CN107790105A - A kind of preparation method of ammonification elasticity silicon substrate composite aerogel - Google Patents

A kind of preparation method of ammonification elasticity silicon substrate composite aerogel Download PDF

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CN107790105A
CN107790105A CN201711056503.0A CN201711056503A CN107790105A CN 107790105 A CN107790105 A CN 107790105A CN 201711056503 A CN201711056503 A CN 201711056503A CN 107790105 A CN107790105 A CN 107790105A
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ammonification
silicon substrate
wet gel
elasticity
preparation
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陈晓勇
李红朝
熊继军
杜栓丽
杨海艳
王新新
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North University of China
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention discloses a kind of preparation method of ammonification elasticity silicon substrate composite aerogel, first using amino silicone, alkylsiloxane or graphene oxide as raw material, intrinsic ammonification elasticity silicon substrate composite aerogel is made through sol-gal process One-step Synthesis ammonification silicon substrate/graphene oxide wet gel, then through aging, freeze-drying.In one pot process of the present invention, monomer is catalyzed without acidic catalyst, but is hydrolyzed at a slow speed in neutral conditions, then is become alkalescence by urea pyrohydrolysis, solution and constantly carried out polycondensation reaction.Ammonification aeroge has strong metal ion chelating capacity, CO2Adsorption capacity, it is significant to reduction greenhouse gas emission, metal ion pollution.

Description

A kind of preparation method of ammonification elasticity silicon substrate composite aerogel
Technical field
The present invention relates to a kind of preparation method of ammonification elasticity silicon substrate composite aerogel, belong to ammonification silicon substrate composite aerogel Technical field.
Background technology
Silica-based aerogel material is a kind of solid matter with porous network structure, and it has bigger serface, low close The characteristics such as degree, lower thermal conductivity, such as heat-insulation and heat-preservation, catalytic carrier, decontamination material can be enriched with various fields application, wherein Application particularly metal ion removing and CO in terms of environmental-protection adsorption2The application of enrichment turns into one of study hotspot.
Non-aminated silica-based aerogel is to metal ion and CO2Absorption be mostly physical absorption, absorption stability and temperature tolerance Difference, therefore there is researcher to start to carry out it ammonification, Jiangsu University's ding-dong benevolence etc. to have delivered paper " the compound dioxy of aminated chitosan The preparation of SiClx aeroge and its to Cu (II), Cd (II), Pb (II) ion Study on adsorption properties "（Silicate is circulated a notice of, 2015,34(7):1953-1958.）, using polysaccharide polymer material chitosan as organic phase, by Co-sol-gel with it is inorganic The silicon dioxide granule progress grafted amino group of phase is compound, obtains a kind of organo-mineral complexing aerogel material, gathers yet with shell Contained amino amount is not abundant enough in sugar subchain while hydrogen bond between contained amino and silicon dioxide gel matrix is weaker, these Factor has a negative impact to adsorption effect.Nanjing University of Technology hole is brave et al.（Amino functional SiC aeroges：It is a kind of new Type CO2Adsorbent；18th national composite academic meeting paper collection .2014:313-317.）, with block SiC aeroges For carrier, a kind of aeroge of new amino functional is prepared by infusion process and constant pressure and dry technique, it has preferable Low concentration CO2Absorption property, but infusion process causes the pore volume for preparing aeroge to be greatly reduced.Existing method mostly first synthesizes Aeroge ammonification again, but the problems such as aeroge internal amino is few, amino easily comes off be present in such method.
The content of the invention
The present invention is intended to provide a kind of preparation method of ammonification elasticity silicon substrate composite aerogel, using one synthesis side in situ Method realizes the preparation of the intrinsic compound wet gel of ammonification elasticity silicon substrate, overcomes aeroge polarity（Amino）Micropore caused by surface Structure water suction avalanche problem, obtains high specific surface area, the intrinsic ammonification elasticity silicon substrate composite aerogel without hydrophobically modified. Present invention also offers the application of above-mentioned ammonification elasticity silicon substrate composite aerogel.
