CN106006717B - A kind of preparation method of zinc sulfide nano aeroge - Google Patents

A kind of preparation method of zinc sulfide nano aeroge Download PDF

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CN106006717B
CN106006717B CN201610309570.8A CN201610309570A CN106006717B CN 106006717 B CN106006717 B CN 106006717B CN 201610309570 A CN201610309570 A CN 201610309570A CN 106006717 B CN106006717 B CN 106006717B
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aeroge
normal heptane
reverse micelle
heptane
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CN106006717A (en
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王生钊
南春娟
杜瑞娟
王璐子
李艳艳
杜艾
沈军
周斌
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Nanyang Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/08—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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Abstract

The present invention relates to a kind of preparation method of zinc sulfide nano aeroge, the aeroge is mainly used in the fields such as conductor photocatalysis, it is characterized in that using nano particle group technology, nano particle (NP) is prepared using reverse micelle system, nano particle is dissolved in polar solvent after centrifuge is handled and forms colloidal sol, recycles oxidant to make zinc sulphide collosol and gel.After its gel aging, pass through CO2The method of supercritical drying prepares ZnS nanoporous aerogels, and the aeroge can be applied not only in terms of photocatalysis, catalysis desulfurization of fossil fuel, can also be applied to the numerous areas such as the processing of nuclear waste water.Zinc sulphide aeroge has the distinctive high-specific surface area of aerogel material and high porosity, it also has the characteristic of metal sulfide semiconductor simultaneously so that ZnS aeroges excite the field all many-sides of such as solar cell, photocatalysis, luminescence generated by light, light hydrogen manufacturing etc. all to have broad application prospects in light.

Description

A kind of preparation method of zinc sulfide nano aeroge
Technical field
The invention belongs to the gentle field of gel of conductor photocatalysis, and in particular to a kind of zinc sulphide (ZnS) nanoporous aerogel Preparation method, the aeroge can also be applied to the field such as processing, luminescence generated by light and its light hydrogen manufacturing of nuclear waste water.
Background technology
ZnS (zinc sulphide) is to belong to II, one kind of VI race's semi-conducting material, and ZnS energy gap is 3.6~3.8eV, is urged in light Change field has very big advantage.Meanwhile, ZnS nanocrystalline particle also has unique physicochemical properties, and such as quantum size is imitated Should, nonlinear optical property, in terms of light, electricity, magnetic, catalysis have potential application prospect.At present, in order that the material such as ZnS Material is applied in industrial production on a large scale as catalysis material, and people have carried out substantial amounts of work.For example：Preparing Other ion is introduced into ZnS systems to be doped, or surface modification is carried out to ZnS particulates in journey, and to ZnS nanometers of materials Material includes the patterns such as nano-powder, micelle, nanometer rods, nano wire and film and synthesized with the control of particle diameter.Substantial amounts of experiment table Bright, ZnS photocatalysis efficiency and its specific surface area and particle size have direct contact, and in general specific surface area is got over Greatly, it with it is bigger by the contact area of catalytic media, then its photocatalysis efficiency will be higher.Therefore, zinc sulfide nano The preparation of aeroge has gradually entered into the sight of people, and causes everybody great attention.
Aeroge is a kind of new light nanoporous amorphous solid-state material, with high porosity, high-specific surface area, low The features such as density, low-refraction, low elastic modulus, low acoustic impedance, lower thermal conductivity, strong absorption property, typical fractal structure.
The content of the invention
Continue to study for the deficiencies in the prior art, the zinc sulfide nano-crystalline aeroge prepared by the present invention has ZnS half concurrently Nanocrystalline and aeroge the characteristic of conductor is in one, so that semiconductor nano aeroge not only has the property of semiconductor, Also there is the unique structural behaviour for possessing aeroge simultaneously, such as big specific surface area and high hole ratio and extremely low close The properties such as degree, this causes zinc sulfide nano-crystalline aeroge in technologies such as conductor photocatalysis in processing organic pollution, catalysisization All many-sides such as stone Desulphurization of fuels, nuclear waste water, solar cell, photocatalysis, luminescence generated by light, the processing of light hydrogen manufacturing have wide Application prospect.
Secondly the present invention is controlled with nano particle combined method and reverse micelle system to the size of ZnS particles, is prepared Zinc sulfide nano aeroge.The ZnS aeroges for containing heavy metal containing sewage (for example, Hg2+、Cd2+、Pb2+) improvement it is highly effective And secondary pollution is not resulted in substantially.Meanwhile, the nano-porous structure of ZnS aeroges makes it in calorifics, absorption, catalysis and electronics Deng field, it is also possible to make insulating barrier, acoustic impedance coupling material, catalyst and catalyst carrier, the gas mistake of ultralow electrical conductivity All many-sides such as filter material material, with very wide application prospect.
To achieve these goals, the technical solution adopted in the present invention is as follows：
A kind of preparation method of zinc sulfide nano aeroge, the preparation method comprises the following steps：
S1 is by 0.1~0.2mol Zn (NO3)2It is added in the beaker for filling 50mL deionized waters, by 0.1~0.2mol Na2S is added in the beaker for the deionized water for filling 50mL, and 30~60min is stirred continuously respectively；
S2 takes the Zn (NO of 20~40ml in S13)2With 20~40ml Na2S solution, instills 50~100 milliliters dropwise respectively In 0.5~1.2mol/L diisooctyl succinate sodium sulfonate (AOT)/n-heptane solution, 30~60min is stirred continuously, is formed Zn(NO3)2/ AOT/ normal heptanes and Na2S/AOT/ normal heptane reverse micelle systems；
S3 is by the Zn (NO of the medium volumes of S23)2/ AOT/ normal heptanes and Na2The inverse micellar solution of S/AOT/ normal heptanes is slowly mixed Close, form ZnS/AOT/ normal heptane reverse micelle systems, 30~90min of stirring is stable to reverse micelle system is arrived；
S4 is by 10~25 milliliters of 0.5~0.8mol/L to fluoro thiophenol (FPhSH)/n-heptane solution and 10~25 milliliters 0.5~0.9mol/L triethylamine (TEA)/n-heptane solution is added dropwise to S3 ZnS/AOT/ normal heptane reverse micelle systems simultaneously In, 60~120min is persistently stirred, the suspension stablized carries out centrifugal treating to suspension, and centrifugation product is used into positive heptan Alkane is cleaned 3~5 times, obtains ZnS nano particles；
ZnS nano particles in S4 are dissolved in 50~100mL acetone by S5 obtains ZnS colloidal sols, is added dropwise into the ZnS colloidal sols 3~20mL weight/mass percentage compositions for 1~4% the solution such as oxidant tetranitromethane (TNM)/acetone, persistently stir 30~ Stood after 90min, ZnS wet gels are obtained after the aging of 2~4 weeks；
ZnS wet gels in S5 are put into critical point drying instrument by S6, coordinate constant temperature circulating water dispenser to carry out conventional titanium dioxide Carbon supercritical drying, with CO2For dried medium, a few hours are replaced in 6~15MPa pressure limit, to ZnS wet gel samples 2~5 supercritical dryings (pressure of slow reduction supercritical drying) are carried out, thus ZnS wet gels are dry by supercritical process It is dry processing and obtain ZnS aeroges.
The present invention prepares ZnS aeroges using double reverse micelle methods, causes that ZnS diameters will not in polar solvent in preparation In more than hundred nanometers, so as to form ZnS colloidal sol of the sol particle size in Nano grade, in the feelings that temperature is 18~28 DEG C Under condition, it is dual or multi S- keys that can prepare intergranular connected mode in stable ZnS gels, ZnS gels prepared by this patent, Therefore cation replacement technology can be combined, it is ensured that gel network structure stability and durability.
Brief description of the drawings
Fig. 1 ZnS aeroge preparation flow schematic diagrames；
ZnS gels after Fig. 2 agings；
Raman spectrogram of Fig. 3 ZnS gels under the differential responses time；
The SEM image of Fig. 4 ZnS aeroge samples.
Embodiment
Below with reference to accompanying drawing, the invention will be further described, it is necessary to which explanation, the present embodiment is with this technology side Premised on case, detailed embodiment and operating process are provided, but protection scope of the present invention is not limited to the present embodiment (each original Material is marketable material, and no special instruction purity is chemical pure or the pure grade of analysis).
The present invention is a kind of preparation method of zinc sulfide nano aeroge, and it comprises the following steps：
S1 is by 0.1~0.2mol Zn (NO3)2It is added in the beaker for filling 50mL deionized waters, by 0.1~0.2mol Na2S is added in the beaker for the deionized water for filling 50mL, and 30~60min, such as Fig. 1 schematic flow sheets are stirred continuously respectively Shown in frame (1), (2).
S2 takes the Zn (NO of 20~40ml in S13)2With 20~40ml Na2S solution, instills 50~100 milliliters dropwise respectively In 0.5~1.2mol/L diisooctyl succinate sodium sulfonate (AOT)/n-heptane solution, 30~60min is stirred continuously, is formed Zn(NO3)2/ AOT/ normal heptanes and Na2Shown in S/AOT/ normal heptane reverse micelle systems, such as Fig. 1 schematic flow sheets frame (3), (4).
S3 is by the Zn (NO of the medium volumes of S23)2/ AOT/ normal heptanes and Na2The inverse micellar solution of S/AOT/ normal heptanes is slowly mixed Close, form ZnS/AOT/ normal heptane reverse micelle systems, 30~90min of stirring is stable to reverse micelle system is arrived, and such as Fig. 1 flows are illustrated Shown in picture frame (5).
S4 is by 10~25 milliliters of 0.5~0.8mol/L to fluoro thiophenol (FPhSH)/n-heptane solution and 10~25 milliliters 0.5~0.9mol/L triethylamine (TEA)/n-heptane solution is added dropwise to S3 ZnS/AOT/ normal heptane reverse micelle systems simultaneously In, 60~120min is persistently stirred, the suspension stablized carries out centrifugal treating to suspension, and centrifugation product is used into positive heptan Alkane is cleaned 3~5 times, obtains ZnS nano particles, and such as Fig. 1 schematic flow sheets frame (6), (7), (8) are shown.
ZnS nano particles in S4 are dissolved in 50~100mL acetone by S5 obtains ZnS colloidal sols, is added dropwise into the ZnS colloidal sols 3~20mL weight/mass percentage compositions for 1~4% the solution such as oxidant tetranitromethane (TNM)/acetone, persistently stir 30~ Stood after 90min, obtain ZnS wet gels after the aging of 2~4 weeks, step for example Fig. 1 schematic flow sheets frame (9), (10), (11), shown in (12), the ZnS gels material object after obtained aging is as shown in Fig. 2 loudspeaker of the ZnS gels under the differential responses time Graceful spectrogram is as shown in figure 3, wherein B is just to be dripped into colloidal sol after oxidant tetranitromethane (TNM)/acetone soln Test result, curve C is the result after being added dropwise 3, and curve D is the result after being added dropwise 7, and curve E is the knot after being added dropwise 15 Really.
ZnS wet gels in S5 are put into critical point drying instrument by S6, coordinate constant temperature circulating water dispenser to carry out conventional titanium dioxide Carbon supercritical drying, with CO2For dried medium, a few hours are replaced in 6~15MPa pressure limit, to ZnS wet gel samples 2~5 supercritical dryings (pressure of slow reduction supercritical drying) are carried out, thus ZnS wet gels are dry by supercritical process Dry processing and obtain ZnS aeroges, shown in such as Fig. 1 schematic flow sheets frame (13), (14), the microstructure of ZnS aeroge samples As shown in SEM image in Fig. 4.
For those skilled in the art, technical scheme that can be as described above and design, make other each It is kind corresponding to change and deform, and all these change and deformation should all belong to the protection model of the claims in the present invention Within enclosing.

Claims (1)

1. a kind of preparation method of zinc sulfide nano aeroge, it is characterised in that the preparation method comprises the following steps：
S1：By 0.1~0.2mol Zn (NO3)2It is added in the beaker for filling 50mL deionized waters, by 0.1~0.2mol's Na2S is added in the beaker for the deionized water for filling 50mL, and 30~60min is stirred continuously respectively；
S2：Take the Zn (NO of 20~40ml in S13)2With 20~40ml Na2S solution, instills 50~100 milliliter 0.5 dropwise respectively In~1.2mol/L diisooctyl succinate sodium sulfonate/n-heptane solution, 30~60min is stirred continuously, Zn (NO are formed3)2/ Diisooctyl succinate sodium sulfonate/normal heptane and Na2S/ diisooctyl succinate sodium sulfonates/normal heptane reverse micelle system；
S3：By the Zn (NO of the medium volumes of S23)2/ diisooctyl succinate sodium sulfonate/normal heptane and Na2S/ succinic acid di-isooctyls The inverse micellar solution of sodium sulfonate/normal heptane is slowly mixed together, and forms ZnS/AOT/ normal heptane reverse micelle systems, stirs 30~90min It is stable to reverse micelle system is arrived；
S4：By 10~25 milliliters of 0.5~0.8mol/L to fluoro thiophenol/n-heptane solution and 10~25 milliliter 0.5~ 0.9mol/L triethylamine/n-heptane solution is added dropwise in S3 ZnS/AOT/ normal heptane reverse micelle systems simultaneously, lasting stirring 60~120min, the suspension stablized carries out centrifugal treating to suspension, and centrifugation product is cleaned into 3~5 with normal heptane Time, obtain ZnS nano particles；
S5：ZnS nano particles in S4 are dissolved in 50~100mL acetone and obtain ZnS colloidal sols, into the ZnS colloidal sols be added dropwise 3~ 20mL weight/mass percentage compositions are 1~4% oxidant tetranitromethane/acetone soln, persistently stir and are stood after 30~90min, ZnS wet gels are obtained after the aging of 2~4 weeks；
S6：ZnS wet gels in S5 are put into critical point drying instrument, coordinates constant temperature circulating water dispenser to carry out conventional carbon dioxide and surpasses Critical drying, with CO2For dried medium, a few hours are replaced in 6~15MPa pressure limit, ZnS wet gels sample is carried out 2~5 supercritical dryings, slow to reduce the pressure of supercritical drying, thus ZnS wet gels pass through supercritical process drying process And obtain ZnS aeroges.
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