CN103663458B - The preparation method of a kind of porous silica material, the porous silica material and application thereof of preparation - Google Patents
The preparation method of a kind of porous silica material, the porous silica material and application thereof of preparation Download PDFInfo
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Abstract
The preparation method that the invention discloses a kind of porous silica material and the porous silica material prepared according to the method.The preparation method of this porous silica material is as follows: with transition metal oxide as catalyst, makes organic solvent react with raw silicon generation situ catalytic, and prepare porous silica material by post processing impurity removing technologies such as pickling under uniform temperature and pressure and mineralizer effect.The regulation kind of transition metal oxide, consumption, organic solvent kind and reaction condition parameter can regulate and control the pore size of silicon materials, distribution and porosity.The present invention can obtain the porous silica material that current prior art is difficult to obtain.Utilizing porous silica material prepared by the method, production cost is low, and technique is simple, can prepare on a large scale, be suitable for industrialized production, have broad application prospects.
Description
Technical field
The present invention relates to porous silica material preparation field, in particular it relates to by making silicon materials one
Under fixed temperature and pressure and mineralizer effect, with transition metal oxide as catalyst, send out in organic solvent
Raw situ catalytic reacts the method preparing porous silica material, and the porous silica material that obtained by the method and
Its purposes.
Background technology
Porous silicon be a kind of aperture by nanometer to millimetre-sized Multifunction porous material, there is unique Jie
Electrical characteristics, optical characteristics, the microelectronics compatibility and big specific surface area and hole controllability so that it is in sensitive unit
Part and sensor, illuminating material, photoelectric device, bioanalysis, immune detection, insulant, integrated electricity
The fields such as road, solaode and lithium ion battery have a wide range of applications.Porous silicon is a kind of novel half
Conductor photoelectric material, at room temperature has the characteristics such as the electroluminescent of excellence, luminescence generated by light, with existing silicon skill
Art is compatible, it is most likely that realize the application in multiple fields such as silicon-based photoelectric device.
The preparation method of porous silicon mainly has wet chemical etching technique method and electrochemical erosion method at present.Patent
CN1212989 discloses and a kind of prepared by the method that silica flour is corroded by fluorion under hydrothermal conditions porous
Silicon.Patent US7514369 proposes a kind of side utilizing stain etch method to prepare porous silicon powder and nano-silicon
Method.Patent CN1974880 proposes a kind of electrochemical method system using Fluohydric acid .-ethanol to be etchant solution
Standby porous silicon.Patent CN1396315 and CN1396316 individually disclose a kind of cathodic reduction and anodic oxidation
Process for treating surface prepare porous silicon.Patent US2008/0166538 and CN101249962 disclose logical
Cross Fluohydric acid. and method that dimethylformamide etching prepares ordered arrangement porous silicon.Patent
CN102211770B discloses the method that silicon prepares porous silica material with halogenated hydrocarbons catalytic reaction.Document is reported
AgNO can be passed through3Porous silicon granule (Hierarchical micro/nano porous is prepared with HF etching
silicon Li-ion battery anodes.Zhao,Y.,et al.Chemical Communications,2012,48
(42): 5079-5081) or by magnesium powder and SiO2Porous silicon granule (Three-Dimensional is prepared in reaction
Porous Silicon Particles for Use in High-Performance Lithium Secondary Batteries.
Kim,H.,et al.Angewandte Chemie-International Edition,2008,47(52):
10151-10154).
Generally there is cost of material height, complicated process of preparation, equipment requirements in these preparation methoies reported above
High, process condition is harsh, seriously polluted (a large amount of HF of use or by-product), use noble metal catalyst (as
Gold, silver etc.), the problem such as batch production difficulty, or performance can not meet business demand, it is impossible to industry metaplasia
Produce.Therefore, the preparation method being badly in need of a kind of process easy clean carrys out a large amount of synthesizing porous silicon materials.
Summary of the invention
For the deficiencies in the prior art, the present inventor, through carefully studying, uses transiting metal oxidation
Thing makees catalyst, under uniform temperature and pressure and mineralizer effect, makes organic solvent occur former with raw silicon
Position catalytic reaction, and control silicon incomplete reaction, prepare porous silicon material by post processing impurity removing technologies such as pickling
Material.
For reaching this purpose, present invention employs techniques below scheme:
The preparation method of a kind of porous silica material, described method comprises the steps: with transition metal oxide
For catalyst, there is situ catalytic reaction, form hole knot in raw silicon under mineralizer effect in organic solvent
Structure, obtains porous silica material.
