CN108147835A - A kind of method that the ceramic block with hierarchical porous structure is prepared using bacteria cellulose as biological template - Google Patents
A kind of method that the ceramic block with hierarchical porous structure is prepared using bacteria cellulose as biological template Download PDFInfo
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Abstract
The invention discloses a kind of methods that the ceramic block with hierarchical porous structure is prepared using bacteria cellulose as biological template.The preparation method is based on bacteria cellulose and Polymer ceramic precursor, using bacteria cellulose as biological template, various elements needed for forming ceramic block are provided as ceramic forerunner, using Freeze Drying Technique and precise controlling sintering process, the multi-stage porous ceramic block material that can be used as catalyst, catalyst carrier or heat-barrier material is prepared.Ceramic block prepared by the method for the present invention replicates the intrinsic hierarchical porous structure of bacteria cellulose well, both larger specific surface area had been provided, there is higher mass transfer ability again, while be easy to detach from reaction system, ideal catalyst and catalyst carrier can be used as to be applied.
Description
Technical field
The present invention relates to the preparing technical fields of hierarchical porous structure ceramic block, and in particular to for catalyst and catalyst
The preparation method of the multi-stage porous ceramic block of carrier.
Background technology
In recent years, with progress, the enhancing of environmental consciousness and the increase of industrial chemicals demand of science and technology, catalyst
It is played an increasingly important role with catalyst carrier in chemical industry.Wherein, aluminium oxide, zirconium oxide and titanium oxide etc. are more
Orifice oxide ceramics are because specific good thermal stability, excellent catalytic activity or co-catalysis activity receive more and more extensively
General concern.Ideal catalyst and catalyst carrier should also have larger specific surface other than it should have above advantages
Product and higher mass transfer ability, can both provide larger reaction compartment, can also accelerate entrance and the product of reactant
It is detached from, so as to improve catalytic efficiency.Meanwhile catalyst and catalyst carrier should also have the energy of the quick separating from reaction system
Power.This requires catalyst and catalyst carrier have hierarchical porous structure and certain appearance and size (such as rodlike and blocky).
However, by traditional method, such as inorganic powder sintering process, template combination slurry perfusion method, sol-gal process, foaming etc.,
The porous ceramics for meeting above-mentioned requirements can not be obtained, otherwise the porous ceramics being prepared with larger pore passage structure, but compares
Surface is smaller or with larger specific surface area, but internal mass transfer ability is relatively low, and shape is powder, is not easy from reaction
It is detached in system.
Polymer ceramic precursor method is from Polymer ceramic precursor, by being molded, curing, being pyrolyzed and being sintered
Process, the method for being eventually converted into inorganic ceramic.It is with the molding ability of macromolecule easy processing, and microcosmic the Nomenclature Composition and Structure of Complexes can
It adjusts, is conducive to prepare the ceramic material with labyrinth and pattern.
On the other hand, bacteria cellulose receives lasting concern as a kind of renewable resource.Bacteria cellulose be by
Bacterial secretory has unique three-dimensional net structure and excellent mechanical strength, is a kind of natural multi-stage porous template material
Material.And compared with the template of synthesis, have many advantages, such as that environment friendly, of low cost and raw material are easy to get.Although in recent years
Scholar both domestic and external is based on bacteria cellulose, has carried out numerous studies in fields such as capacitor, composite material and sensors, but
Seldom have been reported that the application for being related to bacteria cellulose in terms of multi-stage porous ceramics template.Therefore, the present invention is based on bacteria celluloses
And Polymer ceramic precursor, carry out the preparation work of multi-stage porous ceramics.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to one kind is provided using bacteria cellulose as biological template system
The method of the standby ceramic block with hierarchical porous structure.The preparation method is based on bacteria cellulose and Polymer ceramic precursor,
Using bacteria cellulose as biological template, the various elements needed for forming ceramic block are provided as ceramic forerunner, it is dry using freezing
The multi-stage porous pottery that can be used as catalyst, catalyst carrier or heat-barrier material is prepared in dry technology and precise controlling sintering process
Porcelain block materials.
The purpose of the present invention is achieved through the following technical solutions.
A kind of method that the ceramic block with hierarchical porous structure is prepared using bacteria cellulose as biological template, including as follows
Step：
Bacterial cellulose gel is immersed in Polymer ceramic precursor solution, is taken out, freezing, then be freeze-dried
Afterwards, it is sintered, is cooled to room temperature, obtains the ceramic block with hierarchical porous structure.
