CN108335910A - A kind of composite gel material and preparation method thereof, solar cell module and preparation method thereof - Google Patents
A kind of composite gel material and preparation method thereof, solar cell module and preparation method thereof Download PDFInfo
- Publication number
- CN108335910A CN108335910A CN201710048133.XA CN201710048133A CN108335910A CN 108335910 A CN108335910 A CN 108335910A CN 201710048133 A CN201710048133 A CN 201710048133A CN 108335910 A CN108335910 A CN 108335910A
- Authority
- CN
- China
- Prior art keywords
- collagen
- solution
- preparation
- carbon nano
- tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title abstract description 10
- 102000008186 Collagen Human genes 0.000 claims abstract description 75
- 108010035532 Collagen Proteins 0.000 claims abstract description 75
- 229920001436 collagen Polymers 0.000 claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 58
- 239000000243 solution Substances 0.000 claims abstract description 58
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 57
- 239000000499 gel Substances 0.000 claims abstract description 37
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 10
- 239000000017 hydrogel Substances 0.000 claims abstract description 6
- 238000005086 pumping Methods 0.000 claims abstract description 5
- 238000000605 extraction Methods 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 18
- 239000003292 glue Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 108010053210 Phycocyanin Proteins 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 206010070834 Sensitisation Diseases 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 230000008313 sensitization Effects 0.000 claims description 12
- 239000012460 protein solution Substances 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000005213 imbibition Methods 0.000 claims description 10
- 241000894006 Bacteria Species 0.000 claims description 9
- 239000007853 buffer solution Substances 0.000 claims description 9
- 238000000855 fermentation Methods 0.000 claims description 9
- 230000004151 fermentation Effects 0.000 claims description 9
- 101710182850 Allophycocyanin alpha subunit Proteins 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 7
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- 108010004469 allophycocyanin Proteins 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000013604 expression vector Substances 0.000 claims description 5
- 230000031700 light absorption Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001042 affinity chromatography Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- UNFWWIHTNXNPBV-WXKVUWSESA-N spectinomycin Chemical compound O([C@@H]1[C@@H](NC)[C@@H](O)[C@H]([C@@H]([C@H]1O1)O)NC)[C@]2(O)[C@H]1O[C@H](C)CC2=O UNFWWIHTNXNPBV-WXKVUWSESA-N 0.000 claims description 4
- 229960000268 spectinomycin Drugs 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- NNMALANKTSRILL-LXENMSTPSA-N 3-[(2z,5e)-2-[[3-(2-carboxyethyl)-5-[(z)-[(3e,4r)-3-ethylidene-4-methyl-5-oxopyrrolidin-2-ylidene]methyl]-4-methyl-1h-pyrrol-2-yl]methylidene]-5-[(4-ethyl-3-methyl-5-oxopyrrol-2-yl)methylidene]-4-methylpyrrol-3-yl]propanoic acid Chemical compound O=C1C(CC)=C(C)C(\C=C\2C(=C(CCC(O)=O)C(=C/C3=C(C(C)=C(\C=C/4\C(\[C@@H](C)C(=O)N\4)=C\C)N3)CCC(O)=O)/N/2)C)=N1 NNMALANKTSRILL-LXENMSTPSA-N 0.000 claims description 3
- 241000195493 Cryptophyta Species 0.000 claims description 3
- 108090000790 Enzymes Proteins 0.000 claims description 3
- 241001597008 Nomeidae Species 0.000 claims description 3
- 108010004729 Phycoerythrin Proteins 0.000 claims description 3
- 230000001851 biosynthetic effect Effects 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 230000006798 recombination Effects 0.000 claims description 3
- 238000005215 recombination Methods 0.000 claims description 3
- 108090000856 Lyases Proteins 0.000 claims description 2
- 241000193830 Bacillus <bacterium> Species 0.000 claims 1
- 241001062009 Indigofera Species 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 238000011010 flushing procedure Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 210000002429 large intestine Anatomy 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 12
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000011245 gel electrolyte Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- 235000011008 sodium phosphates Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- 206010001497 Agitation Diseases 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- ALSIFQIAIHCPAA-UHFFFAOYSA-N 1,2-dimethyl-3-propyl-2h-imidazole Chemical class CCCN1C=CN(C)C1C ALSIFQIAIHCPAA-UHFFFAOYSA-N 0.000 description 2
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 2
- 241000192700 Cyanobacteria Species 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 230000007850 degeneration Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 101100083210 Cyanophora paradoxa cpcA gene Proteins 0.000 description 1
- 241000199914 Dinophyceae Species 0.000 description 1
- 108010022355 Fibroins Proteins 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 241000206572 Rhodophyta Species 0.000 description 1
- 239000012505 Superdex™ Substances 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 101150039377 cpcE gene Proteins 0.000 description 1
- 101150096251 cpcF gene Proteins 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012149 elution buffer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006052 feed supplement Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 101150075668 pcyA gene Proteins 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Hybrid Cells (AREA)
Abstract
A kind of preparation method of collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, includes the following steps：Extraction collagen is simultaneously configured to collagen aqueous solution；Prepare carboxylic carbon nano-tube solution；Prepare cross-linking agent solution；The collagen aqueous solution, the carboxylic carbon nano-tube solution and the cross-linking agent solution are uniformly mixed, it is ultrasonic at room temperature, closed pumping, it is then respectively adding TEMED solution and ammonium persulfate solution, polymerisation occurs, obtains collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel.A kind of solar cell and preparation method thereof is also provided.The stable and electrically conductive rate of above-mentioned material performance is high.