The present invention is by regulation transition metal oxide, mineralizer and organic solvent kind；Control catalytic reaction
The mass ratio of temperature, response time and reaction thereof regulates and controls the pore size of the porous silica material obtained, hole
Gap rate.Porous silicon yield can be controlled as required simultaneously, and when silicon chip does raw material, yield is preferably
20-95%, when silica flour does raw material, yield is preferably 1-99%, and yield can pass through response time, temperature and urge
Agent consumption is adjusted, and avoids the use of toxic solvent or noble metal catalyst simultaneously, solves porous
The problem such as silicon materials production cost height, complex process, seriously polluted and industrialized production are difficult.
The effect of organic solvent of the present invention mainly has following two aspects: on the one hand as reaction medium,
On the other hand, siliceous Organic substance is formed with pasc reaction.
Described transition metal oxide can be transition single metal oxides or transition poly-metal deoxide or both
Mixture.
Described transition single-metal metal oxide preferably be selected from Cu, Co, Ni, Zn, Mn, Cr, V, Ti or
Any one or the mixture of at least two in the single metal oxides of Fe；Described transition multi-metal oxygen
Thing preferably is selected from the transition poly-metal deoxide of Cu, Co, Ni, Zn, Mn, Cr, V, Ti or Fe and mixes
Compound.Transition single metal oxides such as CuO, NiO, MnO, Co3O4, Fe2O3Deng, the many metals of transition
Oxide such as CuaCobNicZndMneFe2O4, wherein atomic ratio can be a:b:c:d:e:2,
A+b+c+d+e=1,0≤a, b, c, d, e≤1, and be 0 when a, b, c, d are different with e.
The present invention by silicon raw material in the presence of catalyst of transition metal oxide, mineralizer, organic solvent and
Under uniform temperature and pressure, carry out situ catalytic and form pore structure, then remove described transition metal oxide
Porous silica material is obtained after catalyst.
Described mineralizer is in sodium salt, potassium salt, calcium salt, acetate, nitrate, chlorate and sulfate
Any one or the mixture of at least two, preferably be selected from sodium acetate, potassium acetate, sodium chloride, potassium nitrate
Or any one or the mixture of at least two in sodium sulfate.
Preferably, described organic solvent is in alcohols, aldehydes, lipid, benzene class or acids organic solvent
Any one or the mixture of at least two, preferably ethylene glycol, ethanol, acetaldehyde, formaldehyde, acetic acid second
Any one or at least two in ester, ethanedioic acid ethyl ester, toluene, dimethylbenzene, formic acid or acetic acid mixed
Compound.
Preferably, described organic solvent can be containing the deionized water of 0～70wt%.The matter of described deionized water
Amount percentage ratio for example, 0.01wt%, 5wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%,
60wt%, 65wt%, 70wt%, 75wt% or 78wt%.
Preferably, the temperature of described reaction is 100～500 DEG C, such as 100 DEG C, 160 DEG C, 190 DEG C,
220 DEG C, 250 DEG C, 280 DEG C, 310 DEG C, 340 DEG C, 370 DEG C, 400 DEG C, 430 DEG C, 460 DEG C or
500 DEG C, preferably 150～250 DEG C.
Preferably, the pressure of described reaction is more than 0.1MPa, such as 0.1MPa, 0.5MPa,
0.7MPa, 0.9MPa, 1.1MPa, 1.3MPa, 1.5MPa, 1.7MPa or 1.9MPa, be preferably
0.1～2.0MPa.
Preferably, the described response time is more than 2 hours, such as 2 hours, 8 hours, 12 hours, 16
Hour, 18 hours, 22 hours, 24 hours, 28 hours, 31 hours, 35 hours, 40 hours, 45
Hour, 50 hours, 55 hours, 60 hours, 65 hours, 70 hours, 75 hours, 80 hours, 90
Hour, 100 hours or 110 hours, preferably 36～120 hours.
Described reaction can be carried out in autoclave.
Described raw silicon and transition metal oxide reaction mass can be arbitrary proportion, it is preferable that raw silicon
Be 50:1～5:1 with the mass ratio of transition metal oxide, such as 7:1,9:1,11:1,15:1,19:1,
23:1,27:1,31:1,35:1,39:1,43:1 or 47:1, preferably 45:1～10:1.
Described transition metal oxide and mineralizer quality can be arbitrary proportion, it is preferable that oxo transition metal
The mass ratio of compound and mineralizer is 10:1～1:5, such as 9:1,8:1,7:1,6:1,5:1,4:1,3:1,
2:1,1:1,1:4 or 1:3, preferably 6:1～1:3.
Described raw silicon be shaped as lamellar or/and graininess, its crystal formation is appointing in amorphous, monocrystalline or polycrystalline
Anticipate a kind of or combination of at least two.
