CN101249952B - Method for preparing self-doping nitrogen grading porous oxide by using biomass template - Google Patents
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- CN101249952B CN101249952B CN2008100352077A CN200810035207A CN101249952B CN 101249952 B CN101249952 B CN 101249952B CN 2008100352077 A CN2008100352077 A CN 2008100352077A CN 200810035207 A CN200810035207 A CN 200810035207A CN 101249952 B CN101249952 B CN 101249952B
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Abstract
Disclosed is a process for preparing nitrogen self-doped hierarchical porous oxide in the technical field of functional material by employing biological templates, steps of which comprises 1) selecting fresh biomaterial to fix in glutaraldehyde PBS stationary liquid, 2) soaking the biomaterial, after being rinsed by pure water and fixed, in HCl, then rinsing the biomaterial by distilled water fora plurality of times, soaking the biomaterial in salt solution of metal M, 3) rinsing the biomaterial obtained from step 2) by pure water, soaking in the salt solution of metal M, 4) rinsing the obtained biomaterial from step 3) to obtain biomaterial which is naturally dried, then heating within the range of 500-1000 DEG C in an oxygen atmosphere and insulating to obtain the nitrogen-doped porousoxide N-MxOy. The nitrogen self-doped porous oxide prepared by the invention not only is provided with a biological porous structure, but also effectively realizes nitrogen self-doping, and has the obviously strengthened advantage of capturing and absorbing light wave with different wave ranges.
Description
Technical field
The present invention relates to a kind of preparation method of oxide material technical field, particularly a kind of method of utilizing biomass template to prepare self-doping nitrogen grading porous oxide.
Background technology
Oxide powder has been widely used in fields such as photochemical catalysis, luminescent material, magneticsubstance, electromagnetic wave shielding and absorbing material, electron device, dyestuffs.Particularly,, can present unique shielding and absorption characteristic, have good light functionally active at ultraviolet ray, visible light, infrared spectral range according to the difference of oxide compound kind in photocatalysis field.Along with the continuous development and the maturation of oxide material technology of preparing, people can prepare various types of oxide compounds of different-grain diameter, different components, different structure.
Find that through the literature search to prior art the preparation method around oxide compound has many bibliographical informations, as Chinese patent CN1559671, name is called: " manufacture method of poriferous titanium dioxide ".The technical characterstic of this patent is to provide a kind of effect that utilizes chemical ingredients in the tio_2 suspension, make titanium dioxide load on manufacture method on the porous particles securely: to choose following material earlier and carry out thorough mixing, make tio_2 suspension: nano titanium oxide by weight proportion separately; Poly-alkylsiloxane; Polyacrylic ester; Water.In porous particles such as porous silica gel, porousness phosphatic rock, porous ceramics or the porousness aluminum oxide one or more are immersed in the above-mentioned dioxy titanium suspension, fully flood; Perhaps tio_2 suspension is sprayed on a porous surface, the porous particle oven dry after will handling at last.This technology can obtain poriferous titanium dioxide but the porous material that this technology obtains can not realize that nitrogen mixes, and limited the performance and the application of aspects such as product photoelectromagnetism, and this method does not have versatility for the oxide compound for preparing other kinds.Chinese patent CN1565721 for another example, name is called: " a kind of preparation method of nitrogen doping type titanium dioxide visible light catalyzer ".The technical characterstic of this patent is titanic acid ester, hydrolyst, thinner are placed reactor, and stoichiometric number hour under ultra violet lamp is added to ammonium salt aqueous solution in the reactor then, continues reaction, obtains colloidal sol; Solvent flashing obtains behind the titanium gel in 50～200 ℃ air atmosphere getting final product in dry 1～3 hour.This technology adopts the method for collosol and gel, can obtain nitrogen doping type titanium dioxide powder, but the nitrogen doping type titanium dioxide powder that this technology obtains does not have the porous feature, needs simultaneously from external world's introducing nitrogenous source, technology relative complex.
Summary of the invention
The present invention is directed to the deficiencies in the prior art and defective, a kind of method of utilizing biomass template to prepare self-doping nitrogen grading porous oxide is provided, make the oxide powder that makes not only have biological graded porous structure, and effectively realize the nitrogen auto-doping, the light wave of different-waveband is had obvious enhanced catch and absorption characteristic.Raw material sources are wide, with low cost simultaneously, and technology is simple relatively.
