CN101219360B - Process for producing transition metal base silica aerogel, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel - Google Patents
Process for producing transition metal base silica aerogel, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel Download PDFInfo
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- CN101219360B CN101219360B CN2008100330222A CN200810033022A CN101219360B CN 101219360 B CN101219360 B CN 101219360B CN 2008100330222 A CN2008100330222 A CN 2008100330222A CN 200810033022 A CN200810033022 A CN 200810033022A CN 101219360 B CN101219360 B CN 101219360B
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Abstract
The invention pertains to the technical field for preparing aerogel materials, in particular to a method for preparing transition metal aerogel, transition metal oxide aerogel and composite transition metal oxide aerogel. The invention adopts an organic dispersing sol-gel method, namely, the cheap organic metallic salt solution is employed as a precursor, polyacrylic acid as a dispersant and propylene oxide as a gel accelerator. The transition metal aerogel and the transition metal oxide aerogel with a plurality of different periods and different groups are prepared by the sol-gel process combining with the supercritical drying and technology for heating processing. As a universal preparation method, the invention is characterized by cheap and easy obtainable raw materials, simple reaction process, relatively short reaction period, etc.; solving a plurality of problems that the transition metal oxide aerogel is hard to be prepared.
Description
Technical field
The invention belongs to the aerogel material preparing technical field, be specifically related to the preparation method of a kind of transition metal base aeroge, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel.
Background technology
Aeroge is a kind of the gathering mutually by nanometer scale ultrafine dust or high-polymer molecular to constitute the nanoporous network; and in hole, be full of a kind of high dispersive solid-state material of gaseous state decentralized medium; its porosity can reach 80～99.8%; generally between 1-100nm, density range can be at 3～600mg/cm for bore hole size
3Between.
Because aerogel material has particular performances, low as Young's modulus and thermal conductivity, apparent density is little, refractive index is little and specific area is high, but its application is very extensive: SiO for example
2Aeroge has been successfully applied to the aspects such as mezzanine window of particle detector, heat insulation skylight and solar energy collecting effect; SiO
2And Al
2O
3Aeroge is widely used in catalyst carrier; And aspect inertial confinement fusion and light laser experimental study, aerogel material is low with its density, adsorptivity and characteristics such as good moldability and easy control of structure system, becomes a kind of important target candidate material.
At present, use sol-gel process and supercritical drying drying process and prepared multiple aeroge.Wherein, SiO
2, Al
2O
3And TiO
2Deng the preparation technology of oxide silica aerogel comparative maturity.The preparation process of these oxide silica aerogels is generally: the solution (as alcoholic solution) with metal alkoxide is presoma, obtains corresponding colloidal sol by hydrolysis and polycondensation; Along with hydrolysis and polycondensation continue carry out, little sol particle grows up gradually, crosslinked, forms bigger amorphous particle; Colloidal sol continues polycondensation, is cross-linked with each other up to most of particle, makes colloidal sol not flow, and has formed the initial wet gel; The initial wet gel makes crosslinked skeleton further firm through overaging, removes impurity through repeatedly washing again, carries out the supercritical fluid drying process, finally obtains aerogel material.This method also is the classical way in the sol-gal process.
Except above-mentioned several aerogel materials, the aeroge of other many types also can be by being that the method preparation of presoma gets with the metal alkoxide.Yet, a lot of metal alkoxides, particularly transition metal alkoxide, costing an arm and a leg even extremely being difficult to obtains.Bivalent metal oxide (as the oxides, divalent of elements such as copper, nickel, cadmium, manganese, cobalt) is difficult to form three-dimensional net structure, makes that more the preparation of its aeroge is very difficult.People such as Alexander E.Gash have reported the new technology with inorganic nickel solution and the Ni-based aeroge of organic epoxide prepared in reaction, and have prepared Fe with the method
2O
3And Cr
2O
3Etc. a series of transition metal base aeroge.And people such as Brady J.Clapasaddle also use the method to prepare multiple transient metal doped silica aerogel material.People such as Gan Lihua, a big waves have also made many work to the preparation of iron oxide aeroge.But the aeroge kind of people's such as Alexander E.Gash method preparation is limited, intensity is lower and be difficult to moulding, the preparation that people's such as Brady J.Clapasaddle technology has also only solved multiple transition metal element doped aeroge.These methods can't solve fully the transition metal base with and the preparation difficult problem of oxide silica aerogel.