Further, the Polymer ceramic precursor includes polysiloxanes, polyborosiloxane, poly- silicon-carbon alkane, poly- silicon-carbon
Oxygen alkane, polysilazane, PVDF hollow fiber membrane, alumina precursor, zirconium oxide presoma, titania precursor body, tungsten oxide presoma
One or more of with hafnium oxide presoma.
Further, the solvent of the Polymer ceramic precursor solution is water or the tert-butyl alcohol, and solution concentration is more than 0g/mL
Less than or equal to 2g/mL.
Further, the time of the immersion is more than 0 hour and is less than or equal to 240 hours.
Further, the solvent of the bacterial cellulose gel is consistent with the solvent of Polymer ceramic precursor solution, i.e.,
The solvent of bacterial cellulose gel is all water with the solvent of Polymer ceramic precursor solution or is all the tert-butyl alcohol.
When the solvent of Polymer ceramic precursor solution used is the tert-butyl alcohol, bacteria cellulose aquagel can be immersed in
Solvent displacement is carried out in the tert-butyl alcohol, the water in bacteria cellulose aquagel is removed, obtains and Polymer ceramic precursor solution one
Cause the bacteria cellulose alcogel of solvent.
Further, when the solvent of bacterial cellulose gel and the solvent of Polymer ceramic precursor solution are all water,
The temperature of the freezing is 0 DEG C~-197 DEG C, and the time is more than 0 hour and is less than or equal to 240 hours.
Further, the solvent of bacterial cellulose gel and the solvent of Polymer ceramic precursor solution are all the tert-butyl alcohol
When, the temperature of the freezing is 25 DEG C~-197 DEG C, and the time is more than 0 hour and is less than or equal to 240 hours.
Further, when the solvent of bacterial cellulose gel and the solvent of Polymer ceramic precursor solution are all water,
The temperature of the freeze-drying is 0 DEG C~-100 DEG C, and the time is more than 0 hour and is less than or equal to 240 hours.
Further, the solvent of bacterial cellulose gel and the solvent of Polymer ceramic precursor solution are all the tert-butyl alcohol
When, the temperature of the freeze-drying is 25 DEG C~-100 DEG C, and the time is more than 0 hour and is less than or equal to 240 hours.
Further, it is described to be sintered to：Room temperature keeps the temperature 0~24 hour, then be warming up to 300 to 200 DEG C~300 DEG C
DEG C~800 DEG C between, keep the temperature 0~24 hour, be finally warming up to 800 DEG C~2000 DEG C, keep the temperature 0~24 hour, cooling down.
Further, the atmosphere of the sintering is nitrogen, argon gas, carbon dioxide or air atmosphere.
Further, after freeze-drying, cured, solidification temperature is 40 DEG C~400 DEG C, and the time was less than more than 0 hour
Equal to 240 hours；After curing, then it is sintered.
Further, cure, after sintering, then carry out double sintering；Double sintering temperature is 300 DEG C~2000 DEG C, when
Between be more than 0 hour be less than or equal to 240 hours, atmosphere be nitrogen, argon gas, carbon dioxide or air atmosphere.
Further, after sintering, then double sintering is carried out；Double sintering temperature is 300 DEG C~2000 DEG C, and the time is more than 0
Hour is less than or equal to 240 hours, and atmosphere is nitrogen, argon gas, carbon dioxide or air atmosphere.
In the preparation process of the present invention, bacterial fibers not only play the role of template, also play the effect of enhancing mechanical performance
Fruit restrained effectively cracking of the porous ceramics block in sintering process；And Polymer ceramic precursor possess it is good into
Film property by Freeze Drying Technique and fine sintering process, can form one layer of uniform painting in the fiber surface of bacteria cellulose
Layer replicates the microstructure of bacteria cellulose well.
By above-mentioned preparation method, the present invention can be prepared includes Al with composition2O3、ZrO2、TiO2、SiC、SiCO、
Si3N4With the porous ceramics block materials of more than one in SiBCN.
Ceramic block with hierarchical porous structure prepared by the present invention can be used as catalyst, catalyst carrier or heat-insulated material
Material, while the method for the present invention is suitable for the system of oxide ceramics block and non-oxide ceramics block with hierarchical porous structure
It is standby.