Preferably, described method also includes the removal of impurity, described in go deimpurity method to include that deionization is washed
Wash, pickling, alkali cleaning and be dried etc. method.
According to the present invention, described in go removal of impurity concrete grammar as follows: reacted silicon and transition metal oxide
Catalyst etc., are first washed with deionized, and then soak reaction in acid and remove the transiting metal oxidation of residual
Thing, then in sodium hydroxide solution, the silicon dioxide of porous silicon surface is removed in reaction, with deionized water repeatedly
Clean, in vacuum drying oven 80 DEG C be dried within 24 hours, obtain final porous silica material.
In one embodiment, the preparation method of the porous silica material of the present invention comprises the steps: mistake
Cross metal-oxide to be scattered in organic solvent with mineralizer, then load reactor together with raw silicon,
At a temperature of 0.1-2Mpa and 100-500 DEG C, after reacting 36-120 hour, it is cooled to room temperature, table after reacting
Face has the raw silicon of transition metal oxide to be washed with deionized, supersound process in hydrochloric acid, then spend from
Sub-water cleans, then stirring reaction in sodium hydroxide solution, then cleans with deionized water, is then dried
To final porous silica material.
The two of the purpose of the present invention are the porous silica material providing a kind of method from the above mentioned to prepare, institute
Stating porous silica material hole size homogeneous, pore size distribution$ is uniform, and aperture is 2 nanometer-100 microns, and hole
Structure-controllable adjustable.
According to the inventive method by adjusting reaction time, pressure, temperature and transition metal oxide and mineralising
Agent consumption etc. can prepare the porous silica material of any porosity, and exemplary porosity is 10～90%(holes
Rate=1-bulk density/true density).
According to the present invention, described porous silica material pore structure size (by transition metal oxide, mineralizer,
Organic solvent, temperature and pressure etc. regulate) controllable, the size of porous silica material and shape can be according to need
It is adjusted.
Structure, size, pattern, distribution and the porosity in hole can also be carried out micro-by post processing by the present invention
Adjust.
The three of the purpose of the present invention are to provide a kind of porous silica material as above at integrated circuit and the sun
Purposes in the preparation of energy battery, photoelectric device and lithium ion battery etc..
Compared with the prior art, the present invention has the beneficial effect that:
1, utilize the organic solvents such as transition metal oxide, raw silicon, mineralizer and ethylene glycol in a level pressure
Power and at a temperature of situ catalytic reaction prepare porous silica material, solve the porous silicon that current technology is difficult to
Key issue prepared by material；
2, the preparation process of this porous silica material does not use the Fluohydric acid. of hypertoxicity, it is to avoid fluoride waste
Produce, it is achieved that the green cleaning preparation of porous silica material；
3, the preparation process of this porous silica material uses cheap transition metal oxide and mineralizer, it is to avoid
Use noble metal catalyst, it is achieved that the cheap preparation of porous silica material；
4, by regulation transition metal oxide, mineralizer, organic solvent and catalytic reaction condition as anti-
Answer temperature, response time, reaction pressure etc., pore size and the porosity etc. of porous silica material can be regulated and controled
Parameter；
5, as the production technology that porous silica material is novel, have that low production cost, technique is simple, nothing
The advantages such as pollution, easy large-scale production.