The invention provides a kind of preparation method of ammonification elasticity silicon substrate composite aerogel, first with amino silicone, alkane Radical siloxane or graphene oxide（GO）It is wet through sol-gel process One-step Synthesis ammonification silicon substrate/graphene oxide for raw material Gel, then intrinsic ammonification elasticity silicon substrate composite aerogel is made through aging, freeze-drying.
It is double that the amino silicone includes 3- aminopropyl triethoxysilanes, 3- aminopropyl trimethoxysilanes, 1,2-（Two Ethylamino-）- 1,1,2,2- tetramethyls disilane or 1,2- are double（Diethylin）One kind in -1,2- dimethyldisilanes.
The alkylsiloxane includes dimethyldiethoxysilane or diethyldiethoxysilane.
Above-mentioned preparation method, comprises the following steps：
1）The preparation of wet gel
By alkylsiloxane, amino silicone, C12H25SO3Na, urea, deionized water are 1.5~3.2 in mass ratio：1.5~ 3.2：0.4~1.2：1.6~3.2：8 ~ 25 mixing, 3 ~ 8h is reacted in 35~55 DEG C, be then transferred into gel in closed container and be aged 6 ~ 72h, it is made without GO ammonification elasticity silicon substrate wet gels；
（2）Wet gel solvent is replaced and dried
Obtained wet gel is immersed in 18 ~ 48h in t-butanol solution successively at room temperature；The polarity wet gel replaced is used Vacuum freeze-drying method is in -60 DEG C ~ -10 DEG C 24 ~ 48h of drying, obtained elastic silica-based aerogel；It is designated as SA aeroges.
As another preferable technical scheme, above-mentioned preparation method, comprise the following steps：
（1）The preparation of wet gel
1 ~ 5mg/ml graphene oxide dispersion liquid is produced by ultrasonic dispersion, by itself and alkylsiloxane, amino silica Alkane, C12H25SO3Na, urea, deionized water mixing, react 3 ~ 8h in 35 ~ 55 DEG C, wherein, graphene oxide（GO）, alkyl silicon Oxygen alkane, amino silicone, C12H25SO3Na, urea, the mass ratio of deionized water are 0.005 ~ 0.08:1.5~3.2：1.5~ 3.2：0.4~1.2：1.6~3.2：8~25；Above-mentioned mixed liquor is transferred to gel in closed container and is aged 6-72 h, is made and contains The compound wet gel of GO ammonification elasticity silicon substrates；
（2）Wet gel solvent is replaced and dried
Obtained wet gel is immersed in 18 ~ 48h in t-butanol solution successively at room temperature；The polarity wet gel replaced is used Vacuum freeze-drying method is in -60 DEG C ~ -10 DEG C 24 ~ 48h of drying, obtained elastic silica-based aerogel；It is designated as SGA aeroge samples.
The mass fraction of the t-butanol solution is 30% ~ 100%.
By wet gel carry out vacuum freeze drying parameter be：Drying temperature be -60 DEG C ~ -10 DEG C, drying time be 24 ~ 48h。
The principle of the present invention：In one-pot synthesis, monomer is catalyzed without acidic catalyst, but in neutral conditions at a slow speed Hydrolysis, then become alkalescence by urea pyrohydrolysis, solution and constantly carried out polycondensation reaction.Ammonification aeroge has strong metal ion Sequestering power, CO2Adsorption capacity, it is significant to reduction greenhouse gas emission, metal ion pollution.It is provided by the present invention New ammonification elasticity silicon substrate composite aerogel be intrinsic ammonification（One synthesis in situ）Elastic silicon substrate composite aerogel, is avoided First synthesizing aeroge, ammonification causes aeroge internal amino deficiency, amino easily to come off problem again, more with potential applications.Pass through this The strain value in 50% deformation of SGA aeroges sample made from invention is 0.02Mpa, and 70 second compressions load mechanics strength retention Almost 100%, SGA aeroge samples specific surface area is 46.95m2/ g, heat decomposition temperature is at 470 DEG C；SA aeroges sample ratio Surface area is 60.49m2/ g, heat decomposition temperature are 360 DEG C.Both of which has higher heat endurance.Intrinsic ammonification, which avoids, first closes Ammonification after into aeroge and the amino that triggers is easy to fall off, in material without/few amino problem, therefore recycle in metal ion, CO2The fields such as absorption disposal have more preferable application prospect.
