CN103265065B - Preparation method of graded zinc stannate macroporous materials - Google Patents
Preparation method of graded zinc stannate macroporous materials Download PDFInfo
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- CN103265065B CN103265065B CN201310139984.7A CN201310139984A CN103265065B CN 103265065 B CN103265065 B CN 103265065B CN 201310139984 A CN201310139984 A CN 201310139984A CN 103265065 B CN103265065 B CN 103265065B
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- zinc
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- large pore
- graduation
- pore material
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 14
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 title abstract 7
- 239000004793 Polystyrene Substances 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 239000004005 microsphere Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229920002223 polystyrene Polymers 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 4
- 238000010306 acid treatment Methods 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 51
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 49
- 229910052725 zinc Inorganic materials 0.000 claims description 49
- 239000011148 porous material Substances 0.000 claims description 42
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 24
- 229940071182 stannate Drugs 0.000 claims description 20
- 125000005402 stannate group Chemical group 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical group O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 17
- 206010070834 Sensitisation Diseases 0.000 description 13
- 230000008313 sensitization Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 101150090068 PMII gene Proteins 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- ZJYYHGLJYGJLLN-UHFFFAOYSA-N guanidinium thiocyanate Chemical compound SC#N.NC(N)=N ZJYYHGLJYGJLLN-UHFFFAOYSA-N 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 229940116411 terpineol Drugs 0.000 description 1
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Abstract
The invention relates to a preparation method of zinc stannate nano-materials, and discloses a preparation method of graded zinc stannate macroporous materials. The preparation method of the graded zinc stannate macroporous materials comprises: S1, mixing tin salts, zinc salts, and template molecules with a mixed solvent of an organic solvent and water to form a uniform mixed liquor, adjusting a pH value to be alkaline, performing a in-situ hydrothermal reaction, and then separating, washing and drying products after the reaction ends; S2, performing heating calcination or acid treatment for the products obtained in the S1 to remove the template molecules, thereby obtaining the graded zinc stannate macroporous materials composed of zinc stannate nano-particles, wherein the template molecules are polystyrene microspheres (PS), polymethyl methacrylate microspheres, carbon microspheres or silica microspheres. The preparation method provided by the invention is simple, convenient, rapid and good in reappearance; the synthesized graded zinc stannate macroporous materials can be widely applied in fields of catalysis, lithium ion batteries, solar cells and the like.
Description
Technical field
The present invention relates to the preparation field of zine stannate nano material, more specifically, relate to a kind of preparation method of the zinc large pore material of classifying.
Background technology
Large pore material is the important nano structural material of a class, has a lot of important application in fields such as photochemical catalysis, absorption, separation, drug release, gas sensor, lithium ion battery, solar cells.The strategy of synthetic hollow material has hard template method (carbon template, silicon template, organic polymer template and metallic particles template etc.), soft template method (bubble, oil droplet, macromole, micella, microemulsion) and without template (oswald slaking, Kirkendall diffusion).
The controlled preparation of the graduation macroporous structure material being made up of nano particle is the study hotspot of current field of nanometer material technology.The band gap of ternary oxide zinc is 3.6 eV, and its electronic mobility is up to 10 ~ 15 cm
2v
-1s
-1, in acid N719 dyestuff, there is more stable performance, and its performance easily regulates.At present, Hydrothermal Synthesis 8 nm zinc particles have been reported in research in the world, and its photoelectric efficiency has reached 4.7 %.Graduation nano structural material has caused huge concern owing to having the advantage such as electric transmission, good light scattering ability faster, be considered to likely greatly improve the photoelectric transformation efficiency of battery, but about graduation zinc macropore light anode material, on document, also there is no relevant report at present.
Summary of the invention
Technical problem to be solved by this invention is, in order to overcome the above-mentioned deficiency of prior art, provides a kind of preparation method of the zinc large pore material of classifying, and the method has simply, easily and fast and high repeatability and other advantages.
