CN1740096A - Reverse microemulsion process of preparing nanometer monodisperse germanium oxide square - Google Patents

Abstract

The reverse microemulsion process of preparing nanometer monodisperse germanium oxide square adopts germanium chloride as germanium source, heptane as oil phase, water solution in different pH value as water phase, and cetyl trimethyl ammonium bromide and oleyl amine as surfactant to prepare nanometer germanium oxide squares with alpha-quartz structure, regular surface, and edge size of 250-270 nm. The effect of different water solution pH values on the germanium oxide particle size and form are compared, and optimized preparation process is found. The present invention has low cost, simple process and high controllability, is significant in researching the performance and size dependence of nanometer material, and may find its practical application in optical device design and manufacture.

Description

The reverse microemulsion legal system is equipped with single method of disperseing germanium oxide nanometer square

Technical field

The present invention relates to technical field of material, particularly relate to a kind of reverse microemulsion legal system and be equipped with single method of disperseing germanium oxide nanometer square.

Background technology

Nano science and nanotechnology are current one of the most great-hearted research fields, recently the nanometer oxide material that has a special appearance for controlledly synthesis is direction in forward position very in the nano materials research, because the performance of nano material and potential are used the dependency for size and pattern, have reported the nano-oxide that has synthesized such as nanotube, nano wire, nanometer rod, nanometer plate, nanometer square or the like various patterns.Germanium oxide (GeO ₂) be a kind of insulation oxide, have photic blue light-emitting effect, peak position is a kind of very promising material aspect optics, such as the application in the photoconduction integration system at 3.1ev and 2.2ev.Now for GeO ₂Research receive more and more widely concern, this is because GeO ₂With the silicon oxide (SiO that in photoconductive fiber, has been widely used ₂) have similar performance, and GeO in some aspects ₂Have and more be better than SiO ₂Performance, as GeO ₂Compare SiO ₂Have higher thermal expansivity, this can be applied to the vacuum technique aspect.At GeO ₂The GeO with Prepared with Laser Ablation has been reported in the preparation aspect of nano material ₂Nanowhisker cooperates high temperature sintering to prepare nanometer GeO with electroplating spining technology then ₂Fiber, physical evaporation method prepares nano wire, and the restriction by carbon nanotube prepares GeO ₂Nanometer rod and thermal oxidation method prepare nano wire or the like.The nano material of different-shape has broad application prospects because of its unique character, physical preparation method is because apparatus expensive, the preparation process complexity, the cost height, shortcomings such as preparation amount is few are difficult for carrying out scale operation, and advantage is considered to the following method for preparing the potentialization of some practicability nano material and chemical method is because the product cost of preparation is low, equipment is simple, controllability is good etc.

Summary of the invention

The purpose of this invention is to provide easy, a kind of reverse microemulsion legal system is equipped with single method of disperseing germanium oxide nanometer square cheaply.

The technical solution used in the present invention is: its concrete step is as follows:

One. material mixture ratio

Concentration is 99.99% anhydrous germanium tetrachloride GeCl ₄,

Analytical pure heptane C ₇H ₁₆,

Analytical pure tetrahydrofuran (THF) (THF) C ₄H ₈O,

Analytical pure Pentyl alcohol C ₅H ₁₂O,

Analytical pure cetyl trimethyl ammonia bromide (CTAB) C ₁₉H ₄₂BrN,

Concentration is 97% oleyl amine C ₁₈H ₃₇N,

Analytical pure dehydrated alcohol C ₂H ₆O,

With concentration is that 36%～38% hydrochloric acid or concentration are that 25% ammoniacal liquor preparation pH is 1.0～13.5 the aqueous solution,

Above reagent does not all pass through purification process;

Two. preparation process

1) anhydrous GeCl ₄Be dissolved in the tetrahydrofuran (THF) that to form concentration be the transparent solution of 0.5mol/l;

2) component one: be the aqueous solution of heptane: pH=1.0～13.5 with volume ratio: Pentyl alcohol=20: 1: 3, mole proportioning are that four kinds of materials of the aqueous solution=1: 12 of cetyl trimethyl ammonia bromide: pH=1.0～13.5 mix in the container of 100ml, stir under 78HW-3 type constant temperature magnetic agitation instrument and form transparent microemulsion;

3) component two: with volume ratio is heptane: GeCl ₄The tetrahydrofuran (THF) clear solution: three kinds of solution of oleyl amine=10: 1: 2 place 50ml beaker uniform mixing under 78HW-3 type constant temperature magnetic agitation instrument, form transparent microemulsion;

4) component two is slowly splashed in the mixing solutions of component one under powerful magnetic agitation, dropwise back 15～20min solution and muddiness, stopped reaction after 3～4 hours occur.Reacted mixing solutions is through 10000r/min SORVALL LEGEND-T whizzer centrifugation 10～15min, obtain solid product and disperse washing once more with dehydrated alcohol, recentrifuge, the solid that repeats to obtain after 2～4 times at room temperature is dried to pressed powder.

The beneficial effect that the present invention has is: adopt germanium chloride (GeCl ₄) as the germanium source, heptane is as oil phase, cetyl trimethyl ammonia bromide (CTAB) and oleyl amine be as tensio-active agent, with the reverse microemulsion method prepared the alpha-quartz structure, had structured surface, marginal dimension is at the GeO of 250-270nm ₂Square.The method cost that this preparation has monodispersity germanium oxide nanometer square is low, method is simple, controllability is good, is significant for the pattern and the size-dependent of research nano ZnO, simultaneously in the design of optics, have very high practical value in making.

Description of drawings

Fig. 1 is the GeO that adopts the preparation of the pH=1.0 aqueous solution according to embodiment 1 ₂The XRD diffractogram of nanometer square;

Fig. 2 is the GeO that adopts the preparation of the pH=1.0 aqueous solution according to example 1 ₂The TEM of nanometer square, FESEM and SAED photo;

Fig. 3 prepares different-shape GeO when adopting different pH to adopt the different pH value aqueous solution ₂The TEM photo of nano material.

Embodiment

Embodiment 1:

Carry out according to preparation process, with the pH value 1.0 aqueous solution 3ml, heptane 60ml, Pentyl alcohol 9ml, CTAB5g mixes in the 100ml there-necked flask, forms the clear solution of component one under the magnetic agitation, with the 20ml heptane, 0.5MGeCl4 THF solution 2ml, oleyl amine 4ml mixes in the 50ml beaker, forms the clear solution of component two under the magnetic agitation.Component two under stirring, brute force is slowly splashed in the solution of component one.Reaction 4h, centrifugation 15min under the solution 10000r/min centrifugation rate of reaction back, solid dispersed is washed in dehydrated alcohol, and recentrifuge repeats the powder Air drying 4 times.The sample of X-ray diffraction analysis (XRD) is the exsiccant powder, and placing does not have on the back of the body monocrystalline silicon piece at the end, the laboratory apparatus of employing be Rigaku D Max-2200, adopt CuK _αScattering, sweep interval are 15-90 °, and step-length is 0.02 °, per sweep time in step 2s.The test that transmission electron microscope observation and selected area electron diffraction are observed (TEM and SAED) is that dried powder supersound process is dispersed in the toluene, then with drips of solution on the copper mesh that is coated with carbon film, drying at room temperature, TEM model are JEOL200CX.The sample of field emission scanning electron microscope (FESEM) is powdered sample to be dispersed in drop in the ethanol on the sample table, treat ethanol volatilization after, scanning electron microscopic observation, the scanning electron microscope model is FEI SIRION.Fig. 2 and Fig. 3 a are the GeO by embodiment 1 preparation ₂The TEM of nanometer square, SAED and FESEM photo.Wherein (a) is the GeO at regular edge among Fig. 2 ₂The TEM photo of square; (b) be the SAED single crystal diffraction figure of single square; (c) be single GeO ₂The TEM photo of square; (d) be large stretch of GeO ₂The FESEM photo of square; (e) be the high GeO of magnification ₂Square FESEM photo.

Embodiment 2:

Carry out according to preparation process, with the pH value 3.5 aqueous solution 3ml, heptane 60ml, Pentyl alcohol 9ml, CTAB5g mixes in the 100ml there-necked flask, forms the clear solution of component one under the magnetic agitation, with the 20ml heptane, 0.5MGeCl4 THF solution 2ml, oleyl amine 4ml mixes in the 50ml beaker, forms the clear solution of component two under the magnetic agitation.Component two under stirring, brute force is slowly splashed in the solution of component one.Reaction 3.5h, centrifugation 15min under the solution 10000r/min centrifugation rate of reaction back, solid dispersed is washed in dehydrated alcohol, and recentrifuge repeats 3 times.Fig. 3 b is the GeO by embodiment 2 preparations ₂The TEM photo of nanometer square.

Embodiment 3:

Carry out according to preparation process, with the pH value 7.0 aqueous solution 3ml, heptane 60ml, Pentyl alcohol 9ml, CTAB5g mixes in the 100ml there-necked flask, forms the clear solution of component one under the magnetic agitation, with the 20ml heptane, 0.5MGeCl4 THF solution 2m//l, oleyl amine 4ml mixes in the 50ml beaker, forms the clear solution of component two under the magnetic agitation.Component two under stirring, brute force is slowly splashed in the solution of component one.Reaction 4h, centrifugation 20min under the solution 10000r/min centrifugation rate of reaction back, solid dispersed is washed in dehydrated alcohol, and recentrifuge repeats 2 times.Fig. 3 c is the GeO by the different-shape of embodiment 3 preparations ₂The TEM photo of nano material.

Embodiment 4:

Carry out according to preparation process, with the pH value 13.5 aqueous solution 3ml, heptane 60ml, Pentyl alcohol 9ml, CTAB5g mixes in the 100ml there-necked flask, forms the clear solution of component one under the magnetic agitation, with the 20ml heptane, 0.5MGeCl4 THF solution 2ml, oleyl amine 4ml mixes in the 50ml beaker, forms the clear solution of component two under the magnetic agitation.Component two under stirring, brute force is slowly splashed in the solution of component one.Reaction 4h, centrifugation 15min under the solution 10000r/min centrifugation rate of reaction back, solid dispersed is washed in dehydrated alcohol, and recentrifuge repeats 4 times.Fig. 3 d is the GeO by embodiment 4 preparations ₂The TEM photo of nanoclusters aggressiveness particle.

Claims (1)

1, a kind of reverse microemulsion legal system is equipped with single method of disperseing germanium oxide nanometer square, it is characterized in that the step of this method is as follows:

One. material mixture ratio

Concentration is 99.99% anhydrous germanium tetrachloride GeCl ₄,

Analytical pure heptane C ₇H ₁₆,

Analytical pure tetrahydrofuran (THF) C ₄H ₈O,

Analytical pure Pentyl alcohol C ₅H ₁₂O,

Analytical pure cetyl trimethyl ammonia bromide C ₁₉H ₄₂BrN,

Concentration is 97% oleyl amine C ₁₈H ₃₇N,

Analytical pure dehydrated alcohol C ₂H ₆O,

With concentration is that 36%～38% hydrochloric acid or concentration are that 25% ammoniacal liquor preparation pH is 1.0～13.5 the aqueous solution,

Above reagent does not all pass through purification process;

Two. preparation process

1) anhydrous GeCl ₄Be dissolved in the tetrahydrofuran (THF) that to form concentration be the transparent solution of 0.5mol/l;

2) component one: be the aqueous solution of heptane: pH=1.0～13.5 with volume ratio: Pentyl alcohol=20: 1: 3, mole proportioning are that four kinds of materials of the aqueous solution=1: 12 of cetyl trimethyl ammonia bromide: pH=1.0～13.5 mix in the container of 100ml, stir under 78HW-3 type constant temperature magnetic agitation instrument and form transparent microemulsion;

3) component two: with volume ratio is heptane: GeCl ₄The tetrahydrofuran (THF) clear solution: three kinds of solution of oleyl amine=10: 1: 2 place 50ml beaker uniform mixing under 78HW-3 type constant temperature magnetic agitation instrument, form transparent microemulsion;

4) component two is slowly splashed in the mixing solutions of component one under powerful magnetic agitation, dropwise back 15～20min solution and muddiness, stopped reaction after 3～4 hours occur.Reacted mixing solutions is through 10000r/min SORVALL LEGEND-T whizzer centrifugation 10～15min, obtain solid product and disperse washing once more with dehydrated alcohol, recentrifuge, the solid that repeats to obtain after 2～4 times at room temperature is dried to pressed powder.

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