Compared with prior art, the invention has the advantages that and advantageous effect：
(1) porous ceramics block prepared by the method for the present invention replicates the tridimensional network of bacteria cellulose well,
There is the hierarchical porous structure of aperture (＜ 2nm), mesoporous (2-50nm) and macropore (＞ 50nm), typical hierarchical porous structure simultaneously
Not only larger specific surface area had been provided, but also with higher mass transfer ability, can effectively promote catalytic efficiency；
(2) porous ceramics block prepared by the method for the present invention there is relatively low density and good mechanical strength, it can be achieved that
The quick separating of catalyst and reaction system is conducive to the recycling and recycling of catalyst；
(3) the method for the present invention is prepared using cheap biological template and Polymer ceramic precursor with multi-stage porous knot
The ceramic block material of structure, the multi-stage porous ceramic block of preparation can be used as efficient catalyst or catalyst carrier to use,
Chemical industry will have a good application prospect.
Description of the drawings
Fig. 1 is porous ZrO prepared by embodiment 22The SEM figures of the section of ceramic block；
Fig. 2 a are porous ZrO prepared by embodiment 22The absorption of ceramic block/desorption curve figure；
Fig. 2 b are porous ZrO prepared by embodiment 22The pore size distribution curve figure of ceramic block；
Fig. 3 is porous TiO prepared by embodiment 32The SEM figures of the section of ceramic block；
Fig. 4 a are porous TiO prepared by embodiment 32The absorption of ceramic block/desorption curve figure；
Fig. 4 b are porous TiO prepared by embodiment 32The pore size distribution curve figure of ceramic block.
Specific embodiment
Technical scheme of the present invention is described in further detail below in conjunction with specific embodiment and attached drawing, but the present invention
Protection domain and embodiment are without being limited thereto.
In specific embodiment, unless otherwise instructed, the method for use is conventional method, and raw material can be from open business
Approach obtains.
Embodiment 1
The ceramic block with hierarchical porous structure is prepared by biological template of bacteria cellulose, is specifically comprised the following steps：
(1) hydrogel of bacteria cellulose is immersed in the zirconium oxide precursor water solution of a concentration of 0.1g/mL, impregnated
Time is 48 hours；
(2) bacterial cellulose gel for impregnating peroxidating zirconium precursor body aqueous solution is transferred in container, later by container
It is placed at -40 DEG C and is freezed, cooling time is 24 hours；
(3) bacterial cellulose gel of freezing is placed in freeze drier, the cryogenic temperature of freeze drier is -50
DEG C, sublimation drying 24 hours；
(4) sample after freeze-drying is placed in baking oven and cured, solidification temperature and hardening time are respectively 200 DEG C
With 2 hours；After curing, sample is put into desiccator and is stored；
(5) sample after step (4) is cured is sintered, and sintering atmosphere is air, and temperature control program is：Room temperature is extremely
It 300 DEG C, stops 2 hours, then is warming up to 800 DEG C, stop 2 hours, be cooled to room temperature, heating rate is 1 DEG C/min, rate of temperature fall
For 5 DEG C/min；After cooling, white ZrO is obtained2Block materials.
The ZrO of preparation2Block materials replicate the network structure of bacteria cellulose, but the difference is that the network knot well
Structure is the ZrO by below 100nm2Nanofiber is interwoven.Nitrogen adsorption/desorption analysis the result shows that, the ZrO of preparation2Block
Material has hierarchical porous structure and higher specific surface area (25m2/ g), and with relatively low density (0.07g/cm3) and it is good
Mechanical strength (counterweight that 20 times of own wt or more can be born).
Embodiment 2
The ceramic block with hierarchical porous structure is prepared by biological template of bacteria cellulose, is specifically comprised the following steps：
(1) hydrogel of bacteria cellulose is immersed in the zirconium oxide precursor water solution of a concentration of 0.2g/mL, impregnated
Time is 48 hours；
(2) bacterial cellulose gel for impregnating peroxidating zirconium precursor body aqueous solution is transferred in container, later by container
It is placed under liquid nitrogen and is freezed, cooling time is 15 minutes；
(3) bacterial cellulose gel of freezing is placed in freeze drier, the cryogenic temperature of freeze drier is -50
DEG C, sublimation drying 48 hours；
(4) sample after freeze-drying is placed in baking oven and cured, solidification temperature and hardening time are respectively 200 DEG C
With 2 hours；After curing, sample is put into desiccator and is stored；
(5) sample after step (4) is cured is sintered, and sintering atmosphere is nitrogen, and temperature control program is：Room temperature is extremely
It 300 DEG C, stops 2 hours, then is warming up to 800 DEG C, stop 2 hours, be cooled to room temperature, heating rate is 1 DEG C/min, rate of temperature fall
For 5 DEG C/min；
(6) sample being prepared in step (5) is subjected to double sintering again, double sintering atmosphere is air, temperature control journey
Sequence is：Room temperature stops 2 hours to 800 DEG C, is cooled to room temperature, and heating rate is 1 DEG C/min, rate of temperature fall for 5 DEG C/
min；After cooling, white ZrO is obtained2Block materials.