Description
Technical field
The present invention relates to biotechnologies, and in particular to a kind of collagen/carboxylic carbon nano-tube/polyacrylamide
Composite gel material and preparation method thereof, solar cell module and preparation method thereof.
Background technology
Since the 1990s, the invention of solar cell promotes scientist and utilizes large biological molecule assembling dyestuff quick
Change the research and application of solar cell.The feature inexpensive, environmental-friendly and that making is simple of dye-sensitized cell is allowed to have
There is good application prospect.Dye-sensitized cell is mainly made of following components：Conductive basal layer, nano titania are more
Pore electrod, dye-sensitized layer, electrolyte and photocathode.Up to the present, many biological dye sensitizing layers are developed, especially base
It is the most extensive in the exploitation of the artificial photovoltaic apparatus of the photosynthetic albumen composition of the supermolecule of chlorophyll.
Phycobniliprotein is to be present in cyanobacteria, red algae, hidden algae and a handful of dinoflagellate to catch photochromic fibroin, can be capture
Luminous energy efficiently pass to photosystem reaction center, be used for photosynthesis.Wherein, phycocyanin is the most common algae courage of distribution
Albumen can be observed in nearly all biology containing phycobniliprotein.The most of cyanobacteria objects grown in the natural environment
Content is most abundant in kind.The phycobniliprotein of these blues or bluish violet can be absorbed from 580nm to 630nm ranges
Light, and launch red fluorescence 635nm-645nm ranges are intensive.This is carried for the research and utilization of dye-sensitized solar cells
Good material is supplied.
Since phycocyanin dye-sensitized layer exists in liquid form mostly, its application difficult is caused.And according to solid
The problems such as state phycocyanin biological dye sensitizing layer, it will cause albuminous degenerations, leads to the photoelectricity of the dye-sensitized cell of assembling
Transformation efficiency is generally relatively low.
Invention content
Based on this, it is necessary to provide a kind of collagen/carboxylic carbon nano-tube that the stable and electrically conductive rate of performance is high/poly- third
Acrylamide composite gel material and preparation method thereof, solar cell module and preparation method thereof.
A kind of preparation method of collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, including following step
Suddenly：
Extraction collagen is simultaneously configured to collagen aqueous solution；
Prepare carboxylic carbon nano-tube solution；
Prepare cross-linking agent solution；
The collagen aqueous solution, the carboxylic carbon nano-tube solution and the cross-linking agent solution are uniformly mixed,
Ultrasonic at room temperature, closed pumping is then respectively adding TEMED solution and ammonium persulfate solution, and polymerisation occurs, obtains glue
Former albumen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel.
The collagen, the carboxylic carbon nano-tube mass ratio are 15~25 in one of the embodiments,：1.
The volume fraction of the TEMED solution is 0.2~1% in one of the embodiments, the ammonium persulfate solution
Mass concentration be 50mg/mL, the volume ratio of the TEMED solution and the ammonium persulfate solution is 2.5~5:1.
The method extracted collagen and be configured to collagen aqueous solution is in one of the embodiments,：
Fish-skin is added in the NaOH aqueous solutions of a concentration of 0.1~0.15mol/L and impregnates for 24 hours~48h to remove non-collagen
Ingredient obtains degreasing fish-skin；
The degreasing fish-skin is washed to the acetum that a concentration of 0.2mol/L~0.5mol/L is added after neutrality, it is even
Slurry, 4 DEG C of magnetic agitations extract 2~3d, are that 10000r/min centrifuges 30min with rotating speed, obtained supernatant is acid-soluble collagen
Albumen；
The NaCl of 0.9mol/L~1mol/L is added to the acid-soluble collagen, centrifugation is collected precipitation and is dissolved in
In 0.2mol/L~0.5mol/L acetums, using a concentration of 0.02mol/L~0.1mol/L acetum dialysis 1~
2d, then with distilled water dialyse 21~d, the Isin glue collagen is obtained after freeze-drying；
The Isin glue collagen is dissolved in deionized water, pH to 6.0 is adjusted with NaOH, adjusts Isin glue collagen concentration
To 5mg/mL.
The preparation carboxylic carbon nano-tube solution methods are in one of the embodiments,：Take length be 10-30 μm and
Electric conductivity is more than 90s/cm, purity>90% carboxylated single-walled carbon nanotube, is dissolved in pure water, then ultrasonic disperse, obtains
To the carboxylic carbon nano-tube solution of a concentration of 1wt%.
The method for preparing cross-linking agent solution is in one of the embodiments,：By acrylamide solid and methene third
Acrylamide solid is dissolved in the Tris/HCL buffer solutions that pH value is 6.8, and the acrylamide and the methene acrylamide rub
You are than being 55~65：1, the molar ratio of the acrylamide and the Tris/HCl buffer solutions is 8：1.
A kind of collagen/carboxylic carbon nano-tube/polyacrylamide composite gel obtained according to above-mentioned preparation method.
