CN108906128A - A kind of composite photocatalyst material preparation method based on microorganism template - Google Patents
A kind of composite photocatalyst material preparation method based on microorganism template Download PDFInfo
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- CN108906128A CN108906128A CN201810609991.1A CN201810609991A CN108906128A CN 108906128 A CN108906128 A CN 108906128A CN 201810609991 A CN201810609991 A CN 201810609991A CN 108906128 A CN108906128 A CN 108906128A
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- 239000000463 material Substances 0.000 title claims abstract description 83
- 244000005700 microbiome Species 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 54
- 241001515965 unidentified phage Species 0.000 claims abstract description 25
- 229920001184 polypeptide Polymers 0.000 claims abstract description 20
- 102000004196 processed proteins & peptides Human genes 0.000 claims abstract description 20
- 108090000765 processed proteins & peptides Proteins 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 230000006911 nucleation Effects 0.000 claims abstract description 14
- 238000010899 nucleation Methods 0.000 claims abstract description 14
- 238000007146 photocatalysis Methods 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 238000012239 gene modification Methods 0.000 claims abstract description 9
- 230000005017 genetic modification Effects 0.000 claims abstract description 9
- 235000013617 genetically modified food Nutrition 0.000 claims abstract description 9
- 108090000565 Capsid Proteins Proteins 0.000 claims abstract description 6
- 102100023321 Ceruloplasmin Human genes 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 241000723873 Tobacco mosaic virus Species 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 5
- 241000700605 Viruses Species 0.000 claims description 4
- 235000010726 Vigna sinensis Nutrition 0.000 claims description 2
- 244000042314 Vigna unguiculata Species 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- 244000046052 Phaseolus vulgaris Species 0.000 claims 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 238000012216 screening Methods 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000010931 gold Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002082 metal nanoparticle Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FBEKLGNBMJEXTQ-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[S-2].[Cd+2].[Ag+] Chemical compound [O-2].[O-2].[Ti+4].[S-2].[Cd+2].[Ag+] FBEKLGNBMJEXTQ-UHFFFAOYSA-N 0.000 description 1
- LMBUYNIOLGGKOR-UHFFFAOYSA-N [S-2].[Cd+2].[Au+3].[O-2].[Zn+2] Chemical group [S-2].[Cd+2].[Au+3].[O-2].[Zn+2] LMBUYNIOLGGKOR-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of composite photocatalyst material preparation methods based on microorganism template, belong to photocatalysis field.This method has the polypeptide of specific adsorption and nucleation capability first with display technique of bacteriophage screening, then it is expressed by genetic modification technology on the capsid protein of specified microorganisms, is finally respectively put into catalysis material and the colloidal sol of co-catalysis support materials using improved microorganism as template and prepares composite photocatalyst material.Using a kind of composite photocatalyst material preparation method based on microorganism template of the present invention, the preparation of high-volume nano composite photocatalytic material may be implemented, preparation process nanoscale is controllable, effectively improves photocatalysis efficiency.
Description
Technical field
The present invention relates to photocatalysis fields, prepare more particularly to a kind of composite photocatalyst material based on microorganism template
Method.
Background technique
21 century, the energy and environment are facing mankind and urgently to be resolved two big major issues.Photocatalysis technology is because of energy consumption
The advantages that low, without secondary pollution, becomes a kind of ideal environmental pollution treatment technology and clear energy sources production technology, is answered extensively
For the fields such as the energy, water or air cleaning, health care and defense military.It is polynary multiple with zero dimension or one-dimensional nano structure
Light combination catalysis material can be effectively reduced photo-generate electron-hole to recombination rate, raising surface-catalyzed reactions speed and increase wide
Band gap catalysis material spectral absorption range becomes the important means for improving photocatalysis efficiency.
Silver-cadmium sulfide-titanium dioxide is prepared using evaporation-induced self-assembly and Photodeposition in patent CN105363477A
Titanium tri compound catalysis material, this method prepare powder composite material using grinding technics, it is difficult to obtain size uniformity, pattern
The nano material of rule.In addition, tool has been prepared by electrochemical deposition and light deposition process in patent CN105498802A
There is zinc oxide-gold-cadmium sulfide ternary composite type catalysis material of monodimension nano stick array structure, this method is difficult to realize aoxidize
Zinc-CdS semiconduct hetero-junctions and the nanoscale of gold nano grain size, load site are controllable, and hetero-junctions is easily caused to be overlapped
The problems such as with gold nano grain aggregation.Current preparation method is difficult to play to greatest extent between composite photocatalyst material each component
Coupling synergistic effect, it is therefore necessary to explore a kind of composite photocatalyst material preparation method that new nanoscale is controllable.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of composite photocatalysts based on microorganism template
Material preparation method, synthetic method nanoscale is controllable, can utmostly play between composite photocatalyst material each component
Coupling synergistic effect, improves photocatalysis efficiency.