The porous ZrO prepared2The SEM figures of the section of ceramic block are as shown in Figure 1, as seen from Figure 1, the ZrO of preparation2
Block materials replicate the network structure of bacteria cellulose well, the difference is that the network structure is by below 100nm's
ZrO2Nanofiber is interwoven.Nitrogen adsorption/desorption analysis (as shown in Figure 2 a) the result shows that, ZrO2Block materials have compared with
High specific surface area (10m2/ g) and hierarchical porous structure (as shown in Figure 2 b), and with relatively low density (0.13g/cm3) and it is good
Mechanical strength (counterweight that 100 times of own wt or more can be born).
Embodiment 3
The ceramic block with hierarchical porous structure is prepared by biological template of bacteria cellulose, is specifically comprised the following steps：
(1) hydrogel of bacteria cellulose is immersed in the titania precursor body aqueous solution of a concentration of 0.2g/mL, impregnated
Time is 48 hours；
(2) bacterial cellulose gel for impregnating titanium peroxide precursor water solution is transferred in container, later by container
It is placed at -40 DEG C and is freezed, cooling time is 24 hours；
(3) bacterial cellulose gel of freezing is placed in freeze drier, the cryogenic temperature of freeze drier is -50
DEG C, sublimation drying 24 hours；
(4) sample after freeze-drying is placed in baking oven and cured, solidification temperature and hardening time are respectively 200 DEG C
With 2 hours；After curing, sample is put into desiccator and is stored；
(5) the sample progress after step (4) is cured is once sintered, and sintering atmosphere is argon gas, and temperature control program is：Room temperature liter
Temperature stops 2 hours, then be warming up to 500 DEG C to 300 DEG C, stops 2 hours, is cooled to room temperature, and heating rate is 1 DEG C/min, is cooled down
Rate is 5 DEG C/min；
(6) sample being prepared in step (5) is subjected to double sintering again, double sintering atmosphere is air, temperature control journey
Sequence is：Room temperature stops 24 hours to 300 DEG C, is cooled to room temperature, and heating rate is 1 DEG C/min, rate of temperature fall for 5 DEG C/
min；After cooling, white TiO is obtained2Block materials.
The porous TiO prepared2The SEM figures of the section of ceramic block are as shown in figure 3, as seen from Figure 3, the TiO of preparation2
Block materials replicate the network structure of bacteria cellulose well, the difference is that the network structure is by below 100nm's
TiO2Nanofiber is interwoven.Nitrogen adsorption/desorption analysis (as shown in fig. 4 a) the result shows that, TiO2Block materials have compared with
High specific surface area (110m2/ g) and hierarchical porous structure (as shown in Figure 4 b), and with relatively low density (0.04g/cm3) and it is good
Good mechanical strength (counterweight that 50 times of own wt or more can be born).
Embodiment 4
The ceramic block with hierarchical porous structure is prepared by biological template of bacteria cellulose, is specifically comprised the following steps：
(1) bacteria cellulose aquagel is immersed in progress solvent displacement in t-butanol solvent, removes bacteria cellulose and coagulate
Then obtained bacteria cellulose alcogel is immersed in the tertiary fourth of the zirconium oxide presoma of a concentration of 0.06g/mL by the water in glue
In alcoholic solution, soaking time is 48 hours；
(2) bacterial cellulose gel for impregnating peroxidating zirconium precursor body t-butanol solution is transferred in container, later will
Container is placed under liquid nitrogen and is freezed, and cooling time is 15 minutes；
(3) bacterial cellulose gel of freezing is placed in freeze drier, the cryogenic temperature of freeze drier is -20
DEG C, sublimation drying 24 hours；
(4) sample after freeze-drying is placed in baking oven and cured, solidification temperature and hardening time are respectively 200 DEG C
With 2 hours；After curing, sample is put into desiccator and is stored；
(5) the sample progress after step (4) is cured is once sintered, and sintering atmosphere is argon gas, and temperature control program is：Room temperature liter
Temperature stops 2 hours, then be warming up to 1200 DEG C to 300 DEG C, stops 12 hours, is cooled to room temperature, and heating rate is 1 DEG C/min, is dropped
Warm rate is 5 DEG C/min.