A kind of preparation method of solar cell module, includes the following steps：
Such as above-mentioned collagen/carboxylic carbon nano-tube/polyacrylamide composite gel is provided；
Collagen/the carboxylic carbon nano-tube/polyacrylamide composite gel is placed in EDC and NHS solution,
It is protected from light overnight, is rinsed with deionized water at room temperature, room temperature is dried, and film layer is formed, and the film layer is molten in electrolyte
Imbibition in liquid, wherein the molar ratio of the EDC and NHS is 1：2~1:4；
The recombinant allophycocyanin α subunit MF0 containing histidine tag are prepared, and by the weight containing histidine tag
Group phycocyanin alpha subunit MF0 is dissolved in sodium radio-phosphate,P-32 solution, forms MF0 protein solutions；
By TiO2Electrode is immersed in the MF0 protein solutions, after being protected from light absorption at room temperature, is rinsed with deionized water, so
Nitrogen blowing is dried afterwards, obtains the titanium dioxide anode of MF0 sensitizations；
The film after imbibition electrolyte solution is placed on to pair of the titanium dioxide anode and platinum plating of the MF0 sensitizations
Between electrode, both ends are fixed, and obtain the solar cell module.
The preparation side of the recombinant allophycocyanin α subunits MF0 containing histidine tag in one of the embodiments,
Method is：
Phycocyanin alpha subunit sequence of phycoerythrin gene, phycobilin biosynthetic enzyme genes, histidine tag, color base are split
Synthase gene E and F are cloned into the expression vector pCDFDeut-1 of Spectinomycin resistance and are built into expression vector pHMPC, are transferred to
Then Escherichia coli filter out the recombinant allophycocyanin α subunit MF0 engineered strains containing histidine tag；
The engineered strain is connected to fermentation cylinder for fermentation, derivant is added and carries out induced expression, collect bacteria liquid；
By the bacteria liquid ultrasonic disruption, after centrifugation, supernatant is taken, by affinity chromatography column purification, is purified
Recombinant allophycocyanin α subunits MF0 containing histidine tag.
A kind of solar cell module obtained according to above-mentioned preparation method.
In above-mentioned collagen/carboxylic carbon nano-tube/polyacrylamide composite gel and its preparation method and application,
Then it is doped in polyacrylamide network structure, collagen and carboxylic carbon nano-tube wiring solution-forming followed by 1-
(3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDC) and n-hydroxysuccinimide (NHS) are used as crosslinking agent,
Carboxylic carbon nano-tube and collagen are further crosslinked.Not only property is stable for the gel composite, intensity is high, but also is conducive to
Encapsulation, while photoelectric conversion efficiency can be promoted, promote the application of phycocyanin dye-sensitized solar cells.
Description of the drawings
Fig. 1 is collagen/carboxylic carbon nano-tube/polyacrylamide composite gel preparation method of an embodiment
Flow chart；
Fig. 2 is the flow chart of the solar cell module preparation method of an embodiment；
Fig. 3 is the structural schematic diagram of the solar cell module of an embodiment；
Fig. 4 is 100mW/cm2The I-V test curves of solar cell module under light intensity；
Fig. 5 is that the solar cell module open-circuit voltage of an embodiment changes over time situation；
Fig. 6 is that the solar cell module short circuit current of an embodiment changes over time situation；
Fig. 7 is that the solar cell module photoelectric conversion efficiency of an embodiment changes over time situation.
Specific implementation mode
It is compound to a kind of collagen/carboxylic carbon nano-tube/polyacrylamide solidifying with reference to embodiment and attached drawing
Glue material method and the application in biological sensitization solar battery are described in further detail.
A kind of collagen/carboxylic carbon nano-tube/polyacrylamide composite gel MATERIALS METHODS and biology sensitization too
Application in positive energy battery, includes the following steps：
S110, it extracts collagen and is configured to collagen aqueous solution.
In one embodiment, it extracts collagen and the method for being configured to collagen aqueous solution is：
Fish-skin is added in the NaOH aqueous solutions of a concentration of 0.1~0.15mol/L and impregnates for 24 hours~48h to remove non-collagen
Ingredient obtains degreasing fish-skin；
The degreasing fish-skin is washed to the acetum that a concentration of 0.2mol/L~0.5mol/L is added after neutrality, it is even
Slurry, 4 DEG C of magnetic agitations extract 2~3d, are that 10000r/min centrifuges 30min with rotating speed, obtained supernatant is acid-soluble collagen
Albumen；
The NaCl of 0.9mol/L~1mol/L is added to the acid-soluble collagen, centrifugation is collected precipitation and is dissolved in
In 0.2mol/L~0.5mol/L acetums, using a concentration of 0.02mol/L~0.1mol/L acetum dialysis 1~
2d, then with distilled water dialyse 21~d, the Isin glue collagen is obtained after freeze-drying；
The Isin glue collagen is dissolved in deionized water, pH to 6.0 is adjusted with NaOH, adjusts Isin glue collagen concentration
To 5mg/mL.
S120, carboxylic carbon nano-tube solution is prepared.
In one embodiment, preparing carboxylic carbon nano-tube solution methods is：It is 10-30 μm and electric conductivity to take length
More than 90s/cm, purity>90% carboxylated single-walled carbon nanotube, is dissolved in the nonionic surfactant containing aromatic group
Pure water in, then ultrasonic disperse, obtains the carboxylic carbon nano-tube solution of a concentration of 1wt%.