Yet, but the application prospect of transition metal oxide silica aerogel is very extensive, all require material to have high specific area and catalytic activity as multiple efficient oxidation thing catalyst, the transition metal oxide silica aerogel material just in time meets voidage and specific area is high, characteristics such as catalytic active center (unbodied crystal boundary, crystal angle and dislocation are abundant) is extremely many can have good application at aspects such as organic reaction (as the Bian Jihua of aromatic), sewage disposal and vehicle exhaust processing; And along with the light material process that develops into the atomic number oxide of having relatively high expectations from simple lightweight low atomic number material of choosing to target material in the light laser experiment, high atomic number transition metal (as tungsten, tantalum etc.) oxide silica aerogel also more and more comes into one's own.The preparation of multiple aeroge will be satisfied the application demand of multiple aspect.
U.S.'s Lorenz-Li Wo More National Laboratory has reported and has adopted expoxy propane to do the method that gel promoter prepares nickel, iron and chromium base aeroge, people such as Gan Lihua, a big waves have also reported the preparation technology of iron oxide aeroge, are that dispersant and expoxy propane are not seen document and patent report as yet for the method that gel promoter prepares multiple transition metal aeroge and adopt polyacrylic acid.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of with low cost, reaction is simple, reaction time is short, applied widely transition metal base aeroge, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel.
The transition metal base aeroge that the present invention proposes and the preparation method of transition metal oxide silica aerogel adopt inorganic dispersion sol-gal process, and concrete steps are as follows:
(1) the transition metal inorganic salts is dissolved in ethanol, is mixed with the transition metal ions ethanolic solution;
(2) in the solution of step (1) gained, add deionized water, polyacrylic acid and expoxy propane successively, stir, left standstill 1-360 minute, obtain gel; Wherein, the adding proportion of metal ion, ethanol, deionized water, polyacrylic acid, expoxy propane is 6mmol: 6～30ml: 0.5～15ml: 0.5-5ml: 1-10ml;
(3) step (2) gained gel was worn out 12-16 days under 22-28 ℃ of temperature,, obtain wet gel with the ethanol washing;
(4) wet gel that step (3) is obtained adopts Co 2 supercritical fluid drying or constant pressure and dry, promptly gets required transition metal base aeroge;
(5) the transition metal base aeroge that step (4) is obtained is under 450-550 ℃ temperature heat treatment 5-8 hour, promptly obtains required transition metal oxide silica aerogel.
The preparation method of the composite transition metal oxide silica aerogel that the present invention proposes, composite transition metal oxide silica aerogel is any in transition metal base-transition metal base aeroge, binary or polynary composite transition metal oxide-transition metal oxide silica aerogel, transition metal base-major element oxide silica aerogel or binary or the polynary composite transition metal oxide-major element oxide; Adopt inorganic dispersion sol-gal process, concrete steps are as follows:
(1) several transition metal inorganic salts are dissolved in respectively in the ethanol, being mixed with molar concentration is the transition metal ions ethanolic solution of 0.2-1mol/L;
(2) several transition metal ions ethanolic solutions that step (1) is obtained volume ratio is in accordance with regulations mixed, and adds deionized water, polyacrylic acid and expoxy propane in mixed liquor successively, stirs, and leaves standstill 1-360 minute, obtains gel; Wherein, the adding proportion of a few metal ion species sums, ethanol, deionized water, polyacrylic acid, expoxy propane is 6mmol: 6～30ml: 0.5～15ml: 0.5-5ml: 1-10ml;
(3) step (2) gained gel was worn out 12-16 days under 22-28 ℃ of temperature,, obtain wet gel with the ethanol washing;
(4) wet gel that step (3) is obtained adopts Co 2 supercritical fluid drying or constant pressure and dry;
(5) the transition metal base aeroge that step (4) is obtained is under 450-550 ℃ temperature heat treatment 5-8 hour, promptly obtains required composite transition metal oxide silica aerogel.
Among the present invention, the transition metal inorganic salts are transition metal (metallic element of I B, II B, IIIB, IVB, VB, VIB, VIIB and VIII) the muriatic salt of ion.
Among the present invention, constant pressure and dry described in the step (4) is that the solvent of low surface tension such as acetone is replaced atmosphere pressure desiccation or adopted organic molecule that gel is carried out atmosphere pressure desiccation behind the modification.Described organic molecule is trim,ethylchlorosilane or dimethyldiethoxysilane etc.
What utilize that the present invention prepares is the aeroge of main component with the transition metal, and its density is 60～300mg/cm
3, and after heat treatment obtaining its transition metal oxide silica aerogel, its density is 200～500mg/cm
3
The aeroge density of the present invention's preparation is low, porosity is high, structural integrity, and microscopic particles is little, reaches nanometer scale.The present invention has also expanded the preparation scope of aeroge greatly, has successfully solved the difficult problem of multiple aeroge preparation.Its raw material is easy to get, with low cost, for fields such as Catalyst Production, chemical industry and environmental improvements, important meaning is arranged all.
Description of drawings
Fig. 1 is the SEM photo of embodiment 1 bronze medal base aeroge.
Fig. 2 is the XRD figure spectrum of embodiment 2 cupric oxide aeroges.
Fig. 3 is the SEM photo of embodiment 2 cupric oxide aeroges.
Fig. 4 is the FEGSEM photo of embodiment 4 chromium base aeroges.
The specific embodiment
Reach accompanying drawing by the following examples and further specify the present invention.(each raw material is marketable material, does not have the purity of special instruction and is chemical pure or analyzes pure grade)
Embodiment 1: the preparation of copper base aeroge
Ratio with copper chloride, ethanol, deionized water, polyacrylic acid and expoxy propane is 6mmol: 10ml: 15ml: 0.5ml: 1ml, adds each reactant under the well-beaten situation successively, obtains gel after about 40 minutes.Gel carries out the CO 2 supercritical drying process after overaging 2 week and ethanol wash 3 times, can obtain copper base aeroge, and its density is about 80mg/cm
3SEM (SEM) image such as Fig. 1.
Embodiment 2: the preparation of cupric oxide aeroge
Ratio with copper chloride, ethanol, deionized water, polyacrylic acid and expoxy propane is 6mmol: 10ml: 15ml: 0.5ml: 1ml, adds each reactant under the well-beaten situation successively, obtains gel after about 40 minutes.Gel carries out the CO 2 supercritical drying process after overaging 2 week and ethanol wash 3 times, can obtain copper base aeroge.With the 500 ℃ of heat treatment 6 hours in Muffle furnace of copper base aeroge, can prepare cupric oxide aeroge sample again, its density is about 200mg/cm
3
According to the X-ray diffractometer analysis as can be known, the chemical composition of this sample is the monoclinic crystal cupric oxide, as Fig. 2.The microscopic appearance of this product as shown in Figure 3.
Embodiment 3: the preparation of chromium base aeroge
Chromium chloride is dissolved in the ethanol, is mixed with the solution of 0.2mol/L.Get this solution of 30ml, under condition of stirring, drip the deionized water of 0.5ml.After waiting to stir fully, drip the PAA of 0.8ml again, (ratio that is chromium chloride, ethanol, deionized water, polyacrylic acid and expoxy propane is about 6mmol to the last expoxy propane that adds 1.3ml again: 30ml: 0.5ml: 0.8ml: 1.3ml), leave standstill about 360 minutes gels.Gel through overaging and washing, is carried out the CO 2 supercritical drying again, can obtain chromium base aeroge.The density of this aeroge is about 60mg/cm
3
Embodiment 4: the preparation of chromium oxide aeroge
Ratio with chromium chloride, ethanol, deionized water, polyacrylic acid and expoxy propane is 6mmol: 6ml: 0.7ml: 0.8ml: 1.3ml, adds each reactant under the well-beaten situation successively, obtains gel after about 6 minutes.Gel carries out the CO 2 supercritical drying process after overaging 2 week and ethanol wash 3 times, can obtain chromium base aeroge, and its density is about 300mg/cm
3Its microscopic appearance such as Fig. 4.
With the 500 ℃ of heat treatment 6 hours in Muffle furnace of chromium base aeroge, can prepare the chromium oxide aeroge again, its density is about 500mg/cm
3
Embodiment 5: acetone is replaced constant pressure and dry and is prepared the iron-based aeroge
Iron chloride, ethanol, deionized water, polyacrylic acid and the expoxy propane ratio according to 6mmol: 6ml: 0.7ml: 0.8ml: 1.3ml is made an addition in the container successively, left standstill 1 minute after fully stirring, can obtain the iron-based alcogel.This gel soaked for two weeks with acetone again after 2 weeks of overaging, ethanol wash 3 times, wherein changed one time acetone every 3 days.At last gel is taken out, air dry under the room temperature condition can obtain iron oxide aeroge sample, and its density is about 5000mg/cm
3
Embodiment 6: the preparation of nickel oxide/silica nanometer composite aerogel
It is in 3: 1 the mixed solution that nickel chloride is dissolved in ethanol and deionized water volume ratio, is mixed with the solution of 0.75mol/L.Again this solution is mixed with PAA with 10: 1 ratio of volume ratio under condition of stirring, prepare Sol A.In addition, ethyl orthosilicate and ethanol, deionized water were mixed in 1: 2: 0.25 by volume obtain sol B.With Sol A and 6.4: 1 by volume mixed mixed sols C that get of B.Get C colloidal sol 7.4ml, under well-beaten situation, add expoxy propane 2ml and hydrofluoric acid 0.04ml successively, leave standstill several minutes gels.The gained gel carries out ethanol supercritical drying drying process after 2 weeks of overaging, washing 3 times, and the nanometer that can obtain Ni, Si atomic ratio and be 1: 1 is Ni-based/the silica composite aerogel.