In order to achieve the above objectives, the technical scheme is that:
A kind of composite photocatalyst material preparation method based on microorganism template, includes the following steps:
(a) being screened respectively using display technique of bacteriophage there is specificity to inhale catalysis material and co-catalysis support materials
Echo the polypeptide of nucleation capability;
(b) using genetic modification technology by the polypeptide with specific adsorption and nucleation capability the table on specified microorganisms
It reaches;
(c) improved microorganism is put into the colloidal sol of catalysis material, carries out photocatalysis material by template of microorganism
The nanometer of material synthesizes, and centrifugation is simultaneously cleaned.;
(d) microorganism after synthesis catalysis material is put into the colloidal sol of co-catalysis support materials again, is with microorganism
Template carries out the nanometer synthesis of co-catalysis support materials, precipitates and cleans, forms required composite photocatalyst material.
Catalysis material in above-mentioned steps (a) is the semiconductor with photocatalysis, such as TiO2、ZnO、WO3、Fe2O3
Or CdS.
Co-catalysis support materials in above-mentioned steps (a) are noble metal, metal oxide or semiconductor, noble metal such as Au,
Pt, Pd or Ag, metal oxide such as Co3O4、RuO2Or IrO2, semiconductor such as CdS, ZnO, WO3、Fe2O3、TiO2Or NiO, partly lead
Body and catalysis material form homotype hetero-junctions, such as Ti02-Fe2O3、Ti02- CdS, or special-shaped hetero-junctions, such as Ti02-NiO。
Polypeptide in above-mentioned steps (a) is made of 2 or more amino acid.
Microorganism in above-mentioned steps (b) is the virus with particular nanostructure, such as M13 bacteriophage, tobacco mosaic disease
Poison or cowpea sheding green mottled virus.
Polypeptide expression in above-mentioned steps (b) is on the capsid protein of microorganism, such as VIII albumen of P and P III of M13 bacteriophage
The capsid protein of albumen or tobacco mosaic virus (TMV).
The size of composite photocatalyst material in above-mentioned steps (d) is mainly by microorganism template type and nanometer packaging technology
Parameter determines.
Compared with the existing technology, the invention has the advantages that:
Photocatalytic process mainly includes three steps:The generation, photoproduction of electron-hole pair carry in catalysis material under illumination
Flow the catalysis reaction of the separated transmission and catalysis material surface charge of son.For given catalysis material, restricts light and urge
Change the compound and lower surface-catalyzed reactions speed that the principal element that efficiency improves is exactly photo-generate electron-hole pair.Zero dimension knot
The nanosphere of structure and the nanofiber of one-dimentional structure or nanotube have specific surface area height, photo-generated carrier diffusion length short and light
The advantages that scattering properties, it is possible to reduce photo-generated carrier is compound, improves photocatalysis efficiency.Polynary nanometer material can integrate performance
The different component of difference, and make to generate Strong synergy between each component on nanoscale.Noble metal nano particles are urged with light
Change Material cladding, surface plasma resonance effect helps to enhance catalysis material in ultraviolet-visible-near-infrared spectrum range
Interior light absorption, while noble metal nano particles can serve as the separation that electron collector promotes photo-generate electron-hole pair, still
The uneven distribution of noble metal nano particles can reduce the photosensitive area of noble metal nano particles aggregation zone catalysis material, together
When in other void areas can not obtain the humidification of noble metal nano particles;Metal oxide is compound with catalysis material,
Oxidation activity and surface-catalyzed reactions speed can be improved, the orderly controlled distribution of metal oxide can play to greatest extent
Its promoting catalysis;Different forbidden bandwidth catalysis materials are compound, can form heterojunction semiconductor, make broadband gap photocatalytic material
Expect that red shift occurs for absorption spectrum, it is expanded into visible region to the response range of light, so that photocatalysis efficiency is improved, but half
The overlapping of conductor hetero-junctions can only realize photocatalysis efficiency local enhancement.Composite photocatalyst material is carried out using microorganism template
Synthesis, reaction condition is mild, and microorganism has special nanostructure and is single for minimum synthesis with the capsid protein of microorganism
Member can not only obtain with good dispersion, the zero-dimension nano particle of size uniformity and one-dimensional nano line or nanotube, may be used also
To realize the nanoscale controlledly synthesis of multicomponent material simultaneously, effectively prevents noble metal nano particles, metal oxide and partly lead
The aggregation of bulk heterojunction is overlapped, and plays the polynary coupling of composite photocatalyst material to greatest extent, improves photocatalysis efficiency.