(6) sample being prepared in step (5) is subjected to double sintering again, double sintering atmosphere is air, temperature control journey
Sequence is：Room temperature stops 1 hour to 1200 DEG C, is cooled to room temperature, and heating rate is 1 DEG C/min, rate of temperature fall for 5 DEG C/
min；After cooling, white ZrO is obtained2Block materials.
The ZrO of preparation2Block materials replicate the network structure of bacteria cellulose well, the difference is that the network structure
It is the ZrO by below 100nm2Nanofiber is interwoven.Nitrogen adsorption/desorption analysis the result shows that, the ZrO of preparation2Block material
Material has hierarchical porous structure and higher specific surface area (30m2/ g), and with relatively low density (0.05g/cm3) and good machine
Tool intensity (counterweight that 20 times of own wt or more can be born).
Embodiment 5
The ceramic block with hierarchical porous structure is prepared by biological template of bacteria cellulose, is specifically comprised the following steps：
(1) bacteria cellulose aquagel is immersed in progress solvent displacement in t-butanol solvent, removes bacteria cellulose and coagulate
Then obtained bacteria cellulose alcogel is immersed in the tert-butyl alcohol of the alumina precursor of a concentration of 2g/mL by the water in glue
In solution, soaking time is 48 hours；
(2) bacterial cellulose gel for impregnating peroxidating aluminium presoma alcoholic solution is transferred in container, later by container
It is placed under liquid nitrogen and is freezed, cooling time is 15 minutes；
(3) bacterial cellulose gel of freezing is placed in freeze drier, the cryogenic temperature of freeze drier is -20
DEG C, sublimation drying 24 hours；
(4) sample after freeze-drying is placed in baking oven and cured, solidification temperature and hardening time are respectively 200 DEG C
With 2 hours；After curing, sample is put into desiccator and is stored；
(5) the sample progress after step (4) is cured is once sintered, and sintering atmosphere is nitrogen, and temperature control program is：Room temperature liter
Temperature stops 2 hours, then be warming up to 1100 DEG C to 300 DEG C, stops 12 hours, is cooled to room temperature, and heating rate is 1 DEG C/min, is dropped
Warm rate is 5 DEG C/min；
(6) sample being prepared in step (5) is subjected to double sintering again, double sintering atmosphere is air, temperature control journey
Sequence is：Room temperature stops 24 hours to 800 DEG C, is cooled to room temperature, and heating rate is 1 DEG C/min, rate of temperature fall for 5 DEG C/
min；After cooling, white Al is obtained2O3Block materials.
The Al of preparation2O3 block materials replicate the network structure of bacteria cellulose well, the difference is that the network knot
Structure is the Al by below 100nm2O3 nanofibers are interwoven.Nitrogen adsorption/desorption analysis the result shows that, the Al of preparation2O3 blocks
Body material has hierarchical porous structure and higher specific surface area (5m2/ g), and with relatively low density (1.1g/cm3) and it is good
Mechanical strength (counterweight that 1000 times of own wt or more can be born).
Embodiment 6
The ceramic block with hierarchical porous structure is prepared by biological template of bacteria cellulose, is specifically comprised the following steps：
(1) bacteria cellulose aquagel is immersed in progress solvent displacement in t-butanol solvent, removes bacteria cellulose and coagulate
Then obtained bacteria cellulose alcogel is immersed in the t-butanol solution of the polysiloxanes of a concentration of 1g/mL by the water in glue
In, soaking time is 240 hours；
(2) bacterial cellulose gel for impregnating polysiloxanes alcoholic solution is transferred in container, is later placed in container
It is freezed under liquid nitrogen, cooling time is 15 minutes；
(3) bacterial cellulose gel of freezing is placed in freeze drier, the cryogenic temperature of freeze drier is -20
DEG C, sublimation drying 24 hours；
(4) sample after freeze-drying is placed in baking oven and cured, solidification temperature and hardening time are respectively 200 DEG C
With 12 hours；After curing, sample is put into desiccator and is stored；
(5) the sample progress after step (4) is cured is once sintered, and sintering atmosphere is argon gas, and temperature control program is：Room temperature liter
Temperature stops 12 hours to 300 DEG C, is being warming up to 500 DEG C, is stopping 12 hours, is cooled to room temperature, and heating rate is 1 DEG C/min, is dropped
Warm rate is 5 DEG C/min, after cooling, obtains the SiO with hierarchical porous structure2Block materials.