The present invention is achieved by the following technical solutions, and the present invention makes full use of classifying porous fine structure and the chloroplast(id) nanometer laminated structure that the natural phant blade is had, vesicular structure and shaping characteristic that the natural phant fruit is had; Utilize biomass institute inherent abundant non-metallic element N, C etc., by the dipping of presoma in the biomass structure, assemble and fire, prepare oxide functional material with biomass graded porous fine structure and self-doping nitrogen.
The inventive method comprises the steps:
The first step is selected the fresh biomass material, and with biological material fixed number hour in glutaraldehyde PBS stationary liquid;
Described biological material was fixed 12 hours under 4 ℃-24 hours in glutaraldehyde PBS stationary liquid.
Described glutaraldehyde PBS stationary liquid is PBS: glutaraldehyde: redistilled water 50: 8: 42 by volume is formulated, and wherein PBS refers to 21.8g disodium hydrogen phosphate,anhydrous [Na
2HPO
4], 6.4g AMSP [NaH
2PO
4], 180g sodium-chlor [NaCl] is dissolved in the 1000ml pure water, and regulates pH value to 7.2 with sodium hydroxide, the solution that preparation obtains.
Second step, the biomass material with purified rinse water after fixing, soak a few hours with HCl after, clean for several times with distilled water, biomass are immersed in the salts solution of metal M 100 ℃-130 ℃ insulation a few hours down;
Described with the HCl immersion, be that HCl soaked 3 hours-12 hours, wherein the HCl volumetric concentration is 5%-10%.Soaking biological material with HCl is in order to remove the metal ion that itself contains in the biomass material.
Described insulation, its time is 3 hours-24 hours.
The 3rd step, clean the biological material of handling in second step with pure water, it is immersed in the salts solution of metal M is incubated a few hours under the room temperature;
Described insulation, its time is 24 hours-120 hours.
The 4th step, clean the biological material of handling in the 3rd step with pure water, make its seasoning;
In the 5th step, further the biological material of handling in the 4th step is warmed up in 500 ℃ of-1000 ℃ of scopes the nitrating porous oxide N-M that insulation promptly obtains having the biomass form after a few hours again in oxygen atmosphere
XO
yMaterial.Wherein: M is a kind of among metal Ti, Zn, Ce, Cu, Al, Sn, Y, Mn, Zr, Cr, Fe, Ni, Co, La, Pb, Pd, Ru, Sr, In, Ga, Bi or the nonmetal Si, and X is in 1,2 or 3, and Y is in 1,2,3 or 4.
Described intensification, its speed are 1 ℃-20 ℃/minute.
Described insulation, its time is 1 hour-5 hours.
Described biological material, refer to a kind of in plant leaf and the fruit, wherein plant leaf refers to C4 plant corn, sugarcane, Chinese sorghum, broomcorn millet, grain, Herba Setariae Viridis blade, a kind of in C3 plant wheat, paddy rice, cotton, soya bean, soybean, pea, French beans, broad bean, camphor tree, Folium seu Cortex Nerii or the maple blade; Fruit refers to a kind of in rice, millet, black rice, soya bean, soybean, pea, melon seeds or the walnut.