Carboxylic carbon nano-tube has unique structure, not only the spies such as conductive energy, hot property, high specific surface area
Point, and molecular surface has carboxyl so that and dispersibility of the carboxylic carbon nano-tube in aqueous solvent greatly improves.
S130, cross-linking agent solution is prepared.
In one embodiment, the method for preparing cross-linking agent solution is：Acrylamide and methene acrylamide are dissolved in pH
The Tris/HCL buffer solutions that value is 6.8.The molar ratio of the acrylamide and the methene acrylamide is 55~65：1, it is described
The molar ratio of acrylamide and the Tris/HCl buffer solutions is 8：1.
S140, collagen aqueous solution, carboxylic carbon nano-tube solution and cross-linking agent solution are uniformly mixed, at room temperature
Ultrasound, closed pumping are then respectively adding TEMED solution and ammonium persulfate solution, and polymerisation occurs, obtain collagen/
Carboxylic carbon nano-tube/polyacrylamide composite hydrogel.
In one embodiment, the collagen, the carboxylic carbon nano-tube mass ratio are 15~25：1.
In one embodiment, the volume fraction of the TEMED solution is 0.2~1%, the matter of the ammonium persulfate solution
Measure a concentration of 50mg/mL, the volume ratio of the TEMED solution and the ammonium persulfate solution is 2.5~5:1.
A kind of collagen/carboxylic carbon nano-tube/polyacrylamide composite gel obtained according to above-mentioned preparation method.
A kind of preparation method of solar cell module, includes the following steps：
S210, above-mentioned collagen/carboxylic carbon nano-tube/polyacrylamide composite gel is provided.
Above-mentioned collagen/carboxylic carbon nano-tube/polyacrylamide composite gel preparation method is with reference to the above method.
S220, the collagen/carboxylic carbon nano-tube/polyacrylamide composite gel is placed in EDC and NHS solution
In, it is protected from light overnight, is rinsed with deionized water at room temperature, room temperature is dried, and forms film layer, the film layer is being electrolysed
Imbibition in matter solution, wherein the molar ratio of the EDC and NHS is 1：2~1:4.
EDC NHS can be catalyzed carboxyl and amino forms covalent amido bond.Collagen molecules surface there are many amino and
Carboxyl, carboxylic carbon nano-tube surface contain there are many carboxyl, and phycocyanin has free amino and carboxyl.Therefore EDC
In the presence of NHS, not only makes to form stable structure between carboxylic carbon nano-tube and Isin glue collagen inside gel, strengthen solidifying
The characteristics such as the stability and intensity of glue；The carboxylic carbon nano-tube and Isin glue collagen of gel surface can be with phycocyanins simultaneously
Covalent reaction occurs, is fixed on gel surface by what phycocyanin was stablized.And the carbon nanotube inside gel can play electronics
The effect of transmission.
S230, the recombinant allophycocyanin α subunit MF0 containing histidine tag are prepared, and described will contains histidine mark
The recombinant allophycocyanin α subunits MF0 of label is dissolved in sodium radio-phosphate,P-32 solution, forms MF0 protein solutions.
In one embodiment, a concentration of 50mg/mL of albumen of a concentration of 50mM of sodium radio-phosphate,P-32 solution, MF0 protein solution.
In one embodiment, the method for recombinant allophycocyanin α subunit MF0 of the preparation containing histidine tag is：
First by phycocyanin alpha subunit sequence of phycoerythrin gene pcyA, phycobilin biosynthetic enzyme genes hox1, histidine
Label, color base lyase genes cpcE and cpcF are cloned into the expression vector pCDFDeut-1 of Spectinomycin resistance and are built into table
Up to carrier pHMPC, Escherichia coli are converted, the engineering bacteria of expression said gene is filtered out using Spectinomycin resistance, is as carried
The recombination phycocyanin alpha subunit MF0 of histidine tag；
The engineered strain is connected to fermentation cylinder for fermentation, derivant is added and carries out induced expression, collect bacteria liquid；
By the bacteria liquid ultrasonic disruption, after centrifugation, supernatant is taken, by affinity chromatography column purification, is purified
Recombinant allophycocyanin α subunits MF0 containing histidine tag.
Specifically, by above-mentioned structure gained engineering bacteria after 5L fermentation cylinder for fermentation, 4h, thalli growth to logarithmic phase, with
1g/L·min-1Rate carry out glycerine feed supplement, fermentation start 7h after, temperature in tank is first slowly dropped to 28 DEG C, then be added lure
Agent lactose is led to final concentration 4g/L, reduces rotating speed to 150rpm, Fiber differentiation 10h or more.Zymotic fluid 6000rpm is centrifuged
15min obtains the thalline of express express target protein, according to every liter of combination buffer (20mmol/L sodium phosphates, 0.5mol/L chlorinations
Sodium, 20mmol/L imidazoles, pH 7.4) thalline is resuspended the ratio that is added wet thallus 80g, ultrasonication bacterium (150W, work time
Number is 300 times, time interval 2：8), 12000rpm is centrifuged under the conditions of 4 DEG C, is collected supernatant, is splined on Ni2+Affinity chromatography
Column is rinsed with the buffer solution (20mmol/L sodium phosphates, 0.5mol/L sodium chloride, 50mmol/L imidazoles, pH7.4) of 5 times of column volumes
After chromatographic column, washed with elution buffer (20mmol/L sodium phosphates, 0.5mol/L sodium chloride, 400mmol/L imidazoles, pH 7.0)
De-, eluent obtains desalination albumen after millipore protein concentration column desalination and concentrations.Pass through 200 gel colors of Superdex
Column is composed, is eluted with 50mM kaliumphosphate buffers (pH7.0), elution speed 10ml/h, outflow when detection peak-peak is collected
Liquid is purpose albumen to get to the recombinant allophycocyanin α subunits MF0 containing histidine tag after purification.