Detailed description of the invention
Fig. 1 is M13 bacteriophage structural schematic diagram.
Fig. 2 is structural schematic diagram of the M13 bacteriophage after genetic modification in embodiment one.
Fig. 3 is the binary composite photocatalyst material structural schematic diagram finally synthesized using M13 bacteriophage as biological template.
Fig. 4 is structural schematic diagram of the M13 bacteriophage after genetic modification in embodiment two.
Fig. 5 is the tri compound catalysis material structural schematic diagram finally synthesized using M13 bacteriophage as biological template.
Figure label title:1, VIII albumen of M13 bacteriophage P, 2, III albumen of M13 bacteriophage P, 3, Cys-Lys-Arg-Asp-Trp-Thr-Trp-Cys, 4, polypeptide II,
5, catalysis material, 6, co-catalysis support materials I, 7, polypeptide III, 8, co-catalysis support materials II.
Specific embodiment
Specific implementation process of the invention is described further below with reference to Fig. 1, Fig. 2, Fig. 3, Fig. 4 and Fig. 5.
Embodiment one
It for catalysis material 5, Au is that co-catalysis support materials I 6, M13 bacteriophage are made a living that the present embodiment, which uses titanium dioxide,
Object template, M13 bacteriophage structure are as shown in Figure 1.The specific preparation flow of composite photocatalyst material is:
1) there is specific adsorption and nucleation capability to catalysis material titanium dioxide 5 using display technique of bacteriophage screening
Cys-Lys-Arg-Asp-Trp-Thr-Trp-Cys 3 and to I Au6 of co-catalysis support materials have specific adsorption and nucleation capability polypeptide II 4;
2) using genetic modification technology by the Cys-Lys-Arg-Asp-Trp-Thr-Trp-Cys 3 with specific adsorption and nucleation capability M13 bacteriophage P VIII
It is expressed on albumen 1, the polypeptide II 4 with specific adsorption and nucleation capability is expressed on III albumen 2 of P of M13 bacteriophage,
Structure is as shown in Figure 2;
It 3) is 5 × 10 by concentration after 25mL genetic modification13The bacteriophage PBS buffer solution solution of pfu/mL is added to 500mL
Concentration is to be vigorously stirred simultaneously, reaction overnight, catalysis material titanium dioxide 5 exists in the butyl titanate ethanol solution of 1mL/L
On Cys-Lys-Arg-Asp-Trp-Thr-Trp-Cys 3 absorption and nucleating growth, product M13 bacteriophage-titanium dioxide in 3000rpm centrifugation, and with dehydrated alcohol into
Row repeatedly rinses, and is finally diluted to 5 × 10 with PBS buffer solution redissolution13pfu/mL;
4) prepared by aurosol:By 10mgHAuCl4It is dissolved in 100ml water, is heated to boiling, 50mg sodium citrate is dissolved in 5ml
It in water, is added in above-mentioned boiling liquid, is vigorously stirred simultaneously, mixed solution reacts 30min under fluidized state, and the gold of synthesis is molten
Glue is saved at 4 DEG C.M13 bacteriophage-titania solution is mixed with aurosol, is incubated for 12 hours, helps at 4 DEG C under dark condition
Catalysis I Au6 of support materials is adsorbed on polypeptide II 4 and nucleating growth, final product M13 bacteriophage-titanium dioxide-Au standard
Polyethylene glycol and sodium chloride solution precipitating, structure is as shown in Figure 3.
