CN102390856B - Method for preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature - Google Patents
Method for preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature Download PDFInfo
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Abstract
The invention relates to a method for preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature. The method includes the steps as follows: preparing solid-state compound (La (S2CNMe2)3(2,2 '-bipy)) with saturated solution of lanthanum chloride, saturated solution of N,N-Sodium dimethyldithiocarbamate and 2,2'-bipyridyl solution; preparing amorphous La2S3 powder ina closed microwave solvent thermal reaction kettle; and finally preparing the high-stability pure gamma-phase La2S3 powder in an atmosphere tube furnace. In the invention, the experimental temperature is lowered, the temperature keeping time is shortened and the strict requirements for anhydrous and anaerobic environment are eliminated. The gamma-phase La2S3 belongs to a stable phase when the temperature is higher than 1300 DEG C, therefore the lanthanum sulfide powder prepared by the method can be stably kept in a gamma-phase structure in the full temperature range. Simultaneously, the method is simple in technology, low in cost and suitable for preparing high-stability and high-purity gamma-phase lanthanum sulfide powder in large scales.
Description
Technical field
The present invention relates to a kind of method of preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature, the prepared γ phase lanthanum sulfide powder of the method can still remain the γ phase structure under ℃ scope of room temperature～1300, there is very high thermodynamic stability, be well-suited for a hot pressed sintering preparation cube lanthanum sulfide polycrystalline material and supply raw materials.
Background technology
The lanthanum sulfide compound co-exists in 3 kinds of crystal phase structures: α phase, β phase and γ phase, wherein α-La
2s
3belonging to rhombic system is the ambient stable phase; β-La
2s
3for tetragonal, its Thermodynamically stable scope is 900 ℃～1300 ℃; γ-La
2s
3for body-centered cubic structure (with the Th in metal hole
3p
4structure), it is stable phase in temperature during higher than 1300 ℃.In actual technology application, γ phase lanthanum sulfide has the application background mutually even more important with β than the α phase, special γ-La
2s
3crystal has the good character that sees through at the mid and far infrared wave band, can be used as the infrared electromagnetic wave transparent material of 8～14 μ m, and this wave band is the wave band that the technology such as scouting, early warning and military defense are concerned about most as one of important atmospheric window.While γ-La
2s
3crystal has high fusing point (2100-2150 ℃), high hardness, large physical strength, good thermal stability and outstanding anti-weathering sand cutting ability, it has met the infrared window of high-speed aircraft and the multiple requesting that pod proposes material, so γ-La
2s
3polycrystalline, aspect the mid and far infrared window materials such as alternative zinc selenide (ZnSe) at present commonly used, zinc sulphide (ZnS), having great advantage, is the critical material of the infrared window of 8～14 μ m of future generation.Due to high-melting-point and the high affine energy of lanthanum-Sauerstoffatom of lanthanum sulfide, γ-La
2s
3the single crystal preparation difficult, its application mainly is based on γ-La
2s
3the preparation of hot pressed multicrystal, this is owing to γ-La
2s
3cube Th had
3p
4structures shape its because of optical anisotropy, do not cause that when forming hot pressed multicrystal infrared light scattering causes transmitance decline or devitrification.In addition, the lanthanum sulfide polycrystalline as outstanding high temperature thermoelectric material also requires it to possess a cube γ phase structure.Therefore, preparing the lanthanum sulfide powder and controlling its phase structure is the γ phase, particularly prepares and has γ-La that high heating power is learned stability
2s
3powder is significant to the practical application development of this material.
The preparation method of the γ phase lanthanum sulfide powder of reporting for work at present comprises crystalline phase conversion method [V.V.Sokolov, Kamarzin A.A., Trushnikova L.N., et al, Optical materials containing rare earth Ln
2s
3sulfides; Journal of Alloys and Compounds; 1995; 225 (1-2): 567-570] and presoma sulfuration method [P.N.Kamta; S.H.Risbudt; Chemical process of rare earth chalcogenides; Progress Crystal Growth and Characteristics; 22 (1991) 321～383; P.N.Kumta; S.H.Risbud, Low Temperature Synthesis of Cubic lanthanum Sulfide (La2S3) Powders, Material Science& Engineer, B, 2 (1989) 281～286].React under 600 ℃ and obtain α-La after the crystalline phase conversion method mainly adopts metal La and S simple substance powder to mix in silica tube
2s
3, then by α-La
2s
3under 950 ℃, insulation is converted into β-La in 3 days
2s
3, then by β-La
2s
3in 1500 ℃ and 2150 ℃ of tungsten crucibles at vacuum sealing, long heat treatment is to be converted into γ-La
2s
3.Presoma sulfuration method is by the oxide compound La of lanthanum
2o
3or the alkoxide of lanthanum and vulcanizing agent H
2s carries out long-time pyroreaction, finally obtains rare-earth sulfide, and the curing temperature of this method usually will be more than 1000～1300 ℃, and now presoma can not be sulfided into γ-La fully
2s
3.Obviously these methods are to processing unit and conditional request harshness, and curing temperature is high, the time is long, cost is higher.Prior defect is that reaction is incomplete, can't obtain the pure phase product, contains β phase and oxysulfide in various degree in product.
Summary of the invention
The technical problem solved
For fear of the deficiencies in the prior art part, the present invention proposes a kind of method of preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature, overcome exist in prior art expensive, reaction not exclusively, be difficult to obtain the deficiency of pure γ phase product.
Technical scheme
A kind of method of preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature is characterized in that step is as follows:
Step 1 configuration reaction soln: by the saturated solution of Lanthanum trichloride and N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min mixes, under 25～50 ℃, by 2,2 '-dipyridyl solution dropwise adds in two kinds of saturated solutions that mixed with the speed of 30/min, keep the magnetic agitation reaction after 1.0～1.5 hours, generate compound crystal in solution; The amount of substance ratio of three kinds of saturated solutions is 1: 3: 1;
Adopt Büchner funnel to filter compound crystal, be placed in vacuum drier with absolute ethanol washing after obtaining crystalline product, under 60～80 ℃, vacuum tightness 0.1Pa, keep 3 hours dryings, obtain solid compounds [La (S
2cNMe
2)
3(2,2 '-bipy)];
The amorphous La of step 2 preparation
2s
3powder: by solid compounds [La (S
2cNMe
2)
3(2,2 '-bipy)] be dissolved in acetonitrile or chloroform makes the saturated solution under 25 ℃, to filter this solution removal with Büchner funnel and be not transferred in microwave solvent thermal response still after dissolved impurity, compactedness is 90%; Sealing microwave solvent thermal response still, be rapidly heated to 100～150 ℃ of temperature with 5～15 ℃/min of heating rate, after being incubated 0.5～3 hour, open reactor, use the Büchner funnel filtering-depositing, use again the ethanol washing and precipitating, then use the deionized water washing and precipitating, then the precipitation after cleaning is put in the vacuum atmosphere loft drier, argon gas is filled with in loft drier and makes its pressure remain 1.1atm, and loft drier is warming up to 60 ℃ with 5 ℃/min, and be incubated 5 hours, obtain dry amorphous La
2s
3powder;
The pure γ phase of step 3 preparation high stability La
2s
3powder: by the amorphous La of drying
2s
3powder is that 200～300 purpose lead sulfide powders or aluminium sulfide powder are La according to the amount of substance ratio with granularity
3+: M=(12～2): 1 (M=pb
2+or Al
3+) evenly mix and be placed in the atmosphere tube type stove; then, under the hydrogen sulfide that is 20ml/min at flow or carbon disulfide gas protection, with heating rate, 20 ℃/min is rapidly heated to 300～600 ℃, is incubated 1.0 hours; after soaking time finishes, naturally cool to room temperature.Take out the pure γ phase of the high stability La prepared in tube furnace
2s
3powder.
The preparation of the saturated solution of described Lanthanum trichloride is: Lanthanum trichloride is dissolved in dehydrated alcohol, makes the saturated solution of Lanthanum trichloride under 25 ℃.
Described N, the preparation of the saturated solution of N-Sodium dimethyldithiocarbamate 40min is: by N, the N-Sodium dimethyldithiocarbamate 40min is dissolved in dehydrated alcohol, makes the saturated solution of Lanthanum trichloride under 25 ℃.
Described 2, the preparation of the saturated solution of 2 '-dipyridyl is: by 2,2 '-dipyridyl is dissolved in dehydrated alcohol, makes the saturated solution of Lanthanum trichloride under 25 ℃.
Use absolute ethanol washing 2 times after obtaining crystalline product in step 1.
In step 2, the number of times of ethanol washing and precipitating is 3 times.
The number of times of step 2 intermediate ion water washing and precipitating is 3 times.
Beneficial effect
The method of a kind of preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature that the present invention proposes, reduced experimental temperature, shortened soaking time, eliminate the strict demand to the anhydrous and oxygen-free environment, can obtain the lanthanum sulfide powder of the high-purity gamma phase of the stable existence that still remains the γ phase structure under ℃ temperature range of room temperature～1300.Due to γ phase La
2s
3belong to stable phase in temperature during higher than 1300 ℃, so lanthanum sulfide powder prepared by the present invention for stablizing the lanthanum sulfide powder that remains the γ phase structure in the total temperature scope.Simultaneously, its technique is simple, and cost is low, is suitable for preparing on a large scale the high-purity gamma phase lanthanum sulfide powder that stability is high, has broad application prospects.
Embodiment
Now the invention will be further described in conjunction with the embodiments:
The technical scheme that the embodiment of the present invention adopts is:
The first step, the configuration of reaction soln
The amount of substance ratio is respectively to the LaCl of 1: 3: 1
36H
2o, N, N-Sodium dimethyldithiocarbamate 40min (NaS
2cNMe
2) and 2,2 '-dipyridyl (2,2 '-bipy) is dissolved in respectively in few dehydrated alcohol of trying one's best, and under 25 ℃, makes respectively saturated solution, the N of Lanthanum trichloride, the saturated solution of N-Sodium dimethyldithiocarbamate 40min, 2, the saturated solution of 2 '-dipyridyl.Then by the saturated solution of Lanthanum trichloride and N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min mixes, even by magnetic stirrer, again under 25～50 ℃, under magnetic stirrer by 2, 2 '-dipyridyl solution dropwise adds in two kinds of saturated solutions that mixed with the speed of 30/min, keep the magnetic agitation reaction after 1.0～1.5 hours, generate compound crystal in solution, crystal is filtered with Büchner funnel, the crystalline product obtained is placed in vacuum drier for 2 times with absolute ethanol washing, at 60～80 ℃, under vacuum tightness 0.1Pa, keep 3 hours dryings, obtain solid compounds [La (S
2cNMe
2)
3(2,2 '-bipy)].
Second step, amorphous La
2s
3the preparation of powder
Secondly, by solid compounds [La (S
2cNMe
2)
3(2, 2 '-bipy)] be dissolved in the organic solvents such as appropriate acetonitrile or chloroform, make the saturated solution under 25 ℃, filter not dissolved impurity of this solution removal with Büchner funnel, this organic solution partly is transferred in microwave solvent thermal response still again, compactedness is 90%, sealing microwave solvent thermal response still, with 5～15 ℃/min of heating rate, be rapidly heated to 100～150 ℃ of temperature, be incubated after 0.5～3 hour, open reactor, use the Büchner funnel filtering-depositing, first use the ethanol washing and precipitating 3 times, use again the deionized water washing and precipitating 3 times, then the precipitation after cleaning is put in the vacuum atmosphere loft drier, argon gas is filled with in loft drier and makes its pressure remain 1.1atm, and loft drier is warming up to 60 ℃ with 5 ℃/min, and be incubated 5 hours, obtain dry amorphous La
2s
3powder.
The 3rd step, the pure γ phase of high stability La
2s
3the powder preparation
Amorphous La by drying
2s
3powder is that 200～300 purpose lead sulfide powders or aluminium sulfide powder are La according to the amount of substance ratio with granularity
3+: M=(12～2): 1 (M=pb
2+or Al
3+) evenly mix and be placed in the atmosphere tube type stove; then, under the hydrogen sulfide that is 20ml/min at flow or carbon disulfide gas protection, with heating rate, 20 ℃/min is rapidly heated to 300～600 ℃, is incubated 1.0 hours; after soaking time finishes, naturally cool to room temperature.Take out powder in tube furnace, be the pure γ phase of the high stability of preparing La
2s
3powder.
Specific embodiment:
Embodiment 1:
The first step, the configuration of reaction soln
Under 25 ℃, by the analytically pure LaCl of 35.3 gram
36H
2during O is dissolved in dehydrated alcohol under agitation condition, make the saturated solution of Lanthanum trichloride; Again by the analytically pure N of 14.3 gram, N-Sodium dimethyldithiocarbamate 40min (NaS
2cNMe
2) be dissolved in dehydrated alcohol under agitation condition, make N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min; By 2 of 15.6 grams, 2 '-dipyridyl is dissolved in dehydrated alcohol again, makes 2, the saturated solution of 2 '-dipyridyl.Between above solution, the amount of substance of each solute ratio is respectively (LaCl
36H
2o): (NaS
2cNMe
2): (2,2 '-bipy)=1: 3: 1.Then by the saturated solution of Lanthanum trichloride and N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min mixes, by magnetic stirrer extremely evenly, again under 25 ℃, under magnetic stirrer by 2, 2 '-dipyridyl saturated solution dropwise adds in two kinds of saturated solutions that mixed with the speed of 30/min, keep the magnetic agitation reaction after 1.0 hours, generate compound crystal in solution, by crystal Büchner funnel suction filtration, the crystalline product obtained is placed in vacuum drier for 2 times with absolute ethanol washing, at 60 ℃, under vacuum tightness 0.1Pa, keep 3 hours dryings, obtain solid compounds [La (S
2cNMe
2)
3(2,2 '-bipy)], quality is 37.6 grams.
Second step, amorphous La
2s
3the preparation of powder
Solid compounds prepared by the first step [La (S
2cNMe
2)
3(2,2 '-bipy)] 37.6 grams are dissolved in the acetonitrile solvent of 120ml, and fill the Glass Containers to 60 ℃ of solution with common heating by electric cooker, and after vaporing away unnecessary solvent, solution is naturally cooled to 25 ℃, make [La (the S under 25 ℃
2cNMe
2)
3(2, 2 '-bipy)] saturated solution, filter not dissolved impurity of this solution removal with Büchner funnel, again this organic solution partly is transferred in the microwave solvent thermal response still of 100ml capacity, compactedness is 90%, sealing microwave solvent thermal response still, with 15 ℃/min of heating rate, be rapidly heated to 150 ℃ of temperature, be incubated after 3 hours, open reactor, use the Büchner funnel filtering-depositing, first use the ethanol washing and precipitating 3 times, use again the deionized water washing and precipitating 3 times, then the precipitation after cleaning is put in the vacuum atmosphere loft drier, argon gas is filled with in loft drier and makes its pressure remain 1.1atm, and loft drier is warming up to 60 ℃ with 5 ℃/min, and be incubated 5 hours, obtain dry amorphous La
2s
3powder 11.2 grams.
The 3rd step, the pure γ phase of high stability La
2s
3the powder preparation
Dry amorphous La by preparation
2s
3powder 11.2 grams are that 300 purpose lead sulfide powder 0.6 grams evenly mix in agate mortar with granularity, and the amount of substance ratio that two materials are corresponding is La
3+: pb
2+=12: 1, even mixed powder is placed in to the atmosphere tube type stove, under the hydrogen sulfide that is then 20ml/min at flow protection; with 20 ℃/min of heating rate, be rapidly heated to 300 ℃; be incubated 1.0 hours, after soaking time finishes, naturally cool to room temperature.Take out powder in tube furnace, make the pure γ phase of high stability La
2s
3powder 11.7 grams.
Embodiment 2:
The first step, the configuration of reaction soln
Under 25 ℃, by the analytically pure LaCl of 17.7 gram
36H
2during O is dissolved in dehydrated alcohol under agitation condition, make the saturated solution of Lanthanum trichloride; Again by the analytically pure N of 7.2 gram, N-Sodium dimethyldithiocarbamate 40min (NaS
2cNMe
2) be dissolved in dehydrated alcohol under agitation condition, make N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min; By 2 of 7.8 grams, 2 '-dipyridyl is dissolved in dehydrated alcohol again, makes 2, the saturated solution of 2 '-dipyridyl.Between above solution, the amount of substance of each solute ratio is respectively (LaCl
36H
2o): (NaS
2cNMe
2): (2,2 '-bipy)=1: 3: 1.Then by the saturated solution of Lanthanum trichloride and N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min mixes, by magnetic stirrer extremely evenly, again under 50 ℃, under magnetic stirrer by 2, 2 '-dipyridyl saturated solution dropwise adds in two kinds of saturated solutions that mixed with the speed of 30/min, keep the magnetic agitation reaction after 1.5 hours, generate compound crystal in solution, by crystal Büchner funnel suction filtration, the crystalline product obtained is placed in vacuum drier for 2 times with absolute ethanol washing, at 80 ℃, under vacuum tightness 0.1Pa, keep 3 hours dryings, obtain solid compounds [La (S
2cNMe
2)
3(2,2 '-bipy)], quality is 23.3 grams.
Second step, amorphous La
2s
3the preparation of powder
Solid compounds prepared by the first step [La (S
2cNMe
2)
3(2,2 '-bipy)] 23.3 grams are dissolved in the chloroform solvent of 100ml, and fill the Glass Containers to 60 ℃ of solution with common heating by electric cooker, and after vaporing away unnecessary solvent, solution is naturally cooled to 25 ℃, make [La (the S under 25 ℃
2cNMe
2)
3(2, 2 '-bipy)] saturated solution, filter not dissolved impurity of this solution removal with Büchner funnel, again this organic solution partly is transferred in the microwave solvent thermal response still of 100ml capacity, compactedness is 90%, sealing microwave solvent thermal response still, with 5 ℃/min of heating rate, be rapidly heated to 100 ℃ of temperature, be incubated after 3 hours, open reactor, use the Büchner funnel filtering-depositing, first use the ethanol washing and precipitating 3 times, use again the deionized water washing and precipitating 3 times, then the precipitation after cleaning is put in the vacuum atmosphere loft drier, argon gas is filled with in loft drier and makes its pressure remain 1.1atm, and loft drier is warming up to 60 ℃ with 5 ℃/min, and be incubated 5 hours, obtain dry amorphous La
2s
3powder 10.6 grams.
The 3rd step, the pure γ phase of high stability La
2s
3the powder preparation
Dry amorphous La by preparation
2s
3powder 10.6 grams are that 200 purpose aluminium sulfide powder 3.4 grams evenly mix in agate mortar with granularity, and the amount of substance ratio that two materials are corresponding is La
3+: pb
2+=2: 1, even mixed powder is placed in to the atmosphere tube type stove, under the carbon disulfide gas that is then 20ml/min at flow protection; with 20 ℃/min of heating rate, be rapidly heated to 600 ℃; be incubated 1.0 hours, after soaking time finishes, naturally cool to room temperature.Take out powder in tube furnace, make the pure γ phase of high stability La
2s
3powder 13.9 grams.
Embodiment 3:
The first step, the configuration of reaction soln
Under 25 ℃, by the analytically pure LaCl of 26.7 gram
36H
2during O is dissolved in dehydrated alcohol under agitation condition, make the saturated solution of Lanthanum trichloride; Again by the analytically pure N of 10.8 gram, N-Sodium dimethyldithiocarbamate 40min (NaS
2cNMe
2) be dissolved in dehydrated alcohol under agitation condition, make N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min; By 2 of 11.7 grams, 2 '-dipyridyl is dissolved in dehydrated alcohol again, makes 2, the saturated solution of 2 '-dipyridyl.Between above solution, the amount of substance of each solute ratio is respectively (LaCl
36H
2o): (NaS
2cNMe
2): (2,2 '-bipy)=1: 3: 1.Then by the saturated solution of Lanthanum trichloride and N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min mixes, by magnetic stirrer extremely evenly, again under 30 ℃, under magnetic stirrer by 2, 2 '-dipyridyl saturated solution dropwise adds in two kinds of saturated solutions that mixed with the speed of 30/min, keep the magnetic agitation reaction after 1.2 hours, generate compound crystal in solution, crystal is filtered with Büchner funnel, the crystalline product obtained is placed in vacuum drier for 2 times with absolute ethanol washing, at 70 ℃, under vacuum tightness 0.1Pa, keep 3 hours dryings, obtain solid compounds [La (S
2cNMe
2)
3(2,2 '-bipy)], quality is 29.2 grams.
Second step, amorphous La
2s
3the preparation of powder
Solid compounds prepared by the first step [La (S
2cNMe
2)
3(2,2 '-bipy)] 29.2 grams are dissolved in the acetonitrile solvent of 100ml, and fill the Glass Containers to 60 ℃ of solution with common heating by electric cooker, and after vaporing away unnecessary solvent, solution is naturally cooled to 25 ℃, make [La (the S under 25 ℃
2cNMe
2)
3(2, 2 '-bipy)] saturated solution, filter not dissolved impurity of this solution removal with Büchner funnel, again this organic solution partly is transferred in the microwave solvent thermal response still of 100ml capacity, compactedness is 90%, sealing microwave solvent thermal response still, with 10 ℃/min of heating rate, be rapidly heated to 120 ℃ of temperature, be incubated after 2 hours, open reactor, use the Büchner funnel filtering-depositing, first use the ethanol washing and precipitating 3 times, use again the deionized water washing and precipitating 3 times, then the precipitation after cleaning is put in the vacuum atmosphere loft drier, argon gas is filled with in loft drier and makes its pressure remain 1.1atm, and loft drier is warming up to 60 ℃ with 5 ℃/min, and be incubated 5 hours, obtain dry amorphous La
2s
3powder 12.2 grams.
The 3rd step, the pure γ phase of high stability La
2s
3the powder preparation
Dry amorphous La by preparation
2s
3powder 12.2 grams are that 250 purpose aluminium sulfide powder 0.3 grams evenly mix in agate mortar with granularity, and the amount of substance ratio that two materials are corresponding is La
3+: Al
3+=12: 1, even mixed powder is placed in to the atmosphere tube type stove, under the carbon disulfide gas that is then 20ml/min at flow protection; with 20 ℃/min of heating rate, be rapidly heated to 400 ℃; be incubated 1.0 hours, after soaking time finishes, naturally cool to room temperature.Take out powder in tube furnace, make the pure γ phase of high stability La
2s
3powder 12.5 grams.
Embodiment 4:
The first step, the configuration of reaction soln
Under 25 ℃, by the analytically pure LaCl of 22.3 gram
36H
2during O is dissolved in dehydrated alcohol under agitation condition, make the saturated solution of Lanthanum trichloride; Again by the analytically pure N of 9.0 gram, N-Sodium dimethyldithiocarbamate 40min (NaS
2cNMe
2) be dissolved in dehydrated alcohol under agitation condition, make N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min; By 2 of 9.75 grams, 2 '-dipyridyl is dissolved in dehydrated alcohol again, makes 2, the saturated solution of 2 '-dipyridyl.Between above solution, the amount of substance of each solute ratio is respectively (LaCl
36H
2o): (NaS
2cNMe
2): (2,2 '-bipy)=1: 3: 1.Then by the saturated solution of Lanthanum trichloride and N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min mixes, by magnetic stirrer extremely evenly, again under 40 ℃, under magnetic stirrer by 2, 2 '-dipyridyl saturated solution dropwise adds in two kinds of saturated solutions that mixed with the speed of 30/min, keep the magnetic agitation reaction after 1.5 hours, generate compound crystal in solution, crystal is filtered with Büchner funnel, the crystalline product obtained is placed in vacuum drier for 2 times with absolute ethanol washing, at 80 ℃, under vacuum tightness 0.1Pa, keep 3 hours dryings, obtain solid compounds [La (S
2cNMe
2)
3(2,2 '-bipy)], quality is 27.3 grams.
Second step, amorphous La
2s
3the preparation of powder
Solid compounds prepared by the first step [La (S
2cNMe
2)
3(2,2 '-bipy)] 27.3 grams are dissolved in the chloroform solvent of 100ml, and fill the Glass Containers to 60 ℃ of solution with common heating by electric cooker, and after vaporing away unnecessary solvent, solution is naturally cooled to 25 ℃, make [La (the S under 25 ℃
2cNMe
2)
3(2, 2 '-bipy)] saturated solution, filter not dissolved impurity of this solution removal with Büchner funnel, again this organic solution partly is transferred in the microwave solvent thermal response still of 100ml capacity, compactedness is 90%, sealing microwave solvent thermal response still, with 12 ℃/min of heating rate, be rapidly heated to 120 ℃ of temperature, be incubated after 2 hours, open reactor, use the Büchner funnel filtering-depositing, first use the ethanol washing and precipitating 3 times, use again the deionized water washing and precipitating 3 times, then the precipitation after cleaning is put in the vacuum atmosphere loft drier, argon gas is filled with in loft drier and makes its pressure remain 1.1atm, and loft drier is warming up to 60 ℃ with 5 ℃/min, and be incubated 5 hours, obtain dry amorphous La
2s
3powder 13.8 grams.
The 3rd step, the pure γ phase of high stability La
2s
3the powder preparation
Dry amorphous La by preparation
2s
3powder 13.8 grams are that 300 purpose lead sulfide powder 1.8 grams evenly mix in agate mortar with granularity, and the amount of substance ratio that two materials are corresponding is La
3+: pb
2+=5: 1, even mixed powder is placed in to the atmosphere tube type stove, under the hydrogen sulfide that is then 20ml/min at flow protection; with 20 ℃/min of heating rate, be rapidly heated to 600 ℃; be incubated 1.0 hours, after soaking time finishes, naturally cool to room temperature.Take out powder in tube furnace, make the pure γ phase of high stability La
2s
3powder 15.6 grams.
Embodiment 5:
The first step, the configuration of reaction soln
Under 25 ℃, by the analytically pure LaCl of 33.45 gram
36H
2during O is dissolved in dehydrated alcohol under agitation condition, make the saturated solution of Lanthanum trichloride; Again by the analytically pure N of 13.5 gram, N-Sodium dimethyldithiocarbamate 40min (NaS
2cNMe
2) be dissolved in dehydrated alcohol under agitation condition, make N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min; By 2 of 14.6 grams, 2 '-dipyridyl is dissolved in dehydrated alcohol again, makes 2, the saturated solution of 2 '-dipyridyl.Between above solution, the amount of substance of each solute ratio is respectively (LaCl
36H
2o): (NaS
2cNMe
2): (2,2 '-bipy)=1: 3: 1.Then by the saturated solution of Lanthanum trichloride and N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min mixes, by magnetic stirrer extremely evenly, again under 40 ℃, under magnetic stirrer by 2, 2 '-dipyridyl saturated solution dropwise adds in two kinds of saturated solutions that mixed with the speed of 30/min, keep the magnetic agitation reaction after 1.5 hours, generate compound crystal in solution, crystal is filtered with Büchner funnel, the crystalline product obtained is placed in vacuum drier for 2 times with absolute ethanol washing, at 80 ℃, under vacuum tightness 0.1Pa, keep 3 hours dryings, obtain solid compounds [La (S
2cNMe
2)
3(2,2 '-bipy)], quality is 39.3 grams.
Second step, amorphous La
2s
3the preparation of powder
Solid compounds prepared by the first step [La (S
2cNMe
2)
3(2,2 '-bipy)] 39.3 grams are dissolved in the chloroform solvent of 100ml, and fill the Glass Containers to 60 ℃ of solution with common heating by electric cooker, and after vaporing away unnecessary solvent, solution is naturally cooled to 25 ℃, make [La (the S under 25 ℃
2cNMe
2)
3(2, 2 '-bipy)] saturated solution, filter not dissolved impurity of this solution removal with Büchner funnel, again this organic solution partly is transferred in the microwave solvent thermal response still of 100ml capacity, compactedness is 90%, sealing microwave solvent thermal response still, with 12 ℃/min of heating rate, be rapidly heated to 120 ℃ of temperature, be incubated after 2 hours, open reactor, use the Büchner funnel filtering-depositing, first use the ethanol washing and precipitating 3 times, use again the deionized water washing and precipitating 3 times, then the precipitation after cleaning is put in the vacuum atmosphere loft drier, argon gas is filled with in loft drier and makes its pressure remain 1.1atm, and loft drier is warming up to 60 ℃ with 5 ℃/min, and be incubated 5 hours, obtain dry amorphous La
2s
3powder 18.8 grams.
The 3rd step, the pure γ phase of high stability La
2s
3the powder preparation
Dry amorphous La by preparation
2s
3powder 18.8 grams are that 250 purpose aluminium sulfide powder 1.9 grams evenly mix in agate mortar with granularity, and the amount of substance ratio that two materials are corresponding is La
3+: Al
3+=2: 1, even mixed powder is placed in to the atmosphere tube type stove, under the hydrogen sulfide that is then 20ml/min at flow protection; with 20 ℃/min of heating rate, be rapidly heated to 600 ℃; be incubated 1.0 hours, after soaking time finishes, naturally cool to room temperature.Take out powder in tube furnace, make the pure γ phase of high stability La
2s
3powder 20.7 grams.
Embodiment 6:
The first step, the configuration of reaction soln
Under 25 ℃, by the analytically pure LaCl of 31.22 gram
36H
2during O is dissolved in dehydrated alcohol under agitation condition, make the saturated solution of Lanthanum trichloride; Again by the analytically pure N of 12.6 gram, N-Sodium dimethyldithiocarbamate 40min (NaS
2cNMe
2) be dissolved in dehydrated alcohol under agitation condition, make N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min; By 2 of 13.7 grams, 2 '-dipyridyl is dissolved in dehydrated alcohol again, makes 2, the saturated solution of 2 '-dipyridyl.Between above solution, the amount of substance of each solute ratio is respectively (LaCl
36H
2o): (NaS
2cNMe
2): (2,2 '-bipy)=1: 3: 1.Then by the saturated solution of Lanthanum trichloride and N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min mixes, by magnetic stirrer extremely evenly, again under 40 ℃, under magnetic stirrer by 2, 2 '-dipyridyl saturated solution dropwise adds in two kinds of saturated solutions that mixed with the speed of 30/min, keep the magnetic agitation reaction after 1.5 hours, generate compound crystal in solution, crystal is filtered with Büchner funnel, the crystalline product obtained is placed in vacuum drier for 2 times with absolute ethanol washing, at 80 ℃, under vacuum tightness 0.1Pa, keep 3 hours dryings, obtain solid compounds [La (S
2cNMe
2)
3(2,2 '-bipy)], quality is 35.3 grams.
Second step, amorphous La
2s
3the preparation of powder
Solid compounds prepared by the first step [La (S
2cNMe
2)
3(2,2 '-bipy)] 35.3 grams are dissolved in the chloroform solvent of 100ml, and fill the Glass Containers to 60 ℃ of solution with common heating by electric cooker, and after vaporing away unnecessary solvent, solution is naturally cooled to 25 ℃, make [La (the S under 25 ℃
2cNMe
2)
3(2, 2 '-bipy)] saturated solution, filter not dissolved impurity of this solution removal with Büchner funnel, again this organic solution partly is transferred in the microwave solvent thermal response still of 100ml capacity, compactedness is 90%, sealing microwave solvent thermal response still, with 12 ℃/min of heating rate, be rapidly heated to 120 ℃ of temperature, be incubated after 2 hours, open reactor, use the Büchner funnel filtering-depositing, first use the ethanol washing and precipitating 3 times, use again the deionized water washing and precipitating 3 times, then the precipitation after cleaning is put in the vacuum atmosphere loft drier, argon gas is filled with in loft drier and makes its pressure remain 1.1atm, and loft drier is warming up to 60 ℃ with 5 ℃/min, and be incubated 5 hours, obtain dry amorphous La
2s
3powder 16.7 grams.
The 3rd step, the pure γ phase of high stability La
2s
3the powder preparation
Dry amorphous La by preparation
2s
3powder 16.7 grams are that 300 purpose lead sulfide powder 0.7 grams evenly mix in agate mortar with granularity, and the amount of substance ratio that two materials are corresponding is La
3+: Al
3+=5: 1, even mixed powder is placed in to the atmosphere tube type stove, under the hydrogen sulfide that is then 20ml/min at flow protection; with 20 ℃/min of heating rate, be rapidly heated to 600 ℃; be incubated 1.0 hours, after soaking time finishes, naturally cool to room temperature.Take out powder in tube furnace, make the pure γ phase of high stability La
2s
3powder 17.4 grams.
Claims (4)
1. the method for a preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature is characterized in that step is as follows:
Step 1 configuration reaction soln: by the saturated solution of Lanthanum trichloride and N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min mixes, under 25～50 ℃, by 2,2 '-dipyridyl saturated solution dropwise adds in two kinds of saturated solutions that mixed with the speed of 30/min, keep the magnetic agitation reaction after 1.0～1.5 hours, generate compound crystal in solution; The amount of substance of three kinds of saturated solutions is than being 1:3:1; The preparation of the saturated solution of described Lanthanum trichloride is: Lanthanum trichloride is dissolved in dehydrated alcohol, makes the saturated solution of Lanthanum trichloride under 25 ℃; Described N, the preparation of the saturated solution of N-Sodium dimethyldithiocarbamate 40min is: by N, the N-Sodium dimethyldithiocarbamate 40min is dissolved in dehydrated alcohol, under 25 ℃, makes N, the saturated solution of N-Sodium dimethyldithiocarbamate 40min; Described 2, the preparation of the saturated solution of 2 '-dipyridyl is: by 2,2 '-dipyridyl is dissolved in dehydrated alcohol, under 25 ℃, makes 2, the saturated solution of 2 '-dipyridyl;
Adopt Büchner funnel to filter compound crystal, be placed in vacuum drier with absolute ethanol washing after obtaining crystalline product, under 60～80 ℃, vacuum tightness 0.1Pa, keep 3 hours dryings, obtain solid compounds [La (S
2cNMe
2)
3(2,2 '-bipy)];
The amorphous La of step 2 preparation
2s
3powder: by solid compounds [La (S
2cNMe
2)
3(2,2 '-bipy)] be dissolved in acetonitrile or chloroform makes the saturated solution under 25 ℃, to filter this solution removal with Büchner funnel and be not transferred in microwave solvent thermal response still after dissolved impurity, compactedness is 90%; Sealing microwave solvent thermal response still, be rapidly heated to 100～150 ℃ of temperature with 5～15 ℃/min of heating rate, after being incubated 0.5～3 hour, open reactor, use the Büchner funnel filtering-depositing, use again the ethanol washing and precipitating, then use the deionized water washing and precipitating, then the precipitation after cleaning is put in the vacuum atmosphere loft drier, argon gas is filled with in loft drier and makes its pressure remain 1.1atm, and loft drier is warming up to 60 ℃ with 5 ℃/min, and be incubated 5 hours, obtain dry amorphous La
2s
3powder;
The pure γ phase of step 3 preparation high stability La
2s
3powder: by the amorphous La of drying
2s
3powder is that 200～300 purpose lead sulfide powders or aluminium sulfide powder are La according to the amount of substance ratio with granularity
3+: M=(12～2): 1 evenly mixes and is placed in the atmosphere tube type stove, and described M is Pb
2+or Al
3+; Then under the hydrogen sulfide that is 20mL/min at flow or carbon disulfide gas protection; with heating rate, 20 ℃/min is rapidly heated to 300～600 ℃, is incubated 1.0 hours, after soaking time finishes; naturally cool to room temperature, in tube furnace, take out the pure γ phase of the high stability La prepared
2s
3powder.
2. the method for preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature according to claim 1 is characterized in that: in step 1, obtain after crystalline product with absolute ethanol washing 2 times.
3. the method for preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature according to claim 1, it is characterized in that: in step 2, the number of times of ethanol washing and precipitating is 3 times.
4. the method for preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature according to claim 1, it is characterized in that: in step 2, the number of times of washed with de-ionized water precipitation is 3 times.
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