Another technical problem to be solved by this invention is that a kind of graduation zinc large pore material and application thereof being prepared by above-mentioned preparation method is provided.
Above-mentioned technical problem to be solved by this invention is achieved by the following technical programs:
A preparation method for the zinc of classifying large pore material, comprises the steps:
S1. pink salt, zinc salt and template molecule are mixed with the mixed solvent being made up of organic solvent and water, form even mixed solution, regulate pH value to alkalescence, carry out Situ Hydrothermal reaction, reaction finishes rear product is separated, washs, is dried;
S2. the product obtaining in S1. is heated to calcination or template molecule is removed in acid treatment, obtain the graduation zinc large pore material by zine stannate nano granulometric composition;
Wherein, described template molecule is polystyrene microsphere, poly (methyl methacrylate) micro-sphere, carbosphere or silicon dioxide microsphere;
The particle diameter of described zine stannate nano particle is 3 ~ 30 nm; The particle diameter of described graduation zinc large pore material is 50 ~ 2000 nm.
The present invention utilizes polystyrene microsphere, poly (methyl methacrylate) micro-sphere, carbosphere or silicon dioxide microsphere as template first, preparation graduation zinc large pore material, and the method has simply, easily and fast and high repeatability and other advantages.Can control the size of zine stannate nano particle and the aperture of graduation zinc large pore material by optimization experiment condition.
The aperture of described graduation zinc large pore material is mainly controlled by the size of template molecule.
As a kind of preferred version, described template molecule be polystyrene (
polystyrene, PS) and microballoon.
The state of described polystyrene microsphere, can be that PS microballoon is dispersed in the aqueous solution, can be also the emulsion that synthetic PS microballoon forms.
As a kind of preferred version, described polystyrene microsphere is preferably the emulsion that synthetic PS microballoon forms.
The preparation method of the emulsion that described synthetic PS microballoon forms can carry out with reference to prior art, also can carry out as follows: measure 670 mL H
2o joins in 1000 mL three-necked flasks, is heated to 95 DEG C and keep constant temperature, then passes into N
2, after 10 min, add load weighted 42g vinylbenzene, continue to stir 15 min, add 50 mL 0.29 M Potassium Persulphates, under stable condition, react 24h, obtain the PS emulsion of 200nm.
Regulate the concentration of the temperature of reaction in above-mentioned preparation method, cinnamic concentration and Potassium Persulphate, can obtain the PS emulsion varying in size.
As a kind of preferred version, in S1., the volumetric molar concentration of pink salt is 0.005 ~ 1.0 mol/L.
As a kind of preferred version, in S1., the volumetric molar concentration of zinc salt is 0.01 ~ 2.0 mol/L.
As a kind of preferred version, described pink salt is stannous oxalate, stannous sulfate, tin protochloride, the sub-tin of nitric acid or tin chloride.
As a kind of preferred version, described zinc salt is zinc acetate, zinc chloride, zinc nitrate or zinc sulfate.
As a kind of preferred version, organic solvent described in S1 is glycol ether (glycol ether), ethylene glycol, n-propyl alcohol, Virahol, 1,2-PD, propyl carbinol, BDO, Pentyl alcohol, polyoxyethylene glycol or glycerol;
As a kind of preferred version, described in S1., in mixed solvent, the volume of water accounts for 5 ~ 95% of mixed solvent volume.
As a kind of preferred version, described pH value is 8 ~ 14.
As a kind of preferred version, to regulate pH value alkali used be diethanolamine, trolamine, quadrol, sodium hydroxide, potassium hydroxide or/and ammoniacal liquor,
As a kind of preferred version, the heating of the reaction of Situ Hydrothermal described in S1. completes by baking oven, and temperature of reaction is 120 ~ 250 DEG C.
As the further preferred version of one, described temperature of reaction is 150 ~ 200 DEG C.
As most preferably scheme of one, described temperature of reaction is 200 DEG C.
As a kind of preferred version, the time of Situ Hydrothermal reaction is 1 ~ 72 h.
As most preferably scheme of one, the described reaction times is 24h.