Accompanying drawing explanation
Fig. 1 is embodiment 1 silicon wafer raw material and the scanning electron microscope (SEM) photograph of porous silicon chip and XRD figure, wherein, (a)
For the scanning electron microscope (SEM) photograph of silicon wafer raw material, (b) is the metal oxide dispersion scanning electron microscope (SEM) photograph at silicon chip surface,
C () is porous silicon chip and the scanning electron microscopic picture of metal-oxide after catalytic reaction, (d) is porous silicon chip
Scanning electron microscopic picture, (e) is the XRD figure of silicon wafer raw material and the porous silicon chip obtained；
Fig. 2 is embodiment 2 silicon power raw material and the scanning electron microscope (SEM) photograph of porous silicon powder and XRD figure, wherein, (a)
For the scanning electron microscope (SEM) photograph of silicon power raw material, (b) is the scanning electron microscopic picture of porous silicon powder, and (c) is porous silicon powder
High power scanning electron microscopic picture, (d) is the XRD figure of silicon power raw material and the porous silicon powder obtained；
Fig. 3 is the scanning electron microscopic picture that embodiment 3 prepares porous silicon；
Fig. 4 is the scanning electron microscopic picture that embodiment 4 prepares porous silicon；
Fig. 5 is the scanning electron microscopic picture that embodiment 5 prepares porous silicon；
Fig. 6 is the scanning electron microscopic picture that embodiment 6 prepares porous silicon；
Fig. 7 is the scanning electron microscopic picture that embodiment 7 prepares porous silicon；
Fig. 8 is the scanning electron microscopic picture that embodiment 8 prepares porous silicon.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
Following example are (such as CuO, NiO, MnO, Co at transition metal oxide3O4, Fe2O3,
CuaCobNicZndMneFe2O4, a+b+c+d+e=1,0≤a, b, c, d, e≤1 and a, b, c, d and
Be 0 during e difference), mineralizer, under organic solvent and uniform temperature and pressure situ catalytic effect, residue is not
Porous silica material is obtained after the transition metal oxide on the silicon removal surface of reaction.Raw silicon i.e. silica flour used
Or silicon chip is purchased from such as new material company limited by shares of Jiangsu HTC, non-self-control transition metal oxide is purchased from
Such as raw materials such as Beijing Chemical Plant or Chemical Reagent Co., Ltd., Sinopharm Group, mineralizer used and organic solvents
It is routine business product.Self-control transition metal oxide is according to such as Flower-like CuO
microspheres with enhanced catalytic performance for dimethyldichlorosilane
synthesis.Zhang,Z.,et al.RSC Advances.2012,2,2254-2256.Facile solvothermal
synthesis of mesoporous MnFe2O4microspheres as anode materials for Lithium-ion
batteries.Zhang,Z.,et al.Journal of Colloid and Interface Science.2013,
398,185-192.Mesoporous Mn0.5Co0.5Fe2O4nanospheres grown on graphene for
enhanced lithium storage properties.Zhang,Z.,et al.Industrial&Engineering
The document self-controls such as Chemistry Research.2013,52,14906-14912..
Embodiment 1
By homemade 0.1g Mn0.5Co0.5Fe2O4Powder body catalyst and 1.0g sodium acetate are scattered in ethylene glycol solution
In, then with about 1cm2Silicon chip loads polytetrafluoroethyllining lining reactor together, at a temperature of 200 DEG C, and reaction
After 48 hours, it is cooled to room temperature, reacted Mn0.5Co0.5Fe2O4Powder body is recyclable after separating with ethylene glycol
Utilize.Mn will be contained after reaction0.5Co0.5Fe2O4The silicon chip of powder body passes through deionized water wash 5 times, at salt
Supersound process 2 hours under the conditions of 90 DEG C in acid, remove the catalyst of silicon chip surface, the most clear with deionized water
Washing 5 times, then stirring reaction 24 hours in sodium hydroxide solution, remove the titanium dioxide of porous silicon surface
Silicon, cleans repeatedly with deionized water 5 times, in vacuum drying oven 80 DEG C be dried within 24 hours, obtain final many
Hole silicon sheet material.The aperture of porous silicon chip material, at 0.5 micron to 5 micron, is concentrated mainly on 1 micron of left side
Right.
The JSM7001 model Flied emission that the porous silicon chip material of above-mentioned preparation produces in NEC company is swept
Retouch electron microscopy observation surface topography.
X ' the Pert that the porous silicon chip material of above-mentioned preparation is produced in Panalytical company of Holland (PANalytical)
Material crystal formation test is carried out on PRO MPD type Multi-functional X ray diffractometer.
The scanning electron microscope (SEM) photograph of the silicon chip that Fig. 1 (a) is used by embodiment 1, as seen from the figure, this material surface
Smooth densification, non-porous structure；Fig. 1 (b) is the scanning electricity that the catalyst of embodiment 1 is distributed to silicon chip surface
Mirror figure, as seen from the figure, transition metal oxide is uniformly dispersed in silicon chip surface；Fig. 1 (c) is anti-for catalysis
Should the scanning electron microscopic picture of porous silicon chip and metal-oxide afterwards, as seen from the figure, burning after catalytic reaction
Thing is still dispersed in silicon chip surface；It is many that Fig. 1 (d) is that embodiment 1 obtains after overpickling and alkali cleaning
The scanning electron microscope (SEM) photograph of hole silicon sheet material, contains substantial amounts of pore structure, porous silicon chip from figure this silicon sheet material visible
The aperture of material, at 0.5 micron to 5 micron, is concentrated mainly on 1 microns；Fig. 1 (e) is embodiment 1
Silicon wafer raw material and the XRD figure of porous silicon chip that obtains of embodiment 1, contrast two XRD curves and understand,
Their peak position is consistent, illustrates that the porous silicon chip material of gained is pure silicon material.