(6) sample being prepared in step (5) is subjected to double sintering again, double sintering atmosphere is air, temperature control journey
Sequence is：Room temperature stops 2 hours to 500 DEG C, is cooled to room temperature, and heating rate is 1 DEG C/min, rate of temperature fall for 5 DEG C/
min；After cooling, white SiO is obtained2Block materials.
The SiO of preparation2Block materials replicate the network structure of bacteria cellulose well, the difference is that the network structure
It is the SiO by below 100nm2Nanofiber is interwoven.Nitrogen adsorption/desorption analysis the result shows that, the SiO of preparation2Block material
Material has hierarchical porous structure and higher specific surface area (50m2/ g), and with relatively low density (0.6g/cm3) and good machine
Tool intensity (counterweight that 1000 times of own wt or more can be born).
Embodiment 7
The ceramic block with hierarchical porous structure is prepared by biological template of bacteria cellulose, is specifically comprised the following steps：
(1) bacteria cellulose aquagel is immersed in progress solvent displacement in t-butanol solvent, removes bacteria cellulose and coagulate
Water in glue, the then tert-butyl alcohol that obtained bacteria cellulose alcogel is immersed in the poly- silicon-carbon alkane of a concentration of 0.5g/mL are molten
In liquid, soaking time is 120 hours；
(2) bacterial cellulose gel for impregnating poly- silicon-carbon alkanol solution is transferred in container, is later placed in container
It is freezed under liquid nitrogen, cooling time is 15 minutes；
(3) bacterial cellulose gel of freezing is placed in freeze drier, the cryogenic temperature of freeze drier is -20
DEG C, sublimation drying 24 hours；
(4) sample after step (3) is freeze-dried is sintered, and sintering atmosphere is argon gas, and temperature control program is：Room temperature liter
Temperature stops 2 hours, then be warming up to 300 DEG C to 200 DEG C, stops 24 hours, then be warming up to 1600 DEG C, stops 2 hours, is cooled to
Room temperature, heating rate are 1 DEG C/min, and rate of temperature fall is 5 DEG C/min；After cooling, grey SiC block materials are obtained.
The SiC block materials of preparation replicate the network structure of bacteria cellulose well, the difference is that the network structure
It is to be interwoven by the SiC nanofibers of below 100nm.Nitrogen adsorption/desorption analysis the result shows that, the SiC block materials of preparation
Material has hierarchical porous structure and higher specific surface area (105m2/ g), and with relatively low density (0.3g/cm3) and good machine
Tool intensity (counterweight that 1000 times of own wt or more can be born).
Embodiment 8
The ceramic block with hierarchical porous structure is prepared by biological template of bacteria cellulose, is specifically comprised the following steps：
(1) bacteria cellulose aquagel is immersed in progress solvent displacement in t-butanol solvent, removes bacteria cellulose and coagulate
Water in glue, in the t-butanol solution of then polysilazane that bacteria cellulose alcogel is immersed in a concentration of 0.15g/mL,
Soaking time is 48 hours；
(2) bacterial cellulose gel for impregnating polysilazane alcoholic solution is transferred in container, is later placed in container
It is freezed under liquid nitrogen, cooling time is 15 minutes；
(3) bacterial cellulose gel of freezing is placed in freeze drier, the cryogenic temperature of freeze drier is -20
DEG C, sublimation drying 24 hours；
(4) sample after step (3) is freeze-dried is sintered, and sintering atmosphere is argon gas, and temperature control program is：Room temperature liter
Temperature stops 24 hours, then be warming up to 300 DEG C to 200 DEG C, stops 2 hours, then be warming up to 2000 DEG C, stops 2 hours, is cooled to
Room temperature, heating rate are 1 DEG C/min, and rate of temperature fall is 5 DEG C/min；After cooling, grey black Si is obtained3N4Block materials.