As a kind of preferred version, described in S1., dry temperature is 20 ~ 100 DEG C.
As the further preferred version of one, the drying temperature described in S1. is 50 ~ 80 DEG C.
As most preferably scheme of one, described in S1., dry temperature is 70 DEG C.
As a kind of preferred version, the temperature that heats calcination described in S2. is 400 ~ 1000 DEG C, and the heating calcination time is 0.5 ~ 10h.
As most preferably scheme of one, the temperature that heats calcination described in S2. is 500 DEG C, and the heating calcination time is 1h.
S2. in, acid used is the conventional acid that can go out template molecule in this area.
The present invention also provides a kind of graduation zinc large pore material being prepared by above-mentioned preparation method.
The graduation zinc large pore material that the inventive method makes utilizes X-ray powder diffraction, scanning electron microscope, transmission electron microscope, micropore analyser etc. to carry out detailed sign.
The graduation zinc large pore material that the inventive method makes can be widely used in the fields such as photochemical catalysis, gas sensor, lithium ion battery, solar cell.Especially, while being applied to dye-sensitized solar cells field as light anode material, obtained higher photoelectric transformation efficiency.
Graduation zinc large pore material of the present invention can be used as photocatalyst material, gas sensor material or electrode materials.
As a kind of preferred version, described graduation zinc large pore material can be used as the light anode material of dye-sensitized solar cells.
Compared with prior art, the present invention has following beneficial effect:
(1) preparation method of the present invention has simply, easily and fast and high repeatability and other advantages; (2) described graduation zinc large pore material has higher photoelectric transformation efficiency than the common zinc particle of bibliographical information; (3) the graduation zinc large pore material of preparation method's gained of the present invention can be used as the light anode material of dye-sensitized solar cells, this kind of battery is mainly to imitate photosynthesis principle, a kind of novel solar battery of developing, its main advantage is: (a) abundant raw materials, cost is low, Technology is relatively simple, has larger advantage in big area suitability for industrialized production; (b) all raw material and production technique are nontoxic, pollution-free simultaneously, and part material can be reclaimed fully, and the exploitation to new forms of energy and renewable energy source and to protect mankind environment have great importance.
Brief description of the drawings
Fig. 1 is powder diffraction data figure: 1 is the reacted zine stannate nano particle of Situ Hydrothermal, and 2 is the PS@Zn after hydro-thermal reaction
2snO
4mixture, 3 is the graduation zinc large pore material obtaining after calcining.
Fig. 2 is (a) scanning of graduation zinc large pore material and (b) transmission electron microscope picture, and the inset in figure is its high power scanning electron microscope and transmission picture.
Fig. 3 is (a) BET graphic representation of graduation zinc large pore material and (b) pore size distribution curve figure.
Fig. 4 is the photoelectric current-voltage curve of dye sensitization solar battery.
Fig. 5 is the IPCE graphic representation of dye sensitization solar battery.
Fig. 6 is the photoelectric current-voltage curve of the dye sensitization solar battery for preparing of bilayer cells structure dye sensitization solar battery and comparative example 1.
Embodiment
Further explain the present invention below in conjunction with specific embodiment, but embodiment does not limit in any form to invention.
Embodiment 1 classifies synthesizing of zinc large pore material
PS emulsion is synthetic: measure 670 mL H
2o joins in 1000 mL three-necked flasks, is heated to 95 DEG C and keep constant temperature, then passes into N
2, after 10 mins, add load weighted 42g vinylbenzene, continue to stir 15 min, add 50 mL 0.29 M Potassium Persulphates, under stable condition, react 24h, obtain the PS emulsion of 200nm.