Embodiment 2
By homemade 0.1g Mn0.5Co0.5Fe2O4Powder body catalyst and 1.0g sodium acetate are scattered in ethylene glycol solution
In, then with about 2cm2Silica flour loads polytetrafluoroethyllining lining reactor together, at a temperature of 200 DEG C, and reaction
After 48 hours, it is cooled to room temperature, reacted Mn0.5Co0.5Fe2O4Powder body is recyclable after separating with ethylene glycol
Utilize.Mn will be contained after reaction0.5Co0.5Fe2O4The silica flour of powder body passes through deionized water wash 5 times, at salt
Supersound process 2 hours under the conditions of 90 DEG C in acid, remove the catalyst of silicon chip surface, the most clear with deionized water
Washing 5 times, then stirring reaction 24 hours in sodium hydroxide solution, remove the titanium dioxide of porous silicon surface
Silicon, cleans repeatedly with deionized water 5 times, in vacuum drying oven 80 DEG C be dried within 24 hours, obtain final many
Hole silicon sheet material.The aperture of porous silicon chip material, at 0.5 micron to 10 micron, is concentrated mainly on 3 microns of left sides
Right.
The scanning electron microscope (SEM) photograph of Fig. 2 (a) is embodiment 2 use silica flour, as seen from the figure, this material surface light
Slip close, non-porous structure；Fig. 2 (b) is the porous silicon sheet material that embodiment 2 obtains after overpickling and alkali cleaning
The scanning electron microscope (SEM) photograph of material, as seen from the figure, defines porous silica material after catalytic reaction；Fig. 2 (c) is for implementing
The high power scanning electron microscope (SEM) photograph of the porous silicon chip material that example 2 obtains after overpickling and alkali cleaning, from figure this silicon visible
Sheet material contains substantial amounts of pore structure, and the aperture of porous silicon chip material, at 0.5 micron to 10 micron, mainly collects
In at 5 microns；The porous silicon powder that Fig. 2 (d) is the silicon power raw material of embodiment 2 and embodiment 2 obtains
XRD figure, contrast two XRD curves and understand, their peak position is consistent, and the porous silicon of gained is described
Powder material is pure silicon material.
Embodiment 3
By about 1cm2Silicon chip and commercially available 0.4g Fe2O3Powder body catalyst is scattered in 3g potassium acetate
60ml ethylene glycol, with 20ml alcohol mixture solution, is then charged into polytetrafluoroethyllining lining reactor,
At a temperature of 250 DEG C, after reacting 80 hours, it is cooled to room temperature, Fe after reaction2O3Powder body and ethylene glycol, ethanol
Recoverable after separation.Fe will be contained after reaction2O3The silicon chip of powder body passes through deionized water wash 5 times,
Supersound process 2 hours under the conditions of 90 DEG C in hydrochloric acid, remove the catalyst of silicon chip surface, with deionized water repeatedly
Cleaning 5 times, then stirring reaction 24 hours in sodium hydroxide solution, remove the titanium dioxide of porous silicon surface
Silicon, cleans repeatedly with deionized water 5 times, in vacuum drying oven 80 DEG C be dried within 24 hours, obtain final many
Hole silicon sheet material.The aperture of porous silicon chip material, at 0.1 micron to 2.5 micron, is concentrated mainly on 0.8 micron
Left and right.
Fig. 3 is the scanning electron microscope (SEM) photograph of the porous silicon chip material that embodiment 3 obtains after overpickling and alkali cleaning, by
Figure understands, and defines porous silica material after catalytic reaction, and aperture, at 0.1 micron to 2.5 micron, is mainly concentrated
At 0.8 microns.
Embodiment 4
By about 2cm2Silicon chip and the homemade MnFe of 0.5g2O4Powder body catalyst and 1.5g sodium acetate are scattered in
In 40ml ethylene glycol 40ml deionized water mixture solution, it is then charged into polytetrafluoroethyllining lining reactor,
At a temperature of 130 DEG C, after reacting 80 hours, it is cooled to room temperature, MnFe after reaction2O4Powder body divides with ethylene glycol
From rear recoverable.MnFe will be contained after reaction2O4The silicon chip of powder body passes through deionized water wash 5 times,
Supersound process 2 hours under the conditions of 90 DEG C in hydrochloric acid, remove the catalyst of silicon chip surface, anti-with deionized water
Cleaning again 5 times, then stirring reaction 24 hours in sodium hydroxide solution, remove the dioxy of porous silicon surface
SiClx, cleans repeatedly with deionized water 5 times, in vacuum drying oven 80 DEG C be dried within 24 hours, obtain final
Porous silicon chip material.The aperture of porous silicon chip material, at 0.1 micron to 3.0 micron, is concentrated mainly on 0.8 micro-
About meter.
