ of evaporations, promptly gets carbon nanotube loaded copper (CNTs-Cu) nano composite material after the oven dry.
Accurately take by weighing loaded Cu
2+Carbon nanotube 0.2g, add in the 100mL ethanol, use ultra-sonic oscillation, it is uniformly dispersed, join in the PVA-CMC solution of above-mentioned preparation, stir, vacuum deaerator obtains thickness film liquid.Thickness film flow is prolonged in smooth sheet glass at room temperature air-dry film forming.The use massfraction is 6% FeCl earlier
3Crosslinked 15 min of solution soaking, the back is clean with distilled water flushing, and natural air drying promptly gets PVA
-The CMC-CNTs-Cu cationic exchange membrane.
2, the preparation of chitosan cavity block liquid
Take by weighing the CS of 60 grams; Using massfraction is 5% acetic acid aqueous solution stirring and dissolving, and being mixed with massfraction is 6% chitosan acetic acid aqueous solution 1000mL, slowly drips the 8mL volume(tric)fraction while stirring and be 2.5% glutaraldehyde solution; Vacuum deaerator can obtain thickness CS cavity block liquid.
3, PVA
-The CMC-CNTs-Cu/CS PREPARATIOM OF BIPOLAR MEMBRANE
CS cavity block flow is prolonged the PVA in preparation
-On the CMC-CNTs-Cu film, at room temperature air-dry, promptly get PVA
-The CMC-CNTs-Cu/CS Bipolar Membrane.
Embodiment 4
Load Fe is used in preparation
3+The PVA of carbon nano-tube modification anode membrane layer
-The concrete steps of SA-CNTs-Fe/CS Bipolar Membrane are following:
1, load Fe
3+The preparation of carbon nano-tube modification cationic exchange membrane
Accurately take by weighing the SA of 80 grams, be dissolved in the zero(ppm) water, be mixed with massfraction and be 8% the SA aqueous solution.Other gets PVA (PVA is 0.9:1 with the massfraction ratio of SA), with the dissolving of zero(ppm) water heated and stirred, joins in the SA aqueous solution of above-mentioned preparation, stirs, and vacuum deaerator obtains thickness film liquid.
A certain amount of carbon nanotube being put into the concentrated nitric acid reflux 8 hours, cool off the after scouring carbon nanotube, will be 5% Fe (NO then with respect to the carbon nanotube mol ratio
3)
3Join in the finely dispersed carbon nanotube alcohol suspending liquid of ultra-sonic oscillation, induction stirring is heated to 100 ℃ of evaporations, promptly gets carbon nanotube loaded iron (CNTs-Fe) nano composite material after the oven dry.Accurately take by weighing load Fe
3+Carbon nanotube 0.4g, add in the 100mL ethanol, use ultra-sonic oscillation, it is uniformly dispersed.Join in the PVA-SA aqueous solution of above-mentioned preparation, stir, vacuum deaerator obtains thickness film liquid.Thickness film flow is prolonged in smooth sheet glass at room temperature air-dry film forming.The use massfraction is 4% FeCl earlier
3The crosslinked 20min of solution soaking, the back is clean with distilled water flushing, and natural air drying promptly gets PVA
-The SA-CNTs-Fe cationic exchange membrane.
2, the preparation of chitosan cavity block liquid
Take by weighing the CS of 70 grams; Using massfraction is 4% acetic acid aqueous solution stirring and dissolving, and being mixed with massfraction is 7% chitosan acetic acid aqueous solution 1000mL, slowly drips the 7mL volume(tric)fraction while stirring and be 2.5% glutaraldehyde solution; Vacuum deaerator can obtain thickness CS cavity block liquid.Thickness film flow is prolonged in smooth petridish at room temperature air-dry CS anion-exchange membrane.
3, PVA
-The SA-CNTs-Fe/CS PREPARATIOM OF BIPOLAR MEMBRANE
Load Fe with preparation
3+Cationic exchange rete and the CS anion exchange membrane facing of carbon nano-tube modification at 240 ℃
Following hot pressing 12h promptly gets PVA
-The SA-CNTs-Fe/CS Bipolar Membrane.
Claims (6)
1. a loaded with heavy metals ionic carbon nano-tube modification PREPARATIOM OF BIPOLAR MEMBRANE method comprises the intermediate layer between cationic exchange rete, anion exchange membrane facing and two retes, it is characterized in that:
1) preparation of loaded with heavy metals ion carbon nano-tube modification cationic exchange rete
Take by weighing Xylo-Mucine or sodium-alginate, be mixed with massfraction and be 1～10% the CMC aqueous solution or the SA aqueous solution; Other gets Z 150PH, with the dissolving of zero(ppm) water heated and stirred, joins in the CMC aqueous solution or the SA aqueous solution of above-mentioned preparation, stirs, and gets the PVA-SA aqueous solution or the PVA-CMC aqueous solution; Carbon nanotube is carried out pre-treatment, make heavy metal ion in its load; Take by weighing loaded with heavy metals ionic carbon nanotube, add in the ethanol, use ultra-sonic oscillation, it is uniformly dispersed, join in the PVA-SA aqueous solution or the PVA-CMC aqueous solution of above-mentioned preparation, stir, vacuum deaerator obtains thickness film liquid; Thickness film flow is prolonged in smooth petridish, at room temperature air-dry film forming, the use massfraction is 1～10% FeCl earlier
3Crosslinked 10～30 min of solution soaking, the back is clean with distilled water flushing, and natural air drying promptly gets PVA
-CMC-CNTs cationic exchange membrane or SA-CMC-CNTs cationic exchange membrane;
2) preparation of chitosan cavity block liquid
Take by weighing chitosan, using massfraction is 1～10% acetic acid aqueous solution stirring and dissolving, is mixed with 1～10% chitosan acetic acid aqueous solution, slowly drips volume(tric)fraction while stirring and be 2.5% glutaraldehyde solution, and vacuum deaerator can obtain heavy-gravity CS cavity block liquid;
3) PREPARATIOM OF BIPOLAR MEMBRANE
Adopt curtain coating, superimposed, bonding or hot pressed method is with CS cavity block liquid system film and be fixed on the prepared anode membrane layer, and is at room temperature air-dry, promptly gets PVA
-CMC-CNTs-M/CS Bipolar Membrane or SA-CMC-CNTs-M/CS Bipolar Membrane.