The salt of described metal M refers to a kind of in nitrate, chlorate, acetate or the alkoxide of metal M refer to zinc nitrate [Zn (NO especially
3)
2], cerous nitrate [Ce (NO
3)
3], cupric nitrate [Cu (NO
3)
2], aluminum nitrate [Al (NO
3)
3], Yttrium trinitrate [Y (NO
3)
3], manganous nitrate [Mn (NO
3)
2], zirconium nitrate [Zr (NO
3)
2], chromium nitrate [Cr (NO
3)
3], iron nitrate [Fe (NO
3)
3], nickelous nitrate [Ni (NO
3)
2], Xiao Suangu [Co (NO
3)
3], lanthanum nitrate [La (NO
3)
3], nitric acid tin [Sn (NO
3)
2], lead nitrate [Pb (NO
3)
2], Palladous nitrate [Pd (NO
3)
2], nitric acid ruthenium [Ru (NO
3)
3], strontium nitrate [Sr (NO
3)
2], indium nitrate [In (NO
3)
3], gallium nitrate [Ga (NO
3)
3], Bismuth trinitrate [Bi (NO
3)
3], titanous chloride [TiCl
3], zinc chloride [ZnCl
2], Cerium II Chloride [CeCl
3], cupric chloride [CuCl
2], aluminum chloride [AlCl
3], tin tetrachloride [SnCl
4], Yttrium trichloride [YCl
3], Manganous chloride tetrahydrate [MnCl
2], zirconium chloride [ZrCl
2], chromium chloride [CrCl
3], iron(ic) chloride [FeCl
3], iron protochloride [FeCl
2], nickelous chloride [NiCl
2], cobalt chloride [CoCl
3], Lanthanum trichloride [LaCl
3], lead chloride [PbCl
2], Palladous chloride [PdCl
2], ruthenium chloride [RuCl
3], strontium chloride [SrCl
2], indium chloride [InCl
3], gallium chloride [GaCl
3], bismuth chloride [BiCl
3], zinc acetate [Zn (CH
3COO)
2], cerous acetate [Ce (CH
3COO)
3], venus crystals [Cu (CH
3COO)
2], aluminum acetate [Al (CH
3COO)
3], yttium acetate [Y (CH
3COO)
3], manganous acetate [Mn (CH
3COO)
2], zirconium acetate [Zr (CH
3COO)
2], chromium acetate [Cr (CH
3COO)
2], ferrous acetate [Fe (CH
3COO)
2], ironic acetate [Fe (CH
3COO)
3], nickelous acetate [Ni (CH
3COO)
2], cobaltous acetate [Co (CH
3COO)
2], lanthanum acetate [La (CH
3COO)
3], lead acetate [Pb (CH
3COO)
2], acid chloride [Pd (CH
3COO)
2], ruthenium acetate [Ru (CH
3COO)
3], strontium acetate [Sr (CH
3COO)
2], indium acetate [In (CH
3COO)
3], acetate gallium [Ga (CH
3COO)
3], bismuth acetate [Bi (CH
3COO)
3], tetrabutyl titanate [Ti (OC
2H
5)
4] or tetraethoxy [Si (OC
2H
5)
4] in a kind of.
Described nitrating porous oxide N-MxOy refers to N-TiO
2, N-ZnO, N-CeO
2, N-CuO, N-Al
2O
3, N-SnO
2, N-Y
2O
3, N-MnO, N-MnO
2, N-ZrO
2, N-Cr
2O
3, N-FeO, N-Fe
2O
3, N-Fe
3O
4, N-NiO, N-Ni
2O
3, N-Co
3O
4, N-La
2O
3, N-PbO, N-PbO
2, N-PdO, N-PdO
2, N-RuO
2, N-RuO
4, N-SrO, N-SrO
2, N-In
2O
3, N-Ga
2O
3, N-Bi
2O
3Or N-SiO
2In a kind of.
The present invention is based on following principle: the natural biological material, have micron order to nano level promptly unique classifying porous fine structure and chloroplast(id) nano level laminated structure as its inside of plant leaf, but maximum efficiency catch luminous energy and carry out photosynthesis; And for example fruit has the macrostructure of moulding, and its inside also has biological graded porous structure.The intrinsic abundant non-metallic element of biological material itself such as N, C etc. provide valid approach for realizing the non-metallic element auto-doping simultaneously.The present invention is a template with biological material plant leaf, fruit, inherits its classifying porous fine structure, its component that makes a variation, the synchronous heredity of implementation structure and function.
The present invention is by selection, CONTROL PROCESS and the heat decomposition temperature condition of biological material, the self-doping nitrogen grading porous oxide material that can obtain to have the biomass fine structure.The present invention adopts, and plant leaf and fruits with low cost, wide material sources are template, processing is burnt till in salt solution impregnation processing and oxidation through metal M under the certain condition, promptly obtain the grading porous oxide material that composition constitutional chemistry formula is N-MxOy, technology is simple, highly versatile.It is that the self-doping nitrogen grading porous oxide material that template prepares can be applied to fields, forward position such as absorption of electromagnetic wave/shielding field, photochemical catalysis, opto-electronic device, solar cell that the present invention adopts biological material.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment one
Choosing C4 plant leaf-wheat leaf is raw material, fresh wheat leaf is at first fixed 12 hours under 4 ℃ in glutaraldehyde PBS stationary liquid, leaf with purified rinse water after fixing, leaf was soaked 3 hours with 5%HCl, clean for several times with distilled water, leaf immersion was kept 3 hours under 130 ℃ in the aqueous solution of titanous chloride; The leaf of crossing with the pure water clean is immersed in it in ethanolic soln of tetrabutyl titanate and kept 24 hours under the room temperature; With the leaf that the pure water cleaning and dipping is crossed, allow its seasoning; Heat-up rate with 1 ℃/minute in oxygen atmosphere carries out pyroprocessing to it, can obtain having the porous nitrating titanic oxide material of wheat leaf form after 1 hour 500 ℃ of soaking times, have in UV-light that good light is caught, absorptive character to the visible-range, wherein can surpass 12% visible light overall absorption rate.