Fig. 4 is the scanning electron microscope (SEM) photograph of the porous silicon chip material that embodiment 4 obtains after overpickling and alkali cleaning, by
Figure understands, and defines porous silica material after catalytic reaction, and aperture, at 0.1 micron to 3.0 micron, is mainly concentrated
At 0.8 microns.
Embodiment 5
By about 1cm2Silicon chip is scattered in 20ml with commercially available 0.6g CuO powder body catalyst and 2g sodium acetate
Ethylene glycol, with 60ml acetaldehyde mixture solution, is then charged into polytetrafluoroethyllining lining reactor, 160 DEG C of temperature
Under degree, after reacting 50 hours, being cooled to room temperature, after reaction, CuO powder body can after separating with ethylene glycol and acetaldehyde
Recycle.The silicon chip containing CuO powder body after reaction is passed through deionized water wash 5 times, in hydrochloric acid
Supersound process 2 hours under the conditions of 90 DEG C, remove the catalyst of silicon chip surface, repeatedly clean 5 with deionized water
Time, then stirring reaction 24 hours in sodium hydroxide solution, remove the silicon dioxide of porous silicon surface, use
Deionized water cleans 5 times repeatedly, in vacuum drying oven 80 DEG C be dried within 24 hours, obtain final porous silicon chip
Material.The aperture of porous silicon chip material, at 0.1 micron to 5.0 micron, is concentrated mainly on 2.0 microns.
Fig. 5 is the scanning electron microscope (SEM) photograph of the porous silicon chip material that embodiment 5 obtains after overpickling and alkali cleaning, by
Figure understands, and defines porous silica material after catalytic reaction, and aperture, at 0.1 micron to 5.0 micron, is mainly concentrated
At 2.0 microns.
Embodiment 6
By about 0.3g silica flour and homemade 0.3g Cu0.3Co0.3Mn0.4Fe2O4Powder body catalyst and 3.0g sodium acetate
It is scattered in 50ml ethylene glycol and 30ml toluene mixture solution, is then charged into polytetrafluoroethyllining lining reaction
Still, at a temperature of 210 DEG C, after reacting 60 hours, is cooled to room temperature, Cu after reaction0.3Co0.3Mn0.4Fe2O4
Powder body separates rear recoverable with ethylene glycol and toluene.Cu will be contained after reaction0.3Co0.3Mn0.4Fe2O4Powder
The silica flour of body passes through deionized water wash 5 times, supersound process 2 hours under the conditions of 90 DEG C in hydrochloric acid, removes
The catalyst of silicon powder surface, cleans repeatedly with deionized water 5 times, and then in sodium hydroxide solution, stirring is anti-
Answer 24 hours, remove the silicon dioxide of porous silicon surface, repeatedly clean with deionized water 5 times, do in vacuum
In dry case 80 DEG C be dried within 24 hours, obtain final porous silicon powder material.The aperture of porous silicon powder material is 0.1
Micron, to 6.0 microns, is concentrated mainly on 2.4 microns.
Fig. 6 is the scanning electron microscope (SEM) photograph of the porous silicon chip material that embodiment 6 obtains after overpickling and alkali cleaning, by
Figure understands, and defines porous silica material after catalytic reaction, and aperture, at 0.1 micron to 6.0 micron, is mainly concentrated
At 2.5 microns.
Embodiment 7
By about 2.5g silica flour and homemade 1.8g Cu0.3Ni0.2Co0.2Mn0.3Fe2O4Powder body catalyst and 0.6g nitre
Acid is scattered in 60ml ethylene glycol 60ml ethyl acetate mixture solution, is then charged into polytetrafluoroethyllining lining
Reactor, at a temperature of 300 DEG C, after reacting 45 hours, is cooled to room temperature, after reaction
Cu0.3Ni0.2Co0.2Mn0.3Fe2O4Powder body catalyst separates rear recoverable with ethylene glycol and ethyl acetate.Will
Containing Cu after reaction0.3Ni0.2Co0.2Mn0.3Fe2O4The silica flour of powder body passes through deionized water wash 5 times, at hydrochloric acid
In supersound process 2 hours under the conditions of 90 DEG C, remove the catalyst of silicon chip surface, repeatedly clean with deionized water
5 times, then stirring reaction 24 hours in sodium hydroxide solution, remove the silicon dioxide of porous silicon surface,
Repeatedly clean with deionized water 5 times, in vacuum drying oven 80 DEG C be dried within 24 hours, obtain final porous silicon
Powder material.The aperture of porous silicon powder material, at 0.8 micron to 10.0 micron, is concentrated mainly on 2.0 microns of left sides
Right.