2. a kind of loaded with heavy metals ionic carbon nano-tube modification PREPARATIOM OF BIPOLAR MEMBRANE method according to claim 1, it is characterized in that: the massfraction ratio between PVA and CMC or PVA and the SA is 0.5～1:1.
3. a kind of loaded with heavy metals ionic carbon nano-tube modification PREPARATIOM OF BIPOLAR MEMBRANE method according to claim 1, it is characterized in that: described carbon nanotube is 1～100:1000 with the massfraction ratio of CMC or SA.
4. a kind of loaded with heavy metals ionic carbon nano-tube modification PREPARATIOM OF BIPOLAR MEMBRANE method according to claim 1, it is characterized in that: described heavy metal ion is Fe
3+, Ni
2+, Cu
2+, Cd
3+, Sn
4+
5. a kind of loaded with heavy metals ionic carbon nano-tube modification PREPARATIOM OF BIPOLAR MEMBRANE method according to claim 1 is characterized in that: chitosan acetic acid aqueous solution and glutaraldehyde solution volume ratio are 1000 ︰ 2～8
.
6. a kind of loaded with heavy metals ionic carbon nano-tube modification PREPARATIOM OF BIPOLAR MEMBRANE method according to claim 1; It is characterized in that: described pre-treatment is that a certain amount of carbon nanotube was put into the concentrated nitric acid reflux 6 hours; Cooling after scouring carbon nanotube; To be that 5% heavy metal nitrate salt joins in the finely dispersed carbon nanotube alcohol suspending liquid of ultra-sonic oscillation with respect to the carbon nanotube mol ratio then; Induction stirring is heated to 100 ℃ of evaporations, promptly gets the nano composite material of carbon nanotube loaded heavy metal ion after the oven dry.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977716A (en) * | 2014-05-22 | 2014-08-13 | 武汉工程大学 | Separating membrane for filtering heavy metal ions as well as preparation method thereof |
| CN106310981A (en) * | 2016-08-23 | 2017-01-11 | 福建师范大学 | Method for preparing carbon nanopowder modified bipolar membrane by utilizing soaking method |
| CN107051217A (en) * | 2017-05-09 | 2017-08-18 | 河南工程学院 | Preparation method of bipolar membrane with high temperature resistance, low resistance and excellent mechanical properties |
| CN107620160A (en) * | 2016-07-15 | 2018-01-23 | 北京汇益科技股份有限公司 | A kind of method that method of electrostatic spinning prepares Bipolar Membrane |
| CN112827360A (en) * | 2019-11-22 | 2021-05-25 | 宁波方太厨具有限公司 | Heavy metal adsorption membrane chromatographic ultrafiltration membrane, membrane component and manufacturing method thereof |
| CN115245762A (en) * | 2021-09-16 | 2022-10-28 | 上海三及新材料科技有限公司 | MOF-loaded bipolar membrane and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977716A (en) * | 2014-05-22 | 2014-08-13 | 武汉工程大学 | Separating membrane for filtering heavy metal ions as well as preparation method thereof |
| CN103977716B (en) * | 2014-05-22 | 2016-01-06 | 武汉工程大学 | Diffusion barrier of a kind of filtering heavy metal ion and preparation method thereof |
| CN107620160A (en) * | 2016-07-15 | 2018-01-23 | 北京汇益科技股份有限公司 | A kind of method that method of electrostatic spinning prepares Bipolar Membrane |
| CN106310981A (en) * | 2016-08-23 | 2017-01-11 | 福建师范大学 | Method for preparing carbon nanopowder modified bipolar membrane by utilizing soaking method |
| CN107051217A (en) * | 2017-05-09 | 2017-08-18 | 河南工程学院 | Preparation method of bipolar membrane with high temperature resistance, low resistance and excellent mechanical properties |
| CN107051217B (en) * | 2017-05-09 | 2019-10-11 | 河南工程学院 | Preparation method of bipolar membrane with high temperature resistance, low resistance and excellent mechanical properties |
| CN112827360A (en) * | 2019-11-22 | 2021-05-25 | 宁波方太厨具有限公司 | Heavy metal adsorption membrane chromatographic ultrafiltration membrane, membrane component and manufacturing method thereof |
| CN115245762A (en) * | 2021-09-16 | 2022-10-28 | 上海三及新材料科技有限公司 | MOF-loaded bipolar membrane and application thereof |
| CN115245762B (en) * | 2021-09-16 | 2024-03-12 | 上海三及新材料科技有限公司 | MOF-loaded bipolar membrane and application thereof |
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