S1. divide another name 1.4024g SnCl
45H
2o, 1.756g Zn (CH
3cOO)
22H
2o joins in 100 mL beakers, measures respectively 200 nm PS emulsions (0.087g/mL) prepared by 16 mL, 16 mL1,2-propylene glycol, 32 mL H with graduated cylinder
2o and 16 mL diethanolamine join in beaker successively, make pH value for alkalescence, continue to stir 30 min, become homogeneous solution; This solution is all transferred in 100 mL tetrafluoroethylene reactors subsequently, and reactor stainless steel outer sleeve is tamping, put into baking oven, 200 DEG C of isothermal reaction 24h, naturally be down to room temperature, to the precipitation of gained wash, each 3 times of alcohol wash, 70 DEG C of oven dry in baking oven; Obtain mixture (the PS@Zn that Surfaces of Polystyrene Microparticles is coated with zine stannate nano particle
2snO
4mixture);
S2. by dry PS@Zn
2snO
4mixture is heated to 500 DEG C with the heat-up rate of 2 DEG C/min in retort furnace, and constant temperature keeps 1h, obtains the graduation zinc large pore material by zine stannate nano granulometric composition.
The product of S1 and S2, for powdery diffractometry test, is judged to its crystal formation, and result shows that prepared product is zinc (Fig. 1, XRD); Characterize its pattern by scanning electron microscope, the sample that discovery obtains is graduation zinc large pore material (Fig. 2 a, FE-SEM), measure its pattern and crystalline structure (Fig. 2 b with transmission electron microscope, TEM), find that graduation zinc large pore material is by zine stannate nano granulometric composition, the particle diameter of zine stannate nano particle approximately 4.2 nm, the particle diameter of graduation zinc large pore material is 180nm.Surface-area and the pore size distribution (seeing Fig. 3) of BET test graduation macropore zinc, calculating its surface-area is 101.2 m
2/ g, pore size distribution is in 5 nm left and right.
The preparation of comparative example 1 zinc particle
Adopt the preparation method identical with embodiment 1, difference is in preparation process, not add PS microballoon, and all the other raw materials are identical with embodiment, prepare zine stannate nano particle, confirm through transmission electron microscope, the particle diameter of the zine stannate nano particle that comparative example 1 obtains is about 4.2nm.
Embodiment 2
Slurry preparation:
Get graduation zinc large pore material or the synthetic zine stannate nano particle of comparative example 1 that 1g is synthesized by embodiment 1, join in the solution being mixed by 0.2 mL Glacial acetic acid, 3g Terpineol 350,0.5g ethyl cellulose, 9 mL dehydrated alcohols, stir after 24h, by slurry supersound process 20 min after stirring, then it is further disperseed, the zinc of must classifying large pore material slurry or zine stannate nano particle slurry, seal for subsequent use.
Adopt the method for silk screen printing that graduation zinc large pore material slurry is printed on FTO conductive glass, brush after graduation zinc large pore material slurry, in temperature programmed control retort furnace, 500 DEG C of thermal treatment 1h, are cooled to after room temperature, are soaked in 40 mM TiCl under 70 DEG C of conditions
4the aqueous solution in 30 min, from TiCl
4in solution, take out Zn
2snO
4working electrode, uses respectively distilled water and absolute ethanol washing three times, dries, and then 520 DEG C of sintering 30min, while being cooled to 80 DEG C of left and right, are soaked in N719 dyestuff approximately 20 hours, and taking-up can obtain adsorbing the zinc working electrode of N719 dyestuff.Drop on another piece FTO conductive glass with the aqueous isopropanol of Platinic chloride, 400 DEG C of calcinings 15 minutes, make containing Pt to electrode; (formula of electrolytic solution is: 0.6 mol/L PMII, 0.03 mol/L I finally on working electrode, to drip electrolytic solution
20.05 mol/L LiI, 0.1 mol/L Guanidinium thiocyanate (GuSCN), 0.5 mol/L 4-tert-butylpyridine (TBP) is dissolved in the acetonitrile and valeronitrile mixed solution that volume ratio is 85:15), with the method packaged battery of sandwich style, obtain dye sensitization solar battery.Described dye sensitization solar battery, its zinc working electrode contains the 180 nm graduation zinc large pore material films that 15 μ m are thick.The photoelectric transformation efficiency of the dye sensitization solar battery of gained is 5.01% (seeing Fig. 4).Its IPCE integration current and short-circuit current
j sc result consistent (seeing Fig. 5).