Fig. 7 is the scanning electron microscope (SEM) photograph of the porous silicon chip material that embodiment 7 obtains after overpickling and alkali cleaning, by
Figure understands, and defines porous silica material after catalytic reaction, and aperture, at 0.8 micron to 10.0 micron, mainly collects
In at 2.0 microns.
Embodiment 8
By about 1.8g silica flour and homemade 1.2gZn0.2Cu0.2Ni0.2Co0.2Mn0.2Fe2O4Powder body catalyst and 0.3g
Potassium sulfate is scattered in 30ml ethylene glycol and 50ml acetum, is then charged into autoclave, 100 DEG C of temperature
Under degree, regulation pressure is 0.1MPa, after reacting 2 hours, is cooled to room temperature, after reaction
Zn0.2Cu0.2Ni0.2Co0.2Mn0.2Fe2O4Recoverable after powder body and ethylene glycol and acetic acid separated.After reacting
Containing Zn0.2Cu0.2Ni0.2Co0.2Mn0.2Fe2O4The silica flour of powder body passes through deionized water wash 5 times, in hydrochloric acid
Supersound process 2 hours under the conditions of 90 DEG C, remove the catalyst of silicon powder surface, repeatedly clean 5 with deionized water
Time, then stirring reaction 24 hours in sodium hydroxide solution, remove the silicon dioxide of porous silicon surface, use
Deionized water cleans 5 times repeatedly, in vacuum drying oven 80 DEG C be dried within 24 hours, obtain final porous silicon material
Material.Wherein the silicon of 86% does not participates in reaction, and the porosity 12%(computational methods of porous silica material are: hole
Rate=1-bulk density/true density), the aperture of porous silica material, at 1.0 microns to 5.0 microns, is concentrated mainly on
2.0 microns.
Fig. 8 is the scanning electron microscope (SEM) photograph of the porous silicon chip material that embodiment 8 obtains after overpickling and alkali cleaning, by
Figure understands, and defines porous silica material after catalytic reaction, and aperture, at 1.0 microns to 5.0 microns, is mainly concentrated
At 2.0 microns.
Embodiment 9
By about 1.2g silica flour and commercially available 0.5g Co3O4Powder body catalyst and 0.9g calcium acetate are scattered in
In 30ml ethylene glycol, 40ml glycerol, 10ml acetum, it is then charged into autoclave, 500 DEG C of temperature
Under degree, after reacting 50 hours, it is cooled to room temperature, Co after reaction3O4Powder body and ethylene glycol, glycerol, vinegar
Recoverable after acid separation.Co will be contained after reaction3O4The silica flour of powder body passes through deionized water wash 5
Secondary, supersound process 2 hours under the conditions of 90 DEG C in hydrochloric acid, remove the catalyst of silicon powder surface, use deionization
Water cleans 5 times repeatedly, and then stirring reaction 24 hours in sodium hydroxide solution, remove porous silicon surface
Silicon dioxide, cleans repeatedly with deionized water 5 times, in vacuum drying oven 80 DEG C be dried within 24 hours, obtain
Whole porous silica material.Wherein the silicon of 42% does not participates in reaction, and porosity 54%(of porous silica material calculates
Method is: porosity=1-bulk density/true density), it is left that the aperture of porous silica material is concentrated mainly on 10 nanometers
Right.
Embodiment 10
About 4.0g silica flour is scattered in 40ml with commercially available 2.0g NiO powder body catalyst and 3.2g sodium acetate
Ethylene glycol, with 40ml deionized water solution, is then charged into autoclave, at a temperature of 230 DEG C, and regulation pressure
Power is 2MPa, after reacting 120 hours, is cooled to room temperature, after reacted NiO powder body separates with ethylene glycol
Recoverable.The silica flour containing NiO powder body after reaction is passed through deionized water wash 5 times, in hydrochloric acid
Supersound process 2 hours under the conditions of 90 DEG C, remove the catalyst of silicon powder surface, repeatedly clean 5 with deionized water
Time, then stirring reaction 24 hours in sodium hydroxide solution, remove the silicon dioxide of porous silicon surface, use
Deionized water cleans 5 times repeatedly, in vacuum drying oven 80 DEG C be dried within 24 hours, obtain final porous silicon material
Material.Wherein the silicon of 35% does not participates in reaction, and the porosity 84%(computational methods of porous silica material are: hole
Rate=1-bulk density/true density), the aperture of porous silica material is concentrated mainly on 6 microns.
The inventive method prepares that porous silica material production cost is low, production technology simple, industrialized production is held
Easily, pollution-free, and the pore structure of porous silicon, size, controlled porosity is adjustable, it is easy to operation, additionally
This preparation technology is simple to operation, can realize the large-scale production of porous silica material.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention
It is not limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed ability real
Execute.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to product of the present invention
The equivalence of each raw material is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the guarantor of the present invention
Within the scope of protecting scope and disclosure.
Claims (16)
1. a preparation method for porous silica material, including: in the reactor, make with transition metal oxide
For catalyst, make raw silicon that situ catalytic reaction to occur under mineralizer effect in organic solvent, form hole
Structure, obtains porous silica material；
Wherein, described mineralizer selected from sodium salt, potassium salt, calcium salt and acetate, nitrate, chlorate,
Any one or the mixture of at least two in sulfate, described organic solvent contains 0.01～70wt%
Deionized water；
Described reactor is normal pressure or autoclave, when reaction is carried out in autoclave, and reaction pressure
Power is more than 0.1MPa, and the temperature of described reaction is 100-500 DEG C, and the time of described reaction is little more than 2
Time；
Described transition metal oxide is transition single metal oxides or transition poly-metal deoxide or both is mixed
Compound；Described transition single-metal metal oxide selected from Cu, Co, Ni, Zn, Mn, Cr, V, Ti or
Any one in the single metal oxides of Fe；Described transition poly-metal deoxide is Cu, Co, Ni, Zn,
The transition poly-metal deoxide of Mn, Cr, V, Ti or Fe and mixture thereof；
Described organic solvent selected from ethylene glycol, ethanol, acetaldehyde, formaldehyde, ethyl acetate, ethanedioic acid ethyl ester,
Any one or the mixture of at least two in toluene, dimethylbenzene, formic acid and acetic acid.
2. the method for claim 1, it is characterised in that described transition poly-metal deoxide be Cu,
The transition poly-metal deoxide of Co, Ni, Zn, Mn, Cr, V, Ti or Fe and mixture thereof.
3. the method for claim 1, it is characterised in that described transition single metal oxides is selected from
CuO、NiO、MnO、Co3O4、Fe2O3In any one.
4. method as claimed in claim 2, it is characterised in that described transition poly-metal deoxide is
CuaCobNicZndMneFe2O4, wherein a+b+c+d+e=1,0≤a, b, c, d, e≤1, and a, b, c,
It is 0 when d with e is different.
5. the method for claim 1, it is characterised in that described mineralizer is selected from sodium acetate, acetic acid
Any one or the mixture of at least two in potassium, sodium chloride, potassium nitrate and sodium sulfate.
6. the method for claim 1, it is characterised in that the reaction pressure of described reactor is
0.1-2.0MPa。
7. the method for claim 1, it is characterised in that the temperature of described reaction is 150-250 DEG C.
8. the method for claim 1, it is characterised in that the described response time is 36-120 hour.
9. the method for claim 1, it is characterised in that described raw silicon and transition metal oxide
The mass ratio of catalyst is 50:1～5:1.
10. method as claimed in claim 9, it is characterised in that described raw silicon and transiting metal oxidation
The mass ratio of thing catalyst is 30:1～10:1.
11. the method for claim 1, it is characterised in that described catalyst of transition metal oxide
It is 10:1～1:5 with the mass ratio of mineralizer.
12. methods as claimed in claim 11, it is characterised in that described catalyst of transition metal oxide
It is 8:1～1:3 with the mass ratio of mineralizer.
13. the method for claim 1, it is characterised in that described raw silicon be shaped as lamellar or/
And graininess, its crystal formation is any one or the combination of at least two in amorphous, monocrystalline or polycrystalline.
14. the method for claim 1, it is characterised in that described method also includes the removal of impurity,
Described go deimpurity method include deionized water wash, pickling, alkali cleaning and be dried.
15. methods as claimed in claim 14, it is characterised in that described method include by reacted instead
Answer mixture to be washed with deionized, acid is soaked reaction and removes the transition metal oxide of residual, then use
Deionized water cleans, and then in sodium hydroxide solution, the silicon dioxide of porous silicon surface is removed in reaction, then uses
Deionized water wash, is finally dried to obtain final porous silica material.
The preparation method of 16. 1 kinds of porous silica materials, comprises the steps: transition metal oxide and ore deposit
Agent is scattered in organic solvent, then loads reactor together with raw silicon, 0.1-2Mpa and 100-500 DEG C
At a temperature of, after reacting 36-120 hour, it is cooled to room temperature, there is transition metal oxide reaction rear surface
Raw silicon is washed with deionized, supersound process in hydrochloric acid, then cleans with deionized water, then at hydrogen-oxygen
Change stirring reaction in sodium solution, then clean with deionized water, be then dried to obtain final porous silica material.
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