Embodiment two
Choosing C4 plant leaf-corn leaf is raw material, the fresh corn leaf is at first fixed 15 hours under 4 ℃ in glutaraldehyde PBS stationary liquid, leaf with purified rinse water after fixing, leaf was soaked 4 hours with 8%HCl, clean for several times with distilled water, leaf immersion was kept 4 hours under 100 ℃ in the aqueous solution of zinc nitrate; The leaf of crossing with the pure water clean is immersed in it in aqueous solution of zinc nitrate and kept 72 hours under the room temperature; With the leaf that the pure water cleaning and dipping is crossed, allow its seasoning; Heat-up rate with 2 ℃/minute in oxygen atmosphere carries out pyroprocessing to it, can obtain having the porous nitrating zinc oxide material of corn leaf form after 2 hours 600 ℃ of soaking times, have in ultraviolet and middle infra-red range that good light is caught, absorptive character, wherein infrared rays overall absorption rate can reach 20% in middle infra-red range.
Embodiment three
Choosing C3 plant leaf-soybean leaf is raw material, the fresh soyabean leaf is at first fixed 24 hours under 4 ℃ in glutaraldehyde PBS stationary liquid, leaf with purified rinse water after fixing, leaf was soaked 8 hours with 10%HCl, clean for several times with distilled water, leaf immersion was kept 8 hours under 120 ℃ in the aqueous solution of iron(ic) chloride; The leaf of crossing with the pure water clean is immersed in it in aqueous solution of iron(ic) chloride and kept 120 hours under the room temperature; With the leaf that the pure water cleaning and dipping is crossed, allow its seasoning; Heat-up rate with 5 ℃/minute in oxygen atmosphere carries out pyroprocessing, can obtain having the porous nitrating iron oxide material of soybean leaf form after 5 hours 700 ℃ of soaking times, have in visible-range that good light is caught, absorptive character, the overall absorption rate can reach 15%.
Embodiment four
Choosing C3 plant leaf-red maple leaf is raw material, fresh maple leaf is at first fixed 24 hours under 4 ℃ in glutaraldehyde PBS stationary liquid, leaf with purified rinse water after fixing, leaf was soaked 12 hours with 5%HCl, clean for several times with distilled water, leaf immersion was kept 24 hours under 130 ℃ in the aqueous solution of aluminum acetate; The leaf of crossing with the pure water clean is immersed in it in aqueous solution of aluminum acetate and kept 48 hours under the room temperature; With the leaf that the pure water cleaning and dipping is crossed, make its seasoning; Heat-up rate with 10 ℃/minute in oxygen atmosphere carries out pyroprocessing, can obtain having the porous nitrating alumina material of red maple leaf form after 3 hours 800 ℃ of soaking times, have in UV-light that good light is caught, absorptive character to the visible-range, the overall absorption rate can reach 18% in the visible region.
Embodiment five:
Choosing C3 plant leaf-camphor tree leaf is raw material, fresh camphor tree leaf is at first fixed 24 hours under 4 ℃ in glutaraldehyde PBS stationary liquid, leaf with purified rinse water after fixing, leaf was soaked 12 hours with 5%HCl, clean for several times with distilled water, leaf immersion was kept 24 hours under 130 ℃ in the aqueous solution of lanthanum acetate; The leaf of crossing with the pure water clean is immersed in it in aqueous solution of lanthanum acetate and kept 48 hours under the room temperature; With the leaf that the pure water cleaning and dipping is crossed, make its seasoning; Heat-up rate with 10 ℃/minute in oxygen atmosphere carries out pyroprocessing, can obtain having the porous nitrating lanthanum trioxide material of camphor tree leaf form after 2 hours 800 ℃ of soaking times, have in UV-light that good light is caught, absorptive character to the visible-range, the overall absorption rate can reach 21% in the visible region.