Classify zinc large pore material films as zinc working electrode, the dye sensitization solar battery of preparation bilayer cells structure to contain 4.2 nm zine stannate nano membrana granulosas and the 180 thick nm of 4 μ m that 15 μ m are thick.The set of described bilayer cells structure adsorb more dyestuff, electric transmission speed, the slower advantage such as electron recombination speed and superior light scattering ability faster, and then effectively improved the photoelectric transformation efficiency of bilayer cells structure, reach 6.10 %(and see Fig. 6).
The zine stannate nano particle slurry of utilizing comparative example 1 to prepare, prepares dye sensitization solar battery, and the zinc working electrode of described dye sensitization solar battery only contains the 4.2 nm zine stannate nano membrana granulosas that 19 μ m are thick.The photoelectric transformation efficiency of described dye sensitization solar battery is 4.67 % (seeing Fig. 6).
Can find out from above-mentioned comparative example, the photoelectric transformation efficiency of the dye sensitization solar battery of the bilayer cells structure of being made up of graduation zinc large pore material and zine stannate nano particle is than high 30.6 % of the photoelectric transformation efficiency of the dye sensitization solar battery of being only made up of zine stannate nano particle of condition of equivalent thickness.
Claims (8)
1. a preparation method for the zinc of classifying large pore material, is characterized in that, comprises the steps:
S1. pink salt, zinc salt and template molecule are mixed with the mixed solvent being made up of organic solvent and water, form even mixed solution, regulate pH value to alkalescence, carry out Situ Hydrothermal reaction, reaction finishes rear product is separated, washs, is dried;
S2. the product obtaining in S1. is heated to calcination or template molecule is removed in acid treatment, obtain the graduation zinc large pore material by zine stannate nano granulometric composition;
Wherein, described template molecule is polystyrene microsphere, poly (methyl methacrylate) micro-sphere, carbosphere or silicon dioxide microsphere;
The particle diameter of described zine stannate nano particle is 3 ~ 30 nm; The particle diameter of described graduation zinc large pore material is 50 ~ 2000 nm;
S1. organic solvent described in is that glycol ether, ethylene glycol, n-propyl alcohol, Virahol, 1,2-PD, propyl carbinol, BDO, Pentyl alcohol, polyoxyethylene glycol are or/and glycerol; S1. described in, in mixed solvent, the volume of water accounts for 5 ~ 95% of mixed solvent volume;
S1. the temperature of situ hydro-thermal reaction is 150 ~ 200 DEG C.
2. preparation method according to claim 1, is characterized in that, in S1., the volumetric molar concentration of pink salt is 0.005 ~ 1.0 mol/L; S1. the volumetric molar concentration of middle zinc salt is 0.01 ~ 2.0 mol/L.
3. preparation method according to claim 1, is characterized in that, described pink salt is stannous oxalate, stannous sulfate, tin protochloride, the sub-tin of nitric acid or tin chloride; Described zinc salt is zinc acetate, zinc chloride, zinc nitrate or zinc sulfate.
4. preparation method according to claim 1, is characterized in that, the time of S1. situ hydro-thermal reaction is 1 ~ 72 h; Regulating pH value alkali used is that diethanolamine, trolamine, quadrol, sodium hydroxide, potassium hydroxide are or/and ammoniacal liquor.
5. preparation method according to claim 1, is characterized in that, the temperature that heats calcination described in S2. is 400 ~ 1000 DEG C, and the heating calcination time is 0.5 ~ 10h.
6. the graduation zinc large pore material being prepared by claim 1 ~ 5 any one preparation method.
7. graduation zinc large pore material according to claim 6 is as the application of photocatalyst material, gas sensor material or electrode materials.
8. application according to claim 7, is characterized in that, described graduation zinc large pore material can be used as the light anode material of dye-sensitized solar cells.
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