Beneficial effects of the present invention：
（1）Intrinsic ammonification scheme can ensure the uniformity of amino distribution and the reliability that amino is bonded, be advantageous to further carry Chelating ability and CO of the high silica-based aerogel to metal ion2Adsorption capacity.
（2）Because silica-based aerogel fragility is big, low intensity, it is unfavorable for storage and transportation and reuse, the present invention is to it Carry out ammonification simultaneously, the bullet of silica-based aerogel composite is realized using double silicon sources and the step of graphene oxide complex method one Property.
（3）Solves surface polarity（Amino）The microcellular structure water suction avalanche problem of initiation, realizes intrinsic ammonification elasticity Silicon substrate composite aerogel one-step synthesis, it is good and be not required to the aeroge of hydrophobically modified to obtain high specific surface area, pliability；To be new The exploitation of type ammonification elasticity silica-based aerogel provides new approaches and technical support.
Brief description of the drawings
Fig. 1 is SGA aeroge samples in embodiment 1,2（a）With SA aeroge sample silica-based aerogel samples（b）In light Learn microscope partial enlarged drawing；
Fig. 2 is the scanning electron microscopic picture (a) under SA aeroge sample different amplifications, (c) in embodiment 1,2；SGA airsettings Scanning electron microscopic picture (b) under glue sample different amplification, (d)；
Fig. 3 is GO powder, SA aeroges, the FTIR spectrum figure of SGA aeroge samples in embodiment 1,2；
Fig. 4 is the adsorption/desorption curve of SGA aeroges sample and SA aeroge samples in embodiment 1,2；
Fig. 5 is SA aeroges, the thermogravimetric curve figure of SGA aeroge samples in embodiment 1,2；
Fig. 6 is SGA aerogel materials sample 10 times, load-deformation curve of 70 second compressions in 50% deformation in embodiment 2.
Embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Embodiment provided by the invention is first with amino silicone, alkylsiloxane or graphene oxide（GO）For original Material, intrinsic ammonification elasticity silicon substrate composite aerogel is prepared for through sol-gel-freeze drying method；Then infrared spectrum is used （IR）, ESEM（SEM）, specific surface area analysis（BET）, thermogravimetric analysis（TG）Gained aeroge is entered with mechanical property testing Structure and performance characterization are gone.
Experiment raw material include：Multilayer graphene oxide powder（GO contents>90%）：Suzhou Jing Xi electronics scientific technology co；Nothing Water-ethanol（AR）：Tianjin Feng Chuan chemical reagents corporations；The tert-butyl alcohol（AR）：Tianjin recovery fine chemistry industry research institute；Dodecane Base sodium sulfonate C12H25SO3Na (analyzes pure AR）：Tianjin Kai Tong chemical reagents corporations；Dimethyldiethoxysilane DDS (98%):Aladdin reagent；3- aminopropyl triethoxysilanes APTES (98%):Aladdin reagent.
Embodiment 1：Prepare without GO ammonification elasticity silica-based aerogel samples
Comprise the following steps：
（1）Prepared without the compound wet gel of GO ammonification elasticity silicon substrates：
By dimethyldiethoxysilane（DDS）, 3- aminopropyl triethoxysilanes（APTES）, C12H25SO3Na, urea, go Ionized water in mass ratio 3:3:1:4:20 mixing, 5h is reacted in 40 DEG C, be then transferred into gel in closed container and be aged 48h, system Obtain without GO ammonification elasticity silicon substrate wet gels.
（2）Wet gel solvent is replaced and dried
Obtained wet gel is immersed in successively at room temperature each in the t-butanol solution that mass fraction is 30%, 60% and 100% 24h.48h is dried in -15 DEG C in the polarity wet gel vacuum freeze-drying method replaced, elastic silicon substrate airsetting is made Glue；It is designated as SA aeroge samples.