Embodiment six:
Choosing fruit-rice is raw material, fresh rice is at first fixed 24 hours under 4 ℃ in glutaraldehyde PBS stationary liquid, rice with purified rinse water after fixing, rice was soaked 12 hours with 5%HCl, clean for several times with distilled water, rice is immersed in the ethanolic soln of tetraethoxy 130 ℃ and kept 24 hours down; The leaf of crossing with the pure water clean is immersed in it in ethanolic soln of tetraethoxy and kept 48 hours under the room temperature; With the rice that the pure water cleaning and dipping is crossed, allow its seasoning; Heat-up rate with 20 ℃/minute in oxygen atmosphere carries out pyroprocessing, can obtain having the porous nitrating silica oxides of rice form after 3 hours 1000 ℃ of soaking times, have in infra-red range that good light is caught, absorptive character, the overall absorption rate reaches 30%.
Embodiment seven:
Choosing fruit-soya bean is raw material, fresh soya bean is at first fixed 24 hours under 4 ℃ in glutaraldehyde PBS stationary liquid, soya bean with purified rinse water after fixing, soya bean was soaked 10 hours with 5%HCl, clean for several times with distilled water, soybean soaking was kept 24 hours under 130 ℃ in the aqueous solution of cerous nitrate; The soya bean that crosses with the pure water clean is immersed in it in aqueous solution of cerous nitrate and kept 48 hours under the room temperature; With the soya bean that the pure water cleaning and dipping is crossed, allow its seasoning; Heat-up rate with 20 ℃/minute in oxygen atmosphere carries out pyroprocessing, can obtain having the porous nitrating cerium oxide oxide compound of soya bean form after 3 hours 1000 ℃ of soaking times, have in ultraviolet light range that good light is caught, absorptive character, the overall absorption rate can reach 35%.
Embodiment eight:
Choosing fruit-walnut is raw material, fresh walnut is at first fixed 24 hours under 4 ℃ in glutaraldehyde PBS stationary liquid, walnut with purified rinse water after fixing, walnut was soaked 10 hours with 5%HCl, clean for several times with distilled water, walnut is immersed in the aqueous solution of nickelous nitrate 130 ℃ and kept 24 hours down; The walnut of crossing with the pure water clean is immersed in it in aqueous solution of nickelous nitrate and kept 48 hours under the room temperature; With the walnut that the pure water cleaning and dipping is crossed, allow its seasoning; Heat-up rate with 20 ℃/minute in oxygen atmosphere carries out pyroprocessing, can obtain having the porous nitrating nickel oxide oxide compound of walnut form after 4 hours 1000 ℃ of soaking times, have in visible-range that good light is caught, absorptive character, the overall absorption rate can reach 25%.
Claims (7)
1. a method of utilizing biomass template to prepare self-doping nitrogen grading porous oxide is characterized in that, comprises the steps:
The first step is selected the fresh biomass material, and with biological material fixed number hour in glutaraldehyde PBS stationary liquid;
Described biological material refers to a kind of in plant leaf and the fruit, wherein:
Plant leaf refers to a kind of in maize leaf, sugarcane blade, Chinese sorghum blade, broomcorn millet blade, grain blade, Herba Setariae Viridis blade, wheat leaf blade, rice leaf, cotton leaf, soya bean blade, pea blade, French beans blade, broad bean blade, camphor leaf, Folium seu Cortex Nerii or the maple blade;
Fruit refers to a kind of in rice fruit, millet fruit, black rice fruit, soya bean fruit, pea fruit, melon seeds fruit or the Walnut Fruit;
Described glutaraldehyde PBS stationary liquid is PBS: glutaraldehyde: redistilled water 50: 8: 42 by volume is formulated, and wherein PBS refers to 21.8g disodium hydrogen phosphate,anhydrous [Na
2HPO
4], 6.4g AMSP [NaH
2PO
4], 180g sodium-chlor [NaCl] is dissolved in the 1000ml pure water, and regulates pH value to 7.2 with sodium hydroxide, the solution that preparation obtains;
Second step, the biological material with purified rinse water after fixing, soak a few hours with HCl after, clean for several times with distilled water, biological material is immersed in the salts solution of metal M 100 ℃-130 ℃ insulation a few hours down;
The 3rd step, clean the biological material of handling in second step with pure water, it is immersed in the salts solution of metal M is incubated a few hours under the room temperature;
The 4th step, clean the biological material of handling in the 3rd step with pure water, make its seasoning;
In the 5th step, further the biological material of handling in the 4th step is warmed up in 500 ℃ of-1000 ℃ of scopes the nitrating porous oxide N-M that insulation obtains having the biomass form after a few hours again in oxygen atmosphere
XO
yMaterial,
Described nitrating porous oxide N-M
xO
yMaterial refers to N-TiO
2, N-ZnO, N-CeO
2, N-CuO, N-Al
2O
3, N-SnO
2, N-Y
2O
3, N-MnO, N-MnO
2, N-ZrO
2, N-Cr
2O
3, N-FeO, N-Fe
2O
3, N-Fe
3O
4, N-NiO, N-Ni
2O
3, N-Co
3O
4, N-La
2O
3, N-PbO, N-PbO
2, N-PdO, N-PdO
2, N-RuO
2, N-RuO
4, N-SrO, N-SrO
3, N-In
2O
3, N-Ga
2O
3Or N-Bi
2O
3In a kind of.
2. the method for utilizing biomass template to prepare self-doping nitrogen grading porous oxide according to claim 1 is characterized in that, in the first step, biological material was fixed 12 hours under 4 ℃-24 hours in glutaraldehyde PBS stationary liquid.
3. the method for utilizing biomass template to prepare self-doping nitrogen grading porous oxide according to claim 1 is characterized in that, and is described with the HCl immersion in second step, is that HCl soaked 3 hours-12 hours, and wherein the HCl volumetric concentration is 5%-10%.
4. according to claim 1 or the 3 described methods of utilizing biomass template to prepare self-doping nitrogen grading porous oxide, it is characterized in that, in second step, described insulation, its time is 3 hours-24 hours.
5. the method for utilizing biomass template to prepare self-doping nitrogen grading porous oxide according to claim 1 is characterized in that, in the 3rd step, and described insulation, its time is 24 hours-120 hours.
6. the method for utilizing biomass template to prepare self-doping nitrogen grading porous oxide according to claim 1 is characterized in that, in the 5th step, and described intensification, its speed is 1 ℃-20 ℃/minute; Described insulation, its time is 1 hour-5 hours.
7. the method for utilizing biomass template to prepare self-doping nitrogen grading porous oxide according to claim 1 is characterized in that, the salt of described metal M refers to a kind of in nitrate, chlorate, acetate or the alkoxide of metal M.
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| CN1587209A (en) * | 2004-09-02 | 2005-03-02 | 上海交通大学 | Method for preparing porous oxide molecular sieve using plant template |
| CN1609007A (en) * | 2004-10-21 | 2005-04-27 | 上海交通大学 | Process of preparing porous nickel oxide with plant structure |
-
2008
- 2008-03-27 CN CN2008100352077A patent/CN101249952B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587209A (en) * | 2004-09-02 | 2005-03-02 | 上海交通大学 | Method for preparing porous oxide molecular sieve using plant template |
| CN1609007A (en) * | 2004-10-21 | 2005-04-27 | 上海交通大学 | Process of preparing porous nickel oxide with plant structure |
Non-Patent Citations (6)
| Title |
|---|
| Tongxiang Fan, et al..Biomorphic Al2O3 fibers synthesized using cotton as bio-templates.Script Materialia53.2005,53893-897. |
| Tongxiang Fan, et al..Microstructure and Infrared Absorption ofBiomorphicChromium Oxides Templated by Wood Tissues.J. Am. Ceram. Soc.89 11.2006,89(11),3511-3515. |
| Tongxiang Fan,et al..Biomorphic Al2O3 fibers synthesized using cotton as bio-templates.Script Materialia53.2005,53893-897. * |
| Tongxiang Fan,et al..Microstructure and Infrared Absorption ofBiomorphicChromium Oxides Templated by Wood Tissues.J.Am.Ceram.Soc.89 11.2006,89(11),3511-3515. * |
| 赵琳等.模板法制备遗态Al2O3陶瓷的研究.功能材料36 7.2005,36(7),1027-1029. |
| 赵琳等.模板法制备遗态Al2O3陶瓷的研究.功能材料36 7.2005,36(7),1027-1029. * |
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| CN101249952A (en) | 2008-08-27 |
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