The Si of preparation3N4Block materials replicate the network structure of bacteria cellulose well, the difference is that the network structure
It is the Si by below 100nm3N4Nanofiber is interwoven.Nitrogen adsorption/desorption analysis the result shows that, the Si of preparation3N4Block
Material has hierarchical porous structure and higher specific surface area (200m2/ g), and with relatively low density (0.05g/cm3) and it is good
Mechanical strength (counterweight that 200 times of own wt or more can be born).
Above example is only preferrred embodiment of the present invention, is only used for explaining the present invention, be not intended to limit the present invention, this
Any change that field technology personnel are made under without departing from spirit of the invention and principle, replacement, combine, simplification, modification
Deng should be equivalent substitute mode, should be included within the scope of the present invention.
Claims (10)
1. a kind of method that the ceramic block with hierarchical porous structure is prepared using bacteria cellulose as biological template, feature exist
In including the following steps：
Bacterial cellulose gel is immersed in Polymer ceramic precursor solution, is taken out, freezing, then after being freeze-dried,
Sintering, is cooled to room temperature, obtains the ceramic block with hierarchical porous structure.
2. preparation method according to claim 1, which is characterized in that the Polymer ceramic precursor includes poly- silica
Alkane, polyborosiloxane, poly- silicon-carbon alkane, poly- siloxicon alkane, polysilazane, PVDF hollow fiber membrane, alumina precursor, oxidation zirconium precursor
One or more of body, titania precursor body, tungsten oxide presoma and hafnium oxide presoma.
3. preparation method according to claim 1, which is characterized in that the solvent of the Polymer ceramic precursor solution is
Water or the tert-butyl alcohol, solution concentration are more than 0g/mL and are less than or equal to 2g/mL；The solvent of the bacterial cellulose gel is made pottery with polymer
The solvent of porcelain precursor solution is consistent, i.e. the solvent of bacterial cellulose gel and the solvent of Polymer ceramic precursor solution is all
Water is all the tert-butyl alcohol.
4. preparation method according to claim 1, which is characterized in that the time of the immersion was less than or equal to more than 0 hour
240 hours.
5. preparation method according to claim 3, which is characterized in that the solvent and polymer-ceramic of bacterial cellulose gel
When the solvent of precursor solution is all water, the temperature of the freezing is 0 DEG C~-197 DEG C, and the time is more than 0 hour and is less than or equal to 240
Hour；When the solvent of bacterial cellulose gel is all the tert-butyl alcohol with the solvent of Polymer ceramic precursor solution, the freezing
Temperature is 25 DEG C~-197 DEG C, and the time is more than 0 hour and is less than or equal to 240 hours.
6. preparation method according to claim 3, which is characterized in that the solvent and polymer-ceramic of bacterial cellulose gel
When the solvent of precursor solution is all water, the temperature of the freeze-drying is 0 DEG C~-100 DEG C, and the time, which is more than 0 hour, to be less than etc.
In 240 hours；It is described cold when the solvent of bacterial cellulose gel is all the tert-butyl alcohol with the solvent of Polymer ceramic precursor solution
It is 25 DEG C~-100 DEG C that dry temperature, which is lyophilized, and the time is more than 0 hour and is less than or equal to 240 hours.
7. preparation method according to claim 1, which is characterized in that described to be sintered to：Room temperature is to 200 DEG C~300
DEG C, keep the temperature 0~24 hour, then be warming up between 300 DEG C~800 DEG C, keep the temperature 0~24 hour, be finally warming up to 800 DEG C~
2000,0~24 hour is kept the temperature, cooling down；The atmosphere of the sintering is nitrogen, argon gas, carbon dioxide or air atmosphere.
8. according to claim 1~7 any one of them preparation method, which is characterized in that after freeze-drying, cured, Gu
It is 40 DEG C~400 DEG C to change temperature, and the time is more than 0 hour and is less than or equal to 240 hours；After curing, then it is sintered.
9. according to claim 1~7 any one of them preparation method, which is characterized in that after sintering, then carry out double sintering；
Double sintering temperature is 300 DEG C~2000 DEG C, and the time is more than 0 hour and is less than or equal to 240 hours, and atmosphere is nitrogen, argon gas, dioxy
Change carbon or air atmosphere.
10. preparation method according to claim 8, which is characterized in that after curing, sintering, then carry out double sintering；It is secondary
Sintering temperature is 300 DEG C~2000 DEG C, and the time is more than 0 hour and is less than or equal to 240 hours, and sintering atmosphere is nitrogen, argon gas, dioxy
Change carbon or air atmosphere.
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