Embodiment 2：Prepare the elasticity silica-based aerogel sample of ammonification containing GO
Comprise the following steps：
（1）It is prepared by the compound wet gel of the elasticity silicon substrate of ammonification containing GO：
5mg/ml GO dispersion liquids are produced by ultrasonic dispersion, by itself and dimethyldiethoxysilane（DDS）, 3- aminopropyls Triethoxysilane（APTES）, C12H25SO3Na, urea, deionized water are 1 in mass ratio：120：120：40：160：800 is mixed Close, react 5h in 40 DEG C, above-mentioned mixed liquor is transferred into the obtained elasticity silicon substrate of ammonification containing GO of gel ageing in closed container answers Close wet gel.
（2）Wet gel solvent is replaced and dried
Obtained wet gel is immersed in successively at room temperature each in the t-butanol solution that mass fraction is 30%, 60% and 100% 24h.48h is dried in -15 DEG C in the polarity wet gel vacuum freeze-drying method replaced, elastic silicon substrate airsetting is made Glue；It is designated as SGA aeroge samples.
Embodiment 3：Prepare without GO ammonification elasticity silica-based aerogel samples
Comprise the following steps：
（1）Prepared without the compound wet gel of GO ammonification elasticity silicon substrates：
By dimethyldiethoxysilane（DDS）, 3- aminopropyl triethoxysilanes（APTES）, C12H25SO3Na, urea, go Ionized water is by a certain percentage（3:3:1:4:20）Mixing, 5h is reacted in 45 DEG C or so, it is old to be then transferred into gel in closed container Change 36h, be made without GO ammonification elasticity silicon substrate wet gels；
（2）Wet gel solvent is replaced and dried
Obtained wet gel is immersed in successively at room temperature each in the t-butanol solution that mass fraction is 30%, 60% and 100% 24h.24h is dried in -25 DEG C in the polarity wet gel vacuum freeze-drying method replaced, obtained flexible silicon is dried Base aeroge；It is designated as SA aeroge samples.
Embodiment 4：Prepare the elasticity silica-based aerogel sample of ammonification containing GO
Comprise the following steps：
（1）It is prepared by the compound wet gel of the elasticity silicon substrate of ammonification containing GO：
5mg/ml GO dispersion liquids are produced by ultrasonic dispersion, by itself and dimethyldiethoxysilane（DDS）, 3- aminopropyls Triethoxysilane（APTES）, C12H25SO3Na, urea, deionized water press 1：120：120：40：160：800 ratios are mixed Close, react 5h in 50 DEG C, above-mentioned mixed liquor is transferred into the obtained elasticity silicon substrate of ammonification containing GO of gel ageing in closed container answers Close wet gel.
（2）Wet gel solvent is replaced and dried
Obtained wet gel is immersed in successively at room temperature each in the t-butanol solution that mass fraction is 30%, 60% and 100% 24h.24h is dried in -20 DEG C in the polarity wet gel vacuum freeze-drying method replaced obtained flexible silicon is dried Base aeroge；It is designated as SGA aeroge samples.
Embodiment 5：Prepare without GO ammonification elasticity silica-based aerogel samples
Comprise the following steps：
（1）Prepared without the compound wet gel of GO ammonification elasticity silicon substrates：
By dimethyldiethoxysilane（DDS）, 3- aminopropyl triethoxysilanes（APTES）, C12H25SO3Na, urea, go Ionized water is by a certain percentage（3:3:1:4:20）Mixing, about 6h is reacted in 45 DEG C or so, is then transferred into gel in closed container 40h is aged, is made without GO ammonification elasticity silicon substrate wet gels；
（2）Wet gel solvent is replaced and dried
Obtained wet gel is immersed in successively at room temperature each in the t-butanol solution that mass fraction is 30%, 60% and 100% 24h.24h is dried in -20 DEG C in the polarity wet gel vacuum freeze-drying method replaced obtained flexible silicon is dried Base aeroge；It is designated as SA aeroge samples.
Embodiment 6：Prepare the elasticity silica-based aerogel sample of ammonification containing GO
Comprise the following steps：
（1）It is prepared by the compound wet gel of the elasticity silicon substrate of ammonification containing GO：
3mg/ml GO dispersion liquids are produced by ultrasonic dispersion, by itself and dimethyldiethoxysilane（DDS）, 3- aminopropyls Triethoxysilane（APTES）, C12H25SO3Na, urea, deionized water press 1：120：120：40：160：800 ratios are mixed Close, react 5h in 55 DEG C, above-mentioned mixed liquor is transferred into the obtained elasticity silicon substrate of ammonification containing GO of gel ageing in closed container answers Close wet gel.