Embodiment two
It is co-catalysis support materials I 6 and cadmium sulfide for catalysis material 5, Au is to help to urge that the present embodiment, which uses titanium dioxide,
Change support materials II 8, M13 bacteriophage as biological template, M13 bacteriophage structure is as shown in Figure 1.Composite photocatalyst material it is specific
Preparation flow is:
1) there is specific adsorption and nucleation capability to catalysis material titanium dioxide 5 using display technique of bacteriophage screening
Cys-Lys-Arg-Asp-Trp-Thr-Trp-Cys 3, there is the polypeptide II 4 of specific adsorption and nucleation capability to I Au6 of co-catalysis support materials and co-catalysis is loaded
II cadmium sulfide 8 of material has the polypeptide III 7 of specific adsorption and nucleation capability;
2) using genetic modification technology by with specific adsorption and nucleation capability Cys-Lys-Arg-Asp-Trp-Thr-Trp-Cys 3 and polypeptide III 7 bite in M13
It is expressed on VIII albumen 1 of P of thallus different location, by the polypeptide II 4 with specific adsorption and nucleation capability in M13 bacteriophage
It is expressed on III albumen 2 of P, structure is as shown in Figure 4;
It 3) is 5 × 10 by concentration after 25mL genetic modification13The M13 bacteriophage PBS buffer solution solution of pfu/mL is added to
500mL concentration is to be vigorously stirred simultaneously, reaction overnight, catalysis material titanium dioxide in the butyl titanate ethanol solution of 1mL/L
Titanium 5 adsorbs and nucleating growth on Cys-Lys-Arg-Asp-Trp-Thr-Trp-Cys 3, and product M13 bacteriophage-titanium dioxide is in 3000rpm centrifugation, and with anhydrous
Ethyl alcohol is repeatedly rinsed, and is finally diluted to 5 × 10 with PBS buffer solution redissolution13pfu/mL;
4) prepared by aurosol:By 10mgHAuCl4It is dissolved in 100ml water, is heated to boiling, 50mg sodium citrate is dissolved in 5ml
It in water, is added in above-mentioned boiling liquid, is vigorously stirred simultaneously, mixed solution reacts 30min under fluidized state, and the gold of synthesis is molten
Glue is saved at 4 DEG C.M13 bacteriophage-titania solution is mixed with aurosol, is incubated for 12 hours, helps at 4 DEG C under dark condition
Catalysis I Au6 of support materials is adsorbed on polypeptide II 4 and nucleating growth, and product M13 bacteriophage-titanium dioxide-Au standard is poly-
Ethylene glycol and sodium chloride solution precipitating, then with PBS buffer solution dissolved dilution to 5 × 1013pfu/mL.The preparation of cadmium sulfide colloidal sol:It will
The sodium hexametaphosphate solution that the cadmium chloride solution and 2mL concentration that 2mL concentration is 0.1mol/L are 0.1mol/L is added to 100mL's
It in deionized water, and is uniformly mixed, the sodium sulfide solution that 2mL concentration is 0.1mol/L is added dropwise while stirring in the solution,
Stirring 30 minutes.Then M13 bacteriophage-titanium dioxide-Au solution is mixed with cadmium sulfide colloidal sol, reacts 12 hours, helps and urge
Change II cadmium sulfide 8 of support materials and adsorbs simultaneously nucleating growth, final product M13 bacteriophage-titanium dioxide-Au- sulphur on polypeptide III 7
Cadmium is repeatedly rinsed in 3000rpm centrifugation, and with deionized water, and structure is as shown in Figure 5.
Claims (6)
1. a kind of composite photocatalyst material preparation method based on microorganism template, which is characterized in that include the following steps:
(a) using display technique of bacteriophage screen respectively to catalysis material and co-catalysis support materials have specific adsorption and
The polypeptide of nucleation capability;
(b) polypeptide with specific adsorption and nucleation capability is expressed on specified microorganisms using genetic modification technology;
(c) improved microorganism is put into the colloidal sol of catalysis material, carries out catalysis material by template of microorganism
Nanometer synthesis, centrifugation are simultaneously cleaned.;
(d) microorganism after synthesis catalysis material is put into the colloidal sol of co-catalysis support materials again, using microorganism as template
The nanometer synthesis for carrying out co-catalysis support materials, precipitates and cleans, form required composite photocatalyst material.
2. one kind is as described in claim 1 based on the composite photocatalyst material preparation method of microorganism template, feature exists
In the catalysis material in the step (a) is the semiconductor with photocatalysis, such as TiO2、ZnO、WO3、Fe2O3Or
CdS。
3. one kind is as described in claim 1 based on the composite photocatalyst material preparation method of microorganism template, feature exists
In the co-catalysis support materials in the step (a) are noble metal, metal oxide or semiconductor, noble metal such as Au, Pt, Pd
Or Ag, metal oxide such as Co3O4、RuO2Or IrO2, semiconductor such as CdS, ZnO, WO3、Fe2O3、TiO2Or NiO, the semiconductor
Homotype hetero-junctions, such as Ti0 are formed with catalysis material2-Fe2O3、Ti02- CdS, or special-shaped hetero-junctions, such as Ti02-NiO。
4. one kind is as described in claim 1 based on the composite photocatalyst material preparation method of microorganism template, feature exists
In the polypeptide in the step (a) is made of 2 or more amino acid.
5. one kind is as described in claim 1 based on the composite photocatalyst material preparation method of microorganism template, feature exists
In the microorganism in the step (b) is the virus with particular nanostructure, such as M13 bacteriophage, tobacco mosaic virus (TMV) or cowpea
Beans chlorotic mottle virus.
6. one kind is as described in claim 1 based on the composite photocatalyst material preparation method of microorganism template, feature exists
In the polypeptide expression in the step (b) is on the capsid protein of microorganism, such as III albumen of VIII albumen of P and P of M13 bacteriophage
Or the capsid protein of tobacco mosaic virus (TMV).
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