CN110104623A - A kind of preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape - Google Patents
A kind of preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape Download PDFInfo
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- CN110104623A CN110104623A CN201910368874.5A CN201910368874A CN110104623A CN 110104623 A CN110104623 A CN 110104623A CN 201910368874 A CN201910368874 A CN 201910368874A CN 110104623 A CN110104623 A CN 110104623A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention discloses a kind of preparation methods of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape.This method includes mixing the cobalt-based predecessor (cobaltosic oxide, cobalt hydroxide, cobalt-based organic-inorganic presoma etc.) and phosphorus source of different-shape according to atomic ratio 1:4.5 ~ 1:5.5 of cobalt, phosphorus, it is packaged in quartz ampoule by high vacuum, is 5 × 10 in 1100 ~ 1200K of temperature, vacuum degree‑5~5×10‑46 ~ 10h of high-temperature high-voltage reaction under conditions of Pa overcomes four phosphatization cobalts under usual terms to synthesize the chemical potential being unable to reach, then uses CS2Removing extra phosphorus to gained grey black sample treatment can be obtained high-purity and high-crystallinity four phosphatization cobalt of different-shape, and raw material are cheap, synthesis is simple and convenient to operate, morphology controllable, be suitable for preparing and applying on a large scale.
Description
Technical field
The invention belongs to Phos Material Fields, and in particular to a kind of rich four phosphorus of phosphorus transition metal phosphide of different-shape
Change the preparation method of cobalt.
Background technique
Four phosphatization cobalt materials belong to cubic crystal structure, and each cobalt atom is surrounded by eight phosphorus atoms, peripheral phosphorus atoms
Constitute octahedral structure.The four phosphatization cobalts that the structure is formed have very small band gap, and it is defeated to form special electricity and heat
Fortune feature becomes potential electrocatalytic decomposition water, cell negative electrode material and thermoelectric material.In common low-temp low-pressure condition
Under, a phosphatization cobalt material can only be synthesized, be difficult to synthesize four phosphatization cobalt materials, it is even more impossible to regulate and control its pattern.Due to four phosphatizations
The synthesis of cobalt needs to overcome the chemical potential for synthesizing and being unable to reach under usual terms, therefore the pertinent literature of four phosphatization cobalts synthesis is very
Lack.1967, Ronald A. Munson etc. synthesized CoP using transition metal simple substance cobalt and red phosphorus sintering method for the first time4
(Inorg. Chem., nineteen sixty-eight, volume seven, 390-391 pages), later almost without report.This method be synthesized four
Phosphatization cobalt, size all in the micron-scale more than, be easy