Again this aeroge is placed 500 ℃ of heat treatments of Muffle furnace, can obtain 1: 1 mol ratio nickel oxide/silica nanometer composite aerogel.
Embodiment 7: the preparation of cupric oxide/nickel oxide nano composite aerogel
Copper chloride is dissolved in the ethanol, is mixed with the solution of 0.75mol/L.Get this solution of 6.25ml, the deionized water of Dropwise 5 ml under condition of stirring.After waiting to stir fully, drip the PAA of 0.5ml again, obtain Sol A.Again nickel chloride is dissolved in the ethanol, is mixed with the solution of 0.75mol/L.Get this solution of 6.25ml, the deionized water of Dropwise 5 ml under condition of stirring.After waiting to stir fully, drip the PAA of 0.5ml again, obtain sol B.Sol A and sol B are mixed, add the expoxy propane of 6ml again.Leave standstill several minutes gels after fully stirring.Gel through overaging and washing, is carried out the CO 2 supercritical drying again, can obtain copper/Ni-based aeroge.
At last, this aeroge is heated 500 ℃ of processing in Muffle furnace, can obtain mol ratio and be cupric oxide/nickel oxide nano composite aerogel of 1: 1.
Above-described embodiment is only in order to illustrate technological thought of the present invention and characteristics; its purpose is to make those of ordinary skill in the art can understand content of the present invention and implements according to this; the scope of this patent also not only is confined to above-mentioned specific embodiment; be all equal variation or modifications of doing according to disclosed spirit, still be encompassed in the protection domain of the present utility model.
Claims (4)
1. the preparation method of transition metal base aeroge and transition metal oxide silica aerogel is characterized in that adopting inorganic dispersion sol-gal process, and concrete steps are as follows:
(1) transition metal chloride is dissolved in ethanol, is mixed with the transition metal ions ethanolic solution;
(2) in the solution of step (1) gained, add deionized water, polyacrylic acid and expoxy propane successively, stir, left standstill 1-360 minute, obtain gel; Wherein, the adding proportion of metal ion, ethanol, deionized water, polyacrylic acid, expoxy propane is 6mmol: 6～30ml: 0.5～15ml: 0.5-5ml: 1-10ml;
(3) step (2) gained gel was worn out 12-16 days under 22-28 ℃ of temperature,, obtain wet gel with the ethanol washing;
(4) wet gel that step (3) is obtained adopts Co 2 supercritical fluid drying or constant pressure and dry, promptly gets required transition metal base aeroge;
(5) the transition metal base aeroge that step (4) is obtained is under 450-550 ℃ temperature heat treatment 5-8 hour, promptly obtains required transition metal oxide silica aerogel;
Wherein: described transition metal is the element of group vib, VIII family and I B family.
2. the preparation method of a composite transition metal oxide silica aerogel is characterized in that composite transition metal oxide silica aerogel is transition metal base-transition metal base aeroge; Adopt inorganic dispersion sol-gal process, its concrete steps are as follows:
(1) several transition metal chlorides are dissolved in respectively in the ethanol, being mixed with molar concentration is the transition metal ions ethanolic solution of 0.2-1mol/L;
(2) several transition metal ions ethanolic solutions that step (1) is obtained volume ratio is in accordance with regulations mixed, and adds deionized water, polyacrylic acid and expoxy propane in mixed liquor successively, stirs, and leaves standstill 1-360 minute, obtains gel; Wherein, the adding proportion of a few metal ion species sums, ethanol, deionized water, polyacrylic acid, expoxy propane is 6mmol: 6～30ml: 0.5～15ml: 0.5-5ml: 1-10ml;
(3) step (2) gained gel was worn out 12-16 days under 22-28 ℃ of temperature,, obtain wet gel with the ethanol washing;
(4) wet gel that step (3) is obtained adopts Co 2 supercritical fluid drying or constant pressure and dry;
(5) the transition metal base aeroge that step (4) is obtained is under 450-550 ℃ temperature heat treatment 5-8 hour, promptly obtains required composite transition metal oxide silica aerogel;
Wherein, described transition metal is the element of group vib, VIII family and I B family.
3. preparation method according to claim 1 and 2 is characterized in that constant pressure and dry described in the step (4) is that acetone is replaced atmosphere pressure desiccation or adopted organic molecule that gel is carried out atmosphere pressure desiccation behind the modification.
4. preparation method according to claim 3 is characterized in that described organic molecule is trim,ethylchlorosilane or dimethyldiethoxysilane.
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