（2）Wet gel solvent is replaced and dried
Obtained wet gel is immersed in successively at room temperature each in the t-butanol solution that mass fraction is 30%, 60% and 100% 24h.24h is dried in -20 DEG C in the polarity wet gel vacuum freeze-drying method replaced obtained flexible silicon is dried Base aeroge；It is designated as SGA aeroge samples.
Sample test
1st, sample is apparent analyzes with internal morphology
With the apparent density of weight method test sample product；With XPL-3230 types light microscope aeroge sample surfaces are carried out with local put Big surface topography observation；With Quantachrome TouchWin specific surface area analysis instrument test sample product specific surface areas；With HITACHI S4700 scanning electronic microscope observation sample surfaces microscopic appearances structure, FT-IR-4800S FTIR spectrums The characteristic group of instrument analysis sample, METTLER TOLEDO thermogravimetric analyzer test sample thermal weight loss situations；Use The mechanical property of Instron2345 universal testing machine test samples, to the pressure of intrinsic ammonification elasticity silicon substrate composite aerogel Contracting rebound performance is characterized.
Two kinds of ammonification flexible silicon based specimens of gained, are fluffy, soft solids, and there is the inhomogenous pit of size on surface (shown in Fig. 1).Wherein SA aeroges sample is the lightweight flexible solid of White-opalescent, and its apparent density, which is calculated, is 151mg/cm3；SGA aeroges sample is black lightweight flexible solid, and its density is 170mg/cm3。
Fig. 2 is gained aeroge sample section scanning electron microscope (SEM) photograph, it can be seen that：SA aeroge samples（Fig. 2 (a), (c)）For The three-dimensional netted loose structure that more uniform spherical little particle accumulation intertexture is got up, aperture is mostly below 5 μm；SGA aeroges Sample（Fig. 2 (b), (d)）In spherical little particle disappear, the three-dimensional netted porous knot that mostly curling of graphene oxide sheet thing stacks Structure.Spherical particle in aeroge is the aggregation of micella, connected between particle it is less, so as to cause storeroom network structure endless It is kind, therefore its macromechanics intensity difference, fragility are larger；After adding graphene oxide, these particles are disappeared, and cotton-shaped connection is obvious to be increased Adding, it means that aeroge internal micellar, which is reunited, to be reduced, and the increase of internal network Connection Density, network structure are more perfect, thus Its network strength, the increase of macromechanics intensity, and then system pliability, elasticity increase.
2nd, constituent analysis
Infrared spectrum is that the powerful measure of material composition occurs and characterized for confirmation chemical reaction.Fig. 3 is GO, SA aeroges sample, The fourier infrared of SGA aeroge samples（FTIR）Spectrogram.3450cm on GO curves-1For OH stretching vibration characteristic peaks, 1730 cm-1For C=O and COOH stretching vibration characteristic peak, 1620cm-1For C in GO=C framework vibration performance peak.With GO FTIR light Spectrum is compared, and the infrared spectrogram of SA, SGA aeroge sample is in 3400cm-1There is the stretching vibration characteristic peak of corresponding amino, table in place Bright amino has been grafted in gained aeroge sample, and intrinsic ammonification in situ has been carried out to sample.SA and SGA aeroge samples FTIR spectrum curve is in 1096 cm-1With 1022 cm-1Place shows Si-O-C/Si-O-Si group characteristic peaks accordingly, Show to form Si-O-Si network structures there occurs condensation reaction between alkoxy grp.Compared to SA aeroges, SGA aeroge samples FTIR spectrum in had more corresponding GO characteristic peak, such as there is C=C framework vibration performance peak, show SGA aeroge samples Siloxanes and GO constitute silicon substrate composite aerogel there occurs chemically composited in product.
3rd, specific surface area analysis
Specific surface area is the important indicator of material absorption property.Without GO ammonifications elasticity silica-based aerogel sample and the elasticity of ammonification containing GO The adsorption/desorption curve of silica-based aerogel sample is shown in Fig. 4.As seen from Figure 4, the adsorption/desorption curve of two class samples and D classes Loop line is similar, thus can determine whether two class ammonification elasticity silica-based aerogel samples be the slit capillary structure of taper and it is compound after Sample and compound preceding sample difference it is little.The reason for producing this needle-like pyramidal structure is that aeroge sample was freezing The tert-butyl alcohol can produce acicular crystal in journey, after the distillation of needle-like ice crystal, will be left behind substantial amounts of needle-like duct.By Quantachrome TouchWin specific surface area analysis instrument test sample product specific surface areas, wherein being compounded with the airsetting of graphene oxide Glue sample specific surface area is 46.95m2/ g, not compound sample specific surface area are 60.49m2/g.Gas after combined oxidation graphene Gel sample specific surface area is reduced, it may be possible to which, due to GO doping, part GO piece interlayer spacing is smaller, so as to occur to a certain degree Adhesion cause part pore structure to be blocked.
4th, thermogravimetric analysis
SA aeroges sample, SGA aeroge samples are individually positioned in detecting instrument, under a nitrogen atmosphere, are raised to from room temperature 800 DEG C, programming rate is 10 DEG C/min, and it is as shown in Figure 5 to obtain thermogravimetric curve.It is equal that two aerogel-like samples are clearly seen in Fig. 5 Only one big thermal weight loss step；Compared to SGA aeroge samples, SA aeroge sample heat loss initial temperatures are low, Low Temperature Thermal Loss is big, but>Heat loss is slower than SGA aeroge samples at 500 DEG C.SA aeroges sample about has about 3% matter at 250 DEG C Amount loss, and SGA aeroges sample has 5% mass loss at about 380 DEG C, this is the solvent of residual, hydrone evaporation desorption And caused by the decomposition of presoma.Mass loss at about 300 DEG C is surface silanol group than caused by more thoroughly dehydrating condensation, Have the thermal decomposition that obvious mass loss is due to sample between 400 DEG C to 600 DEG C, Si-O-C/Si-O-Si groups and Si-CH3、Si-CH2Caused by radical decomposition.Wherein the most fast temperature spot of SGA aeroges sample decomposition rate is 470 DEG C, SA airsettings Glue sample is then 360 DEG C or so, and this shows that the addition of graphene oxide largely improves the heat of silica-based aerogel material Stability.
5th, the elasticity of ammonification containing GO silicon substrate composite aerogel sample mechanics property analysis
Aeroge sample is carried out using universal testing machine loading compression stress test is repeated several times（50% deformation）, knot Fruit is shown in Fig. 6.As seen from the figure, it is linear elastic region when deformation quantity is less than 35%, i.e., as the growth of stress, strain are presented Cutting edge aligned growth, and the region between 35% to 50% is nonlinear area, non-linear relation is presented in stress and strain.It is obtained The elasticity silicon substrate composite aerogel of ammonification containing GO there is excellent elasticity, even if repeated compression load 70 times（50% deformation）, its power Characteristic is kept approximately constant and sample still can recover to load preceding DEFORMATION POINTS, and aeroge does not have in itself after reply Occur any caving in and rupturing.The excellent possible cause of the aerogel material elastic performance is：（1）Each silicon after formation gel At most only three silicon oxygen bonds, degree of cross linking density are low with respect to tetrasiloxane base aeroge for atom so that the aerogel material Network rigidity declines, and resulting materials macroscopic view fragility weakens；（2）Graphene oxide is compounded with material, on graphene oxide The hydrolysis of-OH groups and siloxanes after Si-OH there occurs condensation cross-linking, so as to Strengthens network intensity.When there is external force effect, Graphene oxide serves the effect of reinforcer, transmits, has disperseed external load so that resulting materials possess it is excellent Elasticity；（3）Gained aeroge network structure is distributed a large amount of methyl groups, and when compression is shunk, methyl can be mutually exclusive, because Gel can finally rebound after the release of this pressure.
Test result confirms that required composite aerogel has generated；Gained composite aerogel has double inierpeneirating network structures, contains GO ammonification elasticity silica-based aerogel sample heat decomposition temperatures are at 470 DEG C, no GO ammonifications elasticity silica-based aerogel sample thermal decomposition temperature Spend for 360 DEG C.Both of which has higher heat endurance.The silica-based aerogel sample of ammonification containing GO has excellent elasticity, 70 pressures Remain to keep 100% resilience after contracting.

Claims (7)

  1. A kind of 1. preparation method of ammonification elasticity silicon substrate composite aerogel, it is characterised in that：First with amino silicone, alkyl silicon Oxygen alkane or graphene oxide are raw material, through sol-gel process One-step Synthesis ammonification silicon substrate/graphene oxide wet gel, then Intrinsic ammonification elasticity silicon substrate composite aerogel is made through aging, freeze-drying.
  2. 2. the preparation method of ammonification elasticity silicon substrate composite aerogel according to claim 1, it is characterised in that：The amino It is double that siloxanes includes 3- aminopropyl triethoxysilanes, 3- aminopropyl trimethoxysilanes, 1,2-（Diethylin）-1,1,2,2- Tetramethyl disilane or 1,2- are double（Diethylin）One kind in -1,2- dimethyldisilanes.
  3. 3. the preparation method of ammonification elasticity silicon substrate composite aerogel according to claim 1, it is characterised in that：The alkyl Siloxanes includes dimethyldiethoxysilane or diethyldiethoxysilane.
  4. 4. the preparation method of ammonification elasticity silicon substrate composite aerogel according to claim 1, it is characterised in that：Including following Step：
    （1）The preparation of wet gel
    By alkylsiloxane, amino silicone, C12H25SO3Na, urea, deionized water are 1.5~3.2 in mass ratio：1.5~ 3.2：0.4~1.2：1.6~3.2：8 ~ 25 mixing, 3 ~ 8h is reacted in 35~55 DEG C, be then transferred into gel in closed container and be aged Ammonification elasticity silicon substrate wet gel is made in 24 ~ 72h；
    （2）Wet gel solvent is replaced and dried
    Obtained wet gel is immersed in 18 ~ 48h in t-butanol solution successively at room temperature；The polarity wet gel replaced is used Vacuum freeze-drying method is dried, and elastic silica-based aerogel is made.
  5. 5. the preparation method of ammonification elasticity silicon substrate composite aerogel according to claim 1, it is characterised in that：Including following Step：
    （1）The preparation of wet gel
    1 ~ 5mg/ml graphene oxide dispersion liquid is produced by ultrasonic dispersion, by itself and alkylsiloxane, amino silica Alkane, C12H25SO3Na, urea, deionized water mixing, react 3 ~ 8h in 35 ~ 55 DEG C, wherein, graphene oxide（GO）, alkyl silicon Oxygen alkane, amino silicone, C12H25SO3Na, urea, the mass ratio of deionized water are 0.005 ~ 0.08:1.5~3.2：1.5~ 3.2：0.4~1.2：1.6~3.2：8~25；Above-mentioned mixed liquor is transferred to gel ageing 6-72h in closed container and is made and contains stone The compound wet gel of ammonification elasticity silicon substrate of black olefinic oxide；
    （2）Wet gel solvent is replaced and dried
    Obtained wet gel is immersed in 18 ~ 48h in t-butanol solution successively at room temperature；The polarity wet gel replaced is used Vacuum freeze-drying method is dried, and the elastic silica-based aerogel of graphene-containing oxide is made.
  6. 6. the preparation method of the ammonification elasticity silicon substrate composite aerogel according to claim 4 or 5, it is characterised in that：It is described The mass fraction of t-butanol solution is 30% ~ 100%.
  7. 7. the preparation method of the ammonification elasticity silicon substrate composite aerogel according to claim 4 or 5, it is characterised in that：Will be wet Gel carry out vacuum freeze drying parameter be：Temperature is -60 DEG C ~ -10 DEG C, and drying time is 24 ~ 48h.
CN201711056503.0A 2017-11-01 2017-11-01 A kind of preparation method of ammonification elasticity silicon substrate composite aerogel Pending CN107790105A (en)

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