S240, by TiO2Electrode is immersed in the MF0 protein solutions, after being protected from light absorption at room temperature, is floated with deionized water
It washes, then nitrogen blowing is dried, and obtains the titanium dioxide anode of MF0 sensitizations.
In one embodiment, fluorine oxidation is all fixed on by nano-porous structure light anode and as the platinum electrode to electrode
On tin (FTO) conducting glass substrate.After FTO glass uses ethyl alcohol, chloroform ultrasonic activation to handle 20min successively, UV ozone disappears
Malicious 10min.Using silk screen print method by the spherical TiO of 20nm grain size scales2Particle deposition in processed FTO glass surfaces,
Deposition thickness is about that 12 μm of areas are about 0.24cm2, obtain the semiconductor film as light anode.Then in Muffle furnace
500 DEG C of heating 30min, make titanium dioxide granule be sintered together, create an infiltrative conductive network.Light anode electrode system
After standby, with 350 DEG C of heating 40min in Muffle furnace, 50 DEG C are subsequently cooled to, TiO2Electrode is immersed in 7.0 phosphoric acid containing 50mM of pH
In the MF0 protein solutions of sodium (a concentration of 50mg/mL of albumen), it is protected from light absorption at room temperature for 24 hours, reaches maximal absorptive capacity.After absorption,
Sensitization light anode is rinsed with deionized water, removes unstable absorption, then nitrogen blowing is dried.
S250, titanium dioxide anode and the plating that the film after imbibition electrolyte solution is placed on to the MF0 sensitizations
Platinum between electrode, both ends are fixed, and the solar cell module is obtained.
In one embodiment, gained film layer is put to electrolyte solution (LiI (lithium iodide) of 0.5M, 0.05M I2
(elemental iodine), 0.3M DMPII (1,2- dimethyl -3- propyl imidazoles salt compounded of iodine)) in imbibition.Gel after imbibition electrolyte is set
In MF0 sensitization titanium dioxide anode and platinum plating between electrode, both ends fix triplicity it is close.Assembled battery exists
25 DEG C, 100mW/cm2Under standard illumination condition, system is tested to assembled solar cell using solar cell I-V
Photovoltaic property is tested.Obtain include short circuit current and open-circuit voltage measured value, and calculate photoelectricity by the two values
Transfer efficiency, as a result as shown in Fig. 4, Fig. 5, Fig. 6, Fig. 7.Fig. 4 and Fig. 5 shows to be replaced with inventive gel electrolyte layer original
Liquid layer of electrolyte (the LiI of 0.5M, 0.05M I2, 0.3M DMPII) after, open-circuit voltage does not change, and current strength increases
Add, shows there are more electronics to participate in opto-electronic conversion.Fig. 6 shows after gel electrolyte layer using the present invention, short-circuit
Electric current extends and increases at any time, this may gradually be penetrated into titanium dioxide layer with gel, has been contacted with more MF0 albumen
It closes.After Fig. 7 shows gel electrolyte layer using the present invention, photoelectric conversion efficiency increases with the extension of testing time.
It is sensitized in above-mentioned collagen/carboxylic carbon nano-tube/polyacrylamide composite gel MATERIALS METHODS and in biology
In application in solar cell, carboxylic carbon nano-tube has unique structure, not only conductive energy, hot property, height
Specific surface area the features such as, and molecular surface have carboxyl so that large dispersion of the carboxylic carbon nano-tube in aqueous solvent
It is big to improve.EDC NHS can be catalyzed carboxyl and amino forms covalent amido bond.There are many amino and carboxylics on collagen molecules surface
Base, carboxylic carbon nano-tube surface carboxyl containing there are many, therefore in the presence of EDC NHS, make carboxylated carbon nanometer inside gel
Stable structure is formed between pipe and Isin glue collagen, strengthens the characteristics such as stability and the intensity of gel, and inside gel
Carbon nanotube can play the role of electron transmission.Not only property is stable for the gel composite, intensity is high, but also is conducive to encapsulation,
It can promote photoelectric conversion efficiency simultaneously, improve photronic short circuit current (Fig. 5, Fig. 6, Fig. 7), promote phycocyanin dye sensitization
The application of solar cell.In addition, carbon nanotube by far infrared after near infrared spectrum radiates, can discharge and largely shake
Kinetic energy can locally generate amount of heat.It is sufficiently strong when radiating, when heat is sufficiently high, electrode surface can be caused to adsorb
MF0 albuminous degenerations, photo-sensitive characteristic is lost, therefore above-mentioned material is also used as special photoswitch.
Embodiment
Embodiment 1
It takes fish-skin to be added in the NaOH aqueous solutions of a concentration of 0.2mol/L to impregnate for 24 hours to remove non-collagen tissue, be washed to
The acetum homogenate of a concentration of 0.6mol/L is added after neutrality, 4 DEG C of magnetic agitations extract 2d, and 12000g centrifuges 30min, upper
NaCl is added in clear liquid, centrifuges, collects precipitation and is dissolved in 0.5mol/L acetums, dialysed with 0.1mol/L acetums
Night, then with distilled water dialyse 1d, acid-soluble Isin glue collagen is lyophilized to obtain.Acid Isin glue collagen is taken to be dissolved in deionized water,
PH to 6.0 is adjusted with NaOH, adjusts Isin glue collagen concentration to 5mg/mL.
It is 10-30 μm to take length, and electric conductivity is more than 90s/cm, purity>90% carboxylated single-walled carbon nanotube, dissolving
In the pure water of the nonionic surfactant containing aromatic group, then ultrasound makes it fully dissolve to get bright to black
Carbon nano-tube solution (content of carbon nanotubes 1wt%).
Acrylamide 17.46g, methene acrylamide 0.54g are taken, with pH 6.8, the Tris/HCL buffer solutions of 0.5mol/L
It is settled to 60ml, 4 DEG C of preservations of brown bottle after filtering.
The recombinant allophycocyanin α subunit MF0 containing histidine tag are prepared, and by the weight containing histidine tag
Group phycocyanin alpha subunit MF0 is dissolved in sodium radio-phosphate,P-32 solution, forms MF0 protein solutions.50mg MF0 are weighed to be dissolved in vain
In the PBS buffer solution of 1mL pH 6.0, the MF0 protein solutions of 50mg/mL are obtained.
Fluorine tin oxide (FTO) electro-conductive glass is all fixed on by nano-porous structure light anode and as the platinum electrode to electrode
On substrate.After FTO glass uses ethyl alcohol, chloroform ultrasonic activation to handle 20min successively, UV ozone sterilizes 10min.Use silk screen
Print process is by the spherical TiO of 20nm grain size scales2For particle deposition in processed FTO glass surfaces, deposition thickness is about 12 μ
M areas are about 0.24cm2, obtain the semiconductor film as light anode.Then 500 DEG C of heating 30min in Muffle furnace, make two
Titan oxide particles are sintered together, and create an infiltrative conductive network.Light anode electrode prepare after, in Muffle furnace with
350 DEG C of heating 40min, are subsequently cooled to 50 DEG C, TiO2Electrode is immersed in the MF0 protein solutions of 7.0 sodium phosphates containing 50mM of pH
(a concentration of 50mg/mL of albumen) is protected from light absorption for 24 hours, reaches maximal absorptive capacity at room temperature.After absorption, rinsed with deionized water quick
Change light anode, remove unstable absorption, then nitrogen blowing is dried.
It is separately added into collagen solution 1mL, carbon nano-tube solution 1ml, cross-linking agent aqueous solution 2ml in beaker, mixing,
Ultrasound 20min at room temperature, closed pumping 10min are then respectively adding the 1%TEMED solution of 1mL and the 50mg/mL mistakes of 0.2mL
Ammonium sulfate makes fully to dissolve, cause polymerization, reaction at 28 DEG C carry out 30min, obtain hydrogel, by composite hydrogel from
It takes out, is placed in 10mL deionized waters in beaker, 5mg EDC and 10mg NHS are added, be protected from light at room temperature overnight.It takes out
Gel is rinsed with deionized water, obtains collagen/carboxylic carbon nano-tube/polyacrylamide composite gel.By gained gel
Room temperature is dried, and forms gel film, film is put to electrolyte solution (LiI (lithium iodide) of 0.5M, 0.05M I2(iodine list
Matter), 0.3M DMPII (1,2- dimethyl -3- propyl imidazoles salt compounded of iodine)) in imbibition.Gel after imbibition electrolyte is placed in MF0
The titanium dioxide anode of sensitization and platinum plating between electrode, it is close that triplicity is fixed at both ends.Assembled battery at 25 DEG C,
100mW/cm2Under standard illumination condition, it is special to the photovoltaic of assembled solar cell to test system using solar cell I-V
Property is tested.Obtain include short circuit current and open-circuit voltage measured value, and by the two values calculate opto-electronic conversion effect
Rate, as a result as shown in Fig. 3, Fig. 4, Fig. 5, Fig. 6.Fig. 3 and Fig. 4 shows to replace original liquid electric with inventive gel electrolyte layer
Solve the matter layer (LiI of 0.5M, 0.05M I2, 0.3M DMPII) after, open-circuit voltage does not change, and current strength increases, table
It is bright to there are more electronics to participate in opto-electronic conversion.Fig. 5 shows after gel electrolyte layer using the present invention, short circuit current with
Time lengthening and increase, this may gradually be penetrated into gel in titanium dioxide layer, be contacted with more MF0 albumen related.Fig. 6 tables
After bright gel electrolyte layer using the present invention, photoelectric conversion efficiency increases with the extension of testing time.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, it is characterised in that：Packet
Include following steps：
Extraction collagen is simultaneously configured to collagen aqueous solution；
Prepare carboxylic carbon nano-tube solution；
Prepare cross-linking agent solution；
The collagen aqueous solution, the carboxylic carbon nano-tube solution and the cross-linking agent solution are uniformly mixed, in room
The lower ultrasound of temperature, closed pumping are then respectively adding TEMED solution and ammonium persulfate solution, polymerisation occur, obtains collagen egg
In vain/carboxylic carbon nano-tube/polyacrylamide composite hydrogel.
2. preparation method according to claim 1, which is characterized in that the collagen, the carboxylic carbon nano-tube
Mass ratio is 15~25：1.
3. preparation method according to claim 1, which is characterized in that the volume fraction of the TEMED solution be 0.2~
1%, the mass concentration of the ammonium persulfate solution is 50mg/mL, the volume of the TEMED solution and the ammonium persulfate solution
Than being 2.5~5:1.
4. preparation method according to claim 1, which is characterized in that the extraction collagen is simultaneously configured to collagen
The method of aqueous solution is：
Fish-skin is added in the NaOH aqueous solutions of a concentration of 0.1~0.15mol/L and impregnates for 24 hours~48h to remove non-collagen tissue,
Obtain degreasing fish-skin；
The degreasing fish-skin is washed to the acetum that a concentration of 0.2mol/L~0.5mol/L is added after neutrality, is homogenized, 4 DEG C
Magnetic agitation extracts 2~3d, is that 10000r/min centrifuges 30min with rotating speed, obtained supernatant is acid-soluble collagen；
The NaCl of 0.9mol/L~1mol/L is added to the acid-soluble collagen, centrifugation collects precipitation and is dissolved in 0.2mol/L
In~0.5mol/L acetums, using a concentration of 0.02mol/L~0.1mol/L acetum dialyse 1~2d, then with steaming
Distilled water 21~d of dialysis, obtains the Isin glue collagen after freeze-drying；
The Isin glue collagen is dissolved in deionized water, with NaOH adjust pH to 6.0, adjust Isin glue collagen concentration to
5mg/mL。
5. preparation method according to claim 1, which is characterized in that the preparation carboxylic carbon nano-tube solution methods
For：It is that 10-30 μm and electric conductivity are more than 90s/cm, purity to take length>90% carboxylated single-walled carbon nanotube, is dissolved in pure
In water, then ultrasonic disperse, obtains the carboxylic carbon nano-tube solution of a concentration of 1wt%.
6. preparation method according to claim 1, which is characterized in that it is described prepare cross-linking agent solution method be：By third
Acrylamide solid and methene acrylamide solid are dissolved in the Tris/HCL buffer solutions that pH value is 6.8, the acrylamide and institute
The molar ratio for stating methene acrylamide is 55~65：1, the molar ratio of the acrylamide and the Tris/HCl buffer solutions is 8：
1。
7. a kind of collagen/carboxylated obtained according to the preparation method of claim 1-6 any one claims
Carbon nanotube/polypropylene amide plural gel.
8. a kind of preparation method of solar cell module, which is characterized in that include the following steps：
Collagen/carboxylic carbon nano-tube/polyacrylamide composite gel as claimed in claim 7 is provided；
Collagen/the carboxylic carbon nano-tube/polyacrylamide composite gel is placed in EDC and NHS solution, in room temperature
Under be protected from light overnight, rinsed with deionized water, room temperature is dried, formed film layer, by the film layer in electrolyte solution
Imbibition, wherein the molar ratio of the EDC and NHS is 1：2~1:4；
The recombinant allophycocyanin α subunit MF0 containing histidine tag are prepared, and the recombination containing histidine tag is other
Phycocyanin alpha subunit MF0 is dissolved in sodium radio-phosphate,P-32 solution, forms MF0 protein solutions；
By TiO2Electrode is immersed in the MF0 protein solutions, after being protected from light absorption at room temperature, is rinsed with deionized water, then nitrogen flushing
Gas is dried, and the titanium dioxide anode of MF0 sensitizations is obtained；
By the film after imbibition electrolyte solution be placed on MF0 sensitization titanium dioxide anode and platinum plating to electrode
Between, both ends are fixed, and the solar cell module is obtained.
9. preparation method according to claim 8, which is characterized in that the other algae indigo plant egg of the recombination containing histidine tag
The preparation method of α subunits MF0 is in vain：
By phycocyanin alpha subunit sequence of phycoerythrin gene, phycobilin biosynthetic enzyme genes, histidine tag, color base lyase
Gene E and F are cloned into the expression vector pCDFDeut-1 of Spectinomycin resistance and are built into expression vector pHMPC, are transferred to large intestine
Then bacillus filters out the recombinant allophycocyanin α subunit MF0 engineered strains containing histidine tag；
The engineered strain is connected to fermentation cylinder for fermentation, derivant is added and carries out induced expression, collect bacteria liquid；
By the bacteria liquid ultrasonic disruption, after centrifugation, supernatant is taken, by affinity chromatography column purification, what is purified contains
The recombinant allophycocyanin α subunits MF0 of histidine tag.
10. the solar cell module that a kind of preparation method according to claim 8 or claim 9 obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710048133.XA CN108335910B (en) | 2017-01-20 | 2017-01-20 | Composite gel material and preparation method thereof, and solar cell module and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710048133.XA CN108335910B (en) | 2017-01-20 | 2017-01-20 | Composite gel material and preparation method thereof, and solar cell module and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108335910A true CN108335910A (en) | 2018-07-27 |
| CN108335910B CN108335910B (en) | 2019-12-27 |
Family
ID=62921897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710048133.XA Active CN108335910B (en) | 2017-01-20 | 2017-01-20 | Composite gel material and preparation method thereof, and solar cell module and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108335910B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499757A (en) * | 2020-04-13 | 2020-08-07 | 鲁东大学 | Novel material based on carbon nanotube coupled phycoerythrin and application |
| WO2023140455A1 (en) * | 2022-01-18 | 2023-07-27 | 숙명여자대학교산학협력단 | Electrolyte for dye-sensitized solar cell, and preparation method therefor |
| PL445948A1 (en) * | 2023-08-30 | 2024-06-03 | Uniwersytet Mikołaja Kopernika W Toruniu | Method of obtaining lyophilized collagen and glycosaminoglycans obtained from fish skin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060174938A1 (en) * | 2005-02-04 | 2006-08-10 | Stmicroelectronics S.R.L. | Water-based electrolyte gel for dye-sensitized solar cells and manufacturing methods |
| CN101440370A (en) * | 2008-10-17 | 2009-05-27 | 中国科学院海洋研究所 | Preparation of allophycocyanin fluorescent protein |
| CN104031274A (en) * | 2014-05-28 | 2014-09-10 | 中国科学院烟台海岸带研究所 | Preparation method of aquatic fish skin collagen hydrogel |
-
2017
- 2017-01-20 CN CN201710048133.XA patent/CN108335910B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060174938A1 (en) * | 2005-02-04 | 2006-08-10 | Stmicroelectronics S.R.L. | Water-based electrolyte gel for dye-sensitized solar cells and manufacturing methods |
| CN101440370A (en) * | 2008-10-17 | 2009-05-27 | 中国科学院海洋研究所 | Preparation of allophycocyanin fluorescent protein |
| CN104031274A (en) * | 2014-05-28 | 2014-09-10 | 中国科学院烟台海岸带研究所 | Preparation method of aquatic fish skin collagen hydrogel |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499757A (en) * | 2020-04-13 | 2020-08-07 | 鲁东大学 | Novel material based on carbon nanotube coupled phycoerythrin and application |
| CN111499757B (en) * | 2020-04-13 | 2022-03-11 | 鲁东大学 | Material based on carbon nanotube coupled phycoerythrin and application thereof |
| WO2023140455A1 (en) * | 2022-01-18 | 2023-07-27 | 숙명여자대학교산학협력단 | Electrolyte for dye-sensitized solar cell, and preparation method therefor |
| PL445948A1 (en) * | 2023-08-30 | 2024-06-03 | Uniwersytet Mikołaja Kopernika W Toruniu | Method of obtaining lyophilized collagen and glycosaminoglycans obtained from fish skin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108335910B (en) | 2019-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Application of poly (acrylic acid-g-gelatin)/polypyrrole gel electrolyte in flexible quasi-solid-state dye-sensitized solar cell | |
| CN108335910A (en) | A kind of composite gel material and preparation method thereof, solar cell module and preparation method thereof | |
| CN103824697A (en) | Dye-sensitized solar cell photoanode active membrane and preparation method thereof | |
| CN106024408B (en) | A kind of ruthenium-oxide-vulcanization carbon/carbon-copper composite material, using and a kind of electrode slice of ultracapacitor | |
| Li et al. | Dye-sensitized solar cells based on natural and artificial phycobiliproteins to capture low light underwater | |
| CA2878406C (en) | Photoelectrically convertible composition comprising an anionic polymer, a laminate, and processes therefor | |
| CN103560014B (en) | Dye-sensitized cell is with to electrode, its preparation method and dye-sensitized cell | |
| CN103390507A (en) | Graphene/ platinum nano particle complex fiber electrode material and preparation method thereof | |
| CN107033513B (en) | A kind of phycocyanin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel preparation method and application | |
| CN107022090B (en) | A kind of plural gel containing phycoerythrin, preparation method and application | |
| Mohamad et al. | ZnO photoanode effect on the efficiency performance of organic based dye sensitized solar cell | |
| CN103680971B (en) | A kind of orient the application as optical sensitization material of the recombinant allophycocyanin trimer | |
| Mazloum‐Ardakani et al. | Synthesis and application of Fe3O4@ nanocellulose/TiCl as a nanofiller for high performance of quasisolid‐based dye‐sensitized solar cells | |
| CN108172401A (en) | Dye-sensitized cell combined counter electrode and its preparation method and application | |
| CN100342555C (en) | Low temp process for preparing TiO2 nano-crystal porous film electrode | |
| Chang et al. | Graphene/ZnO nanoparticle composite photoelectrodes for dye-sensitized solar cells with enhanced photovoltaic performance | |
| CN106531445A (en) | Preparation method for porous carbon material electrode for counter electrode of dye-sensitized solar cell | |
| US10270050B2 (en) | Photoelectric conversion layer composition and photoelectric conversion element | |
| CN105551808B (en) | A kind of optical Response gel electrolyte and its preparation method and application | |
| CN102280256A (en) | Dye-sensitized solar cell quasi solid electrolyte and method for preparing solar cell by using same | |
| CN102543450B (en) | Method for producing solid-state dye sensitization solar battery under magnetic field | |
| Xiao et al. | Preparation of photoanode and its application to flexible dye-sensitized solar cells | |
| CN108320912A (en) | A kind of used by dye sensitization solar battery solid electrolyte based on ionic crystals | |
| CN114804110A (en) | Grape-like cluster Ti with three-dimensional interconnected hollow structure 3 C 2 T x MXene material and preparation and application thereof | |
| CN107833970B (en) | Surface modification method of perovskite film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |