CN114538397A - Preparation method of cadmium phosphide - Google Patents
Preparation method of cadmium phosphide Download PDFInfo
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- CN114538397A CN114538397A CN202210245203.1A CN202210245203A CN114538397A CN 114538397 A CN114538397 A CN 114538397A CN 202210245203 A CN202210245203 A CN 202210245203A CN 114538397 A CN114538397 A CN 114538397A
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- IGPFOKFDBICQMC-UHFFFAOYSA-N 3-phenylmethoxyaniline Chemical compound NC1=CC=CC(OCC=2C=CC=CC=2)=C1 IGPFOKFDBICQMC-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 46
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 37
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- 239000011574 phosphorus Substances 0.000 claims abstract description 26
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 239000012043 crude product Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 42
- 238000004321 preservation Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000001308 synthesis method Methods 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 32
- 239000000843 powder Substances 0.000 description 26
- 229910052786 argon Inorganic materials 0.000 description 18
- 229910052793 cadmium Inorganic materials 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- NRGIRRZWCDKDMV-UHFFFAOYSA-H cadmium(2+);diphosphate Chemical compound [Cd+2].[Cd+2].[Cd+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O NRGIRRZWCDKDMV-UHFFFAOYSA-H 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000011869 dried fruits Nutrition 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a preparation method of cadmium phosphide, belonging to the technical field of solar material synthesis, and the preparation method of cadmium phosphide provided by the invention comprises the following steps: (1) uniformly mixing elemental phosphorus and elemental cadmium, and placing the mixture in an inert gas environment for chemical combination reaction to obtain a cadmium phosphide crude product; (2) melting the crude cadmium phosphide product in an inert gas environment to obtain a cadmium phosphide synthetic material; (3) crushing and removing impurities from the cadmium phosphide synthetic material to obtain cadmium phosphide; the preparation method of cadmium phosphide provided by the invention adopts a two-step synthesis method, so that on one hand, the requirement of high pressure resistance on equipment in a liquid-phase synthesis method can be avoided, thereby ensuring the safety of the preparation process, and on the other hand, the volatilization of elemental phosphorus caused by high temperature in a conventional solid-phase synthesis method can be avoided, thereby ensuring the purity and yield of the synthesized cadmium phosphide.
Description
Technical Field
The invention belongs to the technical field of solar material synthesis, and particularly relates to a preparation method of cadmium phosphide.
Background
Cadmium phosphide, green tetragonal needle-like crystal, density 5.6g/cm3Melting point 700 ℃; it is a p-type semiconductor material with excellent properties, has a direct forbidden band and a narrow band gap of only 0.55eV, and has strong light emission and light absorption in the ultraviolet-visible-infrared region, so that it has strong light emission and light absorption in the aspects of photoelectric devices such as solar cells and the likeHas good application prospect.
At present, the preparation of cadmium phosphide is rarely reported, the conventional compound is generally synthesized by adopting a liquid phase, the pressure resistance of a device needing to be synthesized is larger due to the high vapor pressure of phosphorus and cadmium, and the pressure resistance is usually more than 5MPa above the melting point of the phosphorus and the cadmium, so that the requirements on equipment and the environment for synthesis are higher.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the cadmium phosphate preparation method with high purity and high operation applicability.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of cadmium phosphide comprises the following steps:
(1) uniformly mixing elemental phosphorus and elemental cadmium, and placing the mixture in an inert gas environment for chemical combination reaction to obtain a cadmium phosphide crude product;
(2) melting the crude cadmium phosphide product obtained in the step (1) in an inert gas environment to obtain a cadmium phosphide synthetic material;
(3) and (3) crushing and removing impurities from the cadmium phosphide synthetic material obtained in the step (2) to obtain cadmium phosphide.
The preparation method of cadmium phosphide provided by the technical scheme of the invention adopts a two-step synthesis method, firstly, a chemical combination reaction is carried out under an inert gas environment to synthesize a crude product of cadmium phosphide, then, the crude product is melted and crushed to remove impurities to obtain a cadmium phosphide product, and the introduced two-step synthesis method can avoid the requirement of high pressure resistance on equipment in a liquid phase synthesis method on one hand, thereby ensuring the safety of the preparation process, and can also avoid the volatilization of elemental phosphorus caused by high temperature in a conventional solid phase synthesis method on the other hand, thereby ensuring the purity and the yield of the synthesized cadmium phosphide.
As a preferable embodiment of the preparation method of the present invention, in the step (1), the molar ratio of the elemental phosphorus to the elemental cadmium is 2: 3.
In the application process of the cadmium phosphide as the solar material, the provided material of the cadmium phosphide can ensure that the molar ratio of phosphorus to cadmium is 2:3, so that the molar ratio of the phosphorus to the cadmium in the preparation method provided by the invention is limited to 2:3, and the prepared high-purity cadmium phosphide can be directly applied to the field of solar materials.
As a preferred embodiment of the preparation method of the present invention, the elemental phosphorus is red phosphorus; the melting point of red phosphorus is 590 ℃, the melting point of white phosphorus is 44.1 ℃, and as heating is needed to carry out combination reaction in the synthesis process, in order to avoid the loss of raw materials, the reduction of yield and the pollution to the environment caused by the volatilization of phosphorus, the invention preferably selects the elemental phosphorus as red phosphorus.
As a preferable embodiment of the preparation method, the elemental phosphorus and the elemental cadmium are in powder form, and the particle size of the powder is less than 100 meshes; the powdery elemental phosphorus and the elemental cadmium are uniformly mixed, so that the contact area of the reaction of the elemental phosphorus and the elemental cadmium is favorably enlarged, and the subsequent chemical combination reaction of the elemental phosphorus and the elemental cadmium is facilitated.
As a preferred embodiment of the preparation method of the present invention, in the step (1), the conditions of the combination reaction are: firstly, the temperature is raised from room temperature to 300-350 ℃ at the heating rate of 3-5 ℃/min, the temperature is preserved for 30-50min, then the temperature is raised to 500-550 ℃ at the heating rate of 7-10 ℃/min, and the temperature is preserved for 30-60 min.
Firstly heating to 350 ℃ at a heating rate of 3-5 ℃/min, preserving the heat for a period of time, and then heating to 550 ℃ at a heating rate of 7-10 ℃/min, namely, adopting programmed and gradient heating; the elementary phosphorus and the elementary cadmium in the system can be fully preheated by the early-stage heating procedure, the elementary phosphorus and the elementary cadmium are subjected to chemical combination reaction at a temperature far lower than the melting point of phosphorus, and then the complete chemical combination reaction of the elementary phosphorus and the elementary cadmium can be further promoted by the second-stage heating and heat preservation, so that the reaction yield is ensured.
As a preferable embodiment of the production method of the present invention, in the step (2), the gas pressure of the inert gas atmosphere is 2.5 to 3 MPa.
As a preferred embodiment of the preparation method of the present invention, in the step (2), the melting conditions are: the temperature is raised from room temperature to 600 ℃ at the temperature raising rate of 10-15 ℃/min, the temperature is maintained for 3-5h, then the temperature is raised to 900 ℃ at the temperature raising rate of 5-10 ℃/min, and the temperature is maintained for 2-5 h. As a preferred embodiment of the preparation method of the invention, in the step (2), the temperature is raised to 500-600 ℃ at the temperature raising rate of 10-15 ℃/min, and the rotation speed of the system is 10-15 r/min in the heat preservation process of 3-5 h; the temperature is increased to 800-900 ℃ at the temperature rising rate of 5-10 ℃/min, and the rotating speed of the system is 30-50 r/min in the process of heat preservation for 2-5 h.
In the melting process of the step (2), the pressure and the temperature of the system are controlled, and the formed cadmium phosphide can be further stabilized on the basis of the synthesized crude cadmium phosphide product, so that the cadmium phosphide synthetic material is obtained.
As a preferred embodiment of the preparation method of the present invention, in the step (2), after the cadmium phosphide synthetic material is obtained, a step of removing oxides on the surface of the cadmium phosphide synthetic material is further included, specifically, the oxides on the surface of the synthesized cadmium phosphide synthetic material are cut and removed.
As a preferable embodiment of the preparation method of the present invention, in the step (3), the particle size of the crushed cadmium phosphide is less than 3 mm.
As a preferred embodiment of the preparation method of the present invention, in the step (3), the particle size of the crushed cadmium phosphide is less than 3mm and more than 0.01 mm.
As a preferred embodiment of the preparation method of the present invention, in the step (3), the specific operation of removing impurities is: heating the crushed cadmium phosphide synthetic material to 450-550 ℃ in the environment of continuously introducing hydrogen, and preserving the heat for 5-10 h.
As a preferred embodiment of the preparation method of the present invention, the flow rate of the hydrogen gas is 3 to 10L/min.
As a preferred embodiment of the preparation method, inert gas is introduced into the crushed cadmium phosphide synthetic material before hydrogen is continuously introduced, the flow rate of the introduced inert gas is 3-10L/min, and the time for introducing the inert gas is 30-50 min.
Introducing inert gas to maintain an inert environment in the process of removing impurities, and then introducing hydrogen to react with residual oxygen in the cadmium phosphide synthetic material to remove oxygen elements; meanwhile, in the process of introducing nitrogen and hydrogen at a certain flow, the free substances on the surface of the cadmium phosphide synthetic material can be taken away, and the purity of the product is improved.
Compared with the prior art, the invention has the beneficial effects that:
firstly: according to the preparation method of the cadmium phosphide, provided by the technical scheme of the invention, a two-step synthesis method is adopted, firstly, a crude cadmium phosphide product is synthesized at a lower temperature, and then the cadmium phosphide is further stably synthesized by melting at a relatively higher temperature and pressure, so that the equipment requirement of a high-temperature high-pressure furnace in the traditional liquid phase synthesis method is effectively avoided, the safety in the synthesis process is improved, meanwhile, the two-step synthesis method adopts two temperature gradients for synthesis, the volatilization of phosphorus caused by high temperature is effectively avoided, and the synthesis yield is improved and the method is environment-friendly;
secondly, the method comprises the following steps: the preparation method of the cadmium phosphide provided by the technical scheme of the invention is matched with the subsequent steps of crushing and impurity removal, so that the prepared cadmium phosphide has higher purity, the content of free cadmium is less than 100ppm, the content of oxygen is less than 300ppm, and the total metal impurities are less than 10 ppm.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The preparation method of cadmium phosphide provided by the embodiment of the invention specifically comprises the following steps:
(1) weighing 10kg of simple substance red phosphorus powder and simple substance cadmium powder, wherein the particle sizes of the red phosphorus powder and the cadmium powder are between 100-150 meshes, and the molar ratio of the red phosphorus powder to the cadmium powder is 2: 3; uniformly mixing the weighed elemental red phosphorus powder and elemental cadmium powder, and then putting the mixture into a tubular furnace in an argon gas atmosphere; then, the temperature of the tube furnace is increased from room temperature to 320 ℃ at the heating rate of 3 ℃/min, the temperature is maintained for 50min, then the temperature is increased to 500 ℃ at the heating rate of 10 ℃/min, and the temperature is maintained for 60 min; after the heat preservation reaction is finished, cooling the material along with the furnace to obtain a cadmium phosphide crude product;
(2) putting the cadmium phosphide crude product into a crucible, then putting the crucible into a high-temperature high-pressure furnace, and firstly carrying out gas replacement on the high-temperature high-pressure furnace, wherein the method specifically comprises the following steps: closing the high-temperature high-pressure furnace, vacuumizing until the pressure in the system is less than 10-3pa, then the vacuum pump is closed, argon is filled in, and the process is repeatedDisplacement is carried out for three times; after the replacement is finished, introducing argon into the high-temperature high-pressure furnace until the gas pressure in the system is 2.5Mpa, starting rotation, and keeping the rotation speed at 15 r/min; then heating to 600 ℃ from room temperature at the heating rate of 12 ℃/min, and preserving heat for 4h, wherein the rotating speed of the crucible in the heat preservation process is 15 revolutions per minute; then heating to 900 ℃ at the heating rate of 8 ℃/min, and preserving heat for 2h, wherein the rotating speed of the dried fruits is 50 revolutions per minute in the heat preservation process; after the heat preservation reaction is finished, cooling the material along with the furnace to obtain a cadmium phosphide synthetic material;
(3) cutting to remove an oxide layer on the surface of the cadmium phosphide synthetic material, crushing to the particle size of 2mm, putting the crushed cadmium phosphide synthetic material into a graphite boat, then putting the graphite boat into a horizontal tube furnace, introducing argon at the flow rate of 3L/min for 50min, then introducing hydrogen at the flow rate of 10L/min, heating to the system value of 500 ℃, and keeping the temperature for 5 h; after the heat preservation reaction is finished, the temperature of the materials is reduced along with the furnace, and 9.67kg of cadmium phosphide is obtained.
Example 2
The preparation method of cadmium phosphide provided by the embodiment of the invention specifically comprises the following steps:
(1) weighing 10kg of elemental red phosphorus powder and elemental cadmium powder, wherein the particle sizes of the red phosphorus powder and the elemental cadmium powder are between 100-150 meshes, and the molar ratio of the red phosphorus powder to the cadmium powder is 2: 3; uniformly mixing the weighed elemental red phosphorus powder and elemental cadmium powder, and then putting the mixture into a tubular furnace in an argon gas atmosphere; then, the temperature of the tube furnace is increased from room temperature to 350 ℃ at the heating rate of 5 ℃/min, the temperature is maintained for 40min, then the temperature is increased to 520 ℃ at the heating rate of 8 ℃/min, and the temperature is maintained for 30 min; after the heat preservation reaction is finished, cooling the material along with the furnace to obtain a cadmium phosphide crude product;
(2) putting the cadmium phosphide crude product into a crucible, then putting the crucible into a high-temperature high-pressure furnace, and firstly carrying out gas replacement on the high-temperature high-pressure furnace, wherein the method specifically comprises the following steps: closing the high-temperature high-pressure furnace, vacuumizing until the pressure in the system is less than 10-3pa, then closing the vacuum pump, filling argon, and replacing for three times; after the replacement is finished, introducing argon into the high-temperature high-pressure furnace until the gas pressure in the system is 3Mpa, starting the rotation, and keeping the rotating speed of the rotation at 13 revolutions per minute; then raising the temperature from room temperature to 600 ℃ at the temperature rise rate of 15 ℃/min, and preserving the heat4h, the rotating speed of the crucible in the heat preservation process is 13 revolutions per minute; then heating to 800 ℃ at the heating rate of 10 ℃/min, and preserving heat for 3h, wherein the rotating speed of the crucible in the heat preservation process is 40 revolutions per minute; after the heat preservation reaction is finished, cooling the material along with the furnace to obtain a cadmium phosphide synthetic material;
(3) cutting to remove an oxide layer on the surface of the cadmium phosphide synthetic material, crushing to the particle size of 2mm, putting the crushed cadmium phosphide synthetic material into a graphite boat, then putting the graphite boat into a horizontal tube furnace, introducing argon at the flow rate of 7L/min for 40min, then introducing hydrogen at the flow rate of 6L/min, heating to the system value of 550 ℃, and keeping the temperature for 8 h; after the heat preservation reaction is finished, the temperature of the materials is reduced along with the furnace, and 9.72kg of cadmium phosphide is obtained.
Example 3
The preparation method of cadmium phosphide provided by the embodiment of the invention specifically comprises the following steps:
(1) weighing 10kg of elemental red phosphorus powder and elemental cadmium powder, wherein the particle sizes of the red phosphorus powder and the elemental cadmium powder are between 100-150 meshes, and the molar ratio of the red phosphorus powder to the cadmium powder is 2: 3; uniformly mixing the weighed elemental red phosphorus powder and elemental cadmium powder, and then putting the mixture into a tubular furnace in an argon gas atmosphere; then, the temperature of the tube furnace is increased from room temperature to 350 ℃ at the temperature increasing rate of 5 ℃/min, the temperature is maintained for 30min, then the temperature is increased to 550 ℃ at the temperature increasing rate of 10 ℃/min, and the temperature is maintained for 30 min; after the heat preservation reaction is finished, cooling the material along with the furnace to obtain a cadmium phosphide crude product;
(2) putting the cadmium phosphide crude product into a crucible, then putting the crucible into a high-temperature high-pressure furnace, and firstly carrying out gas replacement on the high-temperature high-pressure furnace, wherein the method specifically comprises the following steps: closing the high-temperature high-pressure furnace, vacuumizing until the pressure in the system is less than 10-3pa, then closing the vacuum pump, filling argon, and replacing for three times; after the replacement is finished, introducing argon into the high-temperature high-pressure furnace until the gas pressure in the system is 2.9Mpa, starting rotation, and keeping the rotation speed at 10 revolutions per minute; then heating to 550 ℃ from room temperature at the heating rate of 15 ℃/min, and preserving heat for 4h, wherein the rotating speed of the crucible in the heat preservation process is 10 revolutions per minute; then heating to 900 ℃ at the heating rate of 10 ℃/min, and preserving heat for 2h, wherein the rotating speed of the crucible in the heat preservation process is 30 revolutions per minute; after the heat preservation reaction is finished, the material is cooled along with the furnace to obtain the cadmium phosphide synthesisFeeding;
(3) cutting off an oxide layer on the surface of the cadmium phosphide synthetic material, crushing the material to the particle size of 2mm, putting the crushed cadmium phosphide synthetic material into a graphite boat, then putting the graphite boat into a horizontal tube furnace, introducing argon at the flow rate of 10L/min for 30min, introducing hydrogen at the flow rate of 10L/min, heating the material to the temperature of 450 ℃, and preserving the heat for 10 h; after the heat preservation reaction is finished, the temperature of the materials is reduced along with the furnace, and 9.75kg of cadmium phosphide is obtained.
Comparative example 1
The preparation method of cadmium phosphide of the comparative example of the invention specifically comprises the following steps:
(1) weighing simple substance red phosphorus powder and simple substance cadmium powder, wherein the particle size of the red phosphorus powder and the cadmium powder is between 100-plus-150 meshes, and the molar ratio of the red phosphorus powder to the cadmium powder is 2: 3; the method comprises the following steps of uniformly mixing weighed elemental red phosphorus powder and elemental cadmium powder, putting the mixture into a crucible, putting the crucible into a high-temperature high-pressure furnace, and firstly carrying out gas replacement on the high-temperature high-pressure furnace, wherein the method specifically comprises the following steps: closing the high-temperature high-pressure furnace, vacuumizing until the pressure in the system is less than 10-3pa, then closing the vacuum pump, filling argon, and replacing for three times; after the replacement is finished, introducing argon into the high-temperature high-pressure furnace until the gas pressure in the system is 2.9Mpa, starting rotation, and keeping the rotation speed at 10 revolutions per minute; then heating to 550 ℃ from room temperature at the heating rate of 15 ℃/min, and preserving heat for 4h, wherein the rotating speed of the crucible in the heat preservation process is 10 revolutions per minute; then heating to 900 ℃ at the heating rate of 10 ℃/min, and preserving heat for 2h, wherein the rotating speed of the crucible in the heat preservation process is 30 revolutions per minute; after the heat preservation reaction is finished, cooling the material along with the furnace to obtain a cadmium phosphide synthetic material;
(2) cutting off an oxide layer on the surface of the cadmium phosphide synthetic material, crushing the cadmium phosphide synthetic material into particles with the particle size of 2mm, putting the crushed cadmium phosphide synthetic material into a graphite boat, then putting the graphite boat into a horizontal tube furnace, introducing argon gas at the flow rate of 10L/min for 30min, then introducing hydrogen at the flow rate of 10L/min, heating the material to the system value of 450 ℃, and keeping the temperature for 10 hours; and after the heat preservation reaction is finished, cooling the material along with the furnace to obtain the cadmium phosphide.
Comparative example 2
The only difference between the comparative example and the example 1 is that in the step (1), the temperature is increased to 320 ℃ at the temperature increase rate of 10 ℃/min, the temperature is kept for 50min, and then the temperature is increased to 500 ℃ at the temperature increase rate of 10 ℃/min, and the temperature is kept for 60 min.
Comparative example 3
The only difference between the comparative example and the example 1 is that in the step (1), the temperature is raised to 320 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 50min, and then the temperature is raised to 650 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 60 min.
Comparative example 4
The only difference between the comparative example of the invention and the example 1 is that argon is introduced into the high-temperature high-pressure furnace after the replacement in the step (2) is finished until the gas pressure in the system is 0.5 MPa.
Comparative example 5
The only difference between the comparative example and the example 1 is that in the step (2), the temperature is increased to 600 ℃ from room temperature at the heating rate of 12 ℃/min, the temperature is kept for 4h, and the rotating speed of the crucible in the heat preservation process is 15 revolutions per minute; then the temperature is raised to 1000 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 2h, and the rotating speed of the crucible in the heat preservation process is 50 revolutions per minute.
Comparative example 6
The only difference between the comparative example and the example 1 is that in the step (2), the temperature is increased to 600 ℃ from room temperature at the heating rate of 12 ℃/min, the temperature is kept for 4h, and the rotating speed of the crucible in the heat preservation process is 15 revolutions per minute; then the temperature is increased to 900 ℃ at the heating rate of 15 ℃/min, the temperature is kept for 2h, and the rotating speed of the crucible in the heat preservation process is 50 revolutions per minute.
Comparative example 7
The only difference between the comparative example and the example 1 is that in the step (3), argon is introduced for 50min at the flow rate of 3L/min, then hydrogen is introduced at the flow rate of 10L/min, the system value is heated to 200 ℃, and the temperature is kept for 5 h.
Comparative example 8
The only difference between the comparative example and the example 1 is that in the step (3), argon is introduced for 50min at the flow rate of 3L/min, then hydrogen is introduced at the flow rate of 1L/min, the system value is heated to 500 ℃, and the temperature is kept for 5 h.
Examples of effects
The effect example verifies the yield of the cadmium phosphide product prepared in the examples 1-3 and the comparative examples 1-8 and the content of other elements in the product, and the specific detection result is shown in the table 1-2;
TABLE 1
| Yield (%) | Purity (%) | Free cadmium (ppm) | Oxygen (ppm) | |
| Example 1 | 96.7 | 5N | ＜100 | 238 |
| Example 2 | 97.2 | 5N | ＜100 | 277 |
| Example 3 | 97.5 | 5N | ＜100 | 293 |
| Comparative example 1 | 65.3 | 5N | ＜100 | 289 |
| Comparative example 2 | 92.5 | 5N | ＜100 | 254 |
| Comparative example 3 | 90.7 | 5N | ＜100 | 306 |
| Comparative example 4 | 83.5 | 5N | ＜100 | 268 |
| Comparative example 5 | 91.7 | 5N | ＜100 | 301 |
| Comparative example 6 | 94.8 | 5N | ＜100 | 265 |
| Comparative example 7 | 98.5 | 5N | ＞2000 | 1203 |
| Comparative example 8 | 97.9 | 5N | ＞2000 | 946 |
TABLE 2
As can be seen from table 1-2, when the technical scheme provided by the present invention is adopted, although a part of cadmium phosphide is inevitably removed when the oxide on the surface of the cadmium phosphide synthetic material is removed by cutting in the preparation process, overall, the preparation yield of the cadmium phosphide obtained by the technical scheme provided by the present invention is high, and is more than 97.2%; meanwhile, as can be seen from table 1, the cadmium phosphide obtained by the technical scheme of the invention has high purity, can reach 5N purity, and has low content of other impurity elements, which are all below 2 ppm;
as can be seen from the comparison between the example 1 and the comparative example 1, because the synthesis of the cadmium phosphide crude product is not carried out at a lower temperature in the comparative example 1, but the cadmium phosphide crude product is directly placed in a crucible and put into a high-temperature high-pressure furnace for reaction, and a large amount of volatilized phosphorus and cadmium can be seen in the process of furnace temperature reduction and furnace discharge, the yield of the comparative example 1 is obviously reduced; as can be seen from example 1 and comparative examples 2 and 3, when the temperature rise rate is too fast or the temperature after temperature rise is too high during the first step of the reaction, the yield of the obtained cadmium phosphide is reduced, because the too fast temperature rise or the too high temperature after temperature rise causes partial volatilization of phosphorus and cadmium in the first step, thereby reducing the yield; as can be seen from example 1 and comparative example 4, when the pressure of the system during the second-step reaction is too small, the yield of the product is lowered; as can be seen from example 1 and comparative examples 5 and 6, when the temperature rise rate is too high or the temperature after temperature rise is too high during the second-step reaction, the yield of the obtained cadmium phosphide is reduced, because the too high temperature rise rate or the too high temperature after temperature rise causes partial volatilization of phosphorus and cadmium in the second step, thereby reducing the yield; as can be seen from example 1 and comparative examples 7 and 8, the content of free cadmium in the cadmium phosphide product prepared is remarkably increased when the temperature in the impurity removal process is reduced or the hydrogen flow rate in the impurity removal process is reduced.
Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the cadmium phosphide is characterized by comprising the following steps of:
(1) uniformly mixing elemental phosphorus and elemental cadmium, and placing the mixture in an inert gas environment for chemical combination reaction to obtain a cadmium phosphide crude product;
(2) melting the crude cadmium phosphide product obtained in the step (1) in an inert gas environment to obtain a cadmium phosphide synthetic material;
(3) and (3) crushing and removing impurities from the cadmium phosphide synthetic material obtained in the step (2) to obtain cadmium phosphide.
2. The method according to claim 1, wherein in the step (1), the molar ratio of the elemental phosphorus to the elemental cadmium is 2: 3.
3. The production method according to claim 1, wherein in the step (1), the conditions of the combination reaction are: the temperature is raised from room temperature to 350 ℃ at the heating rate of 3-5 ℃/min, the temperature is maintained for 30-50min, then the temperature is raised to 550 ℃ at the heating rate of 7-10 ℃/min, and the temperature is maintained for 30-60 min.
4. The production method according to claim 1, wherein in the step (2), the gas pressure of the inert gas atmosphere is 2.5 to 3 Mpa.
5. The production method according to claim 1, wherein in the step (2), the melting conditions are: the temperature is raised from room temperature to 600 ℃ at the temperature raising rate of 10-15 ℃/min, the temperature is maintained for 3-5h, then the temperature is raised to 900 ℃ at the temperature raising rate of 5-10 ℃/min, and the temperature is maintained for 2-5 h.
6. The preparation method according to claim 5, wherein the temperature is raised to 500-600 ℃ at a temperature raising rate of 10-15 ℃/min, and the rotation speed of the system is 10-15 rpm in the process of heat preservation for 3-5 h; the temperature is increased to 800-900 ℃ at the temperature rising rate of 5-10 ℃/min, and the rotating speed of the system is 30-50 r/min in the process of heat preservation for 2-5 h.
7. The method according to claim 1, wherein in the step (3), the particle size of the crushed cadmium phosphide is less than 3 mm.
8. The preparation method according to claim 1, wherein in the step (3), the specific operation of removing impurities is as follows: heating the crushed cadmium phosphide synthetic material to 450-550 ℃ in the environment of continuously introducing hydrogen, and preserving the heat for 5-10 h.
9. The production method according to claim 8, wherein the flow rate of the hydrogen gas is 3 to 10L/min.
10. The preparation method according to claim 8, wherein inert gas is introduced into the crushed cadmium phosphide synthetic material before hydrogen is continuously introduced, the flow rate of the introduced inert gas is 3-10L/min, and the time for introducing the inert gas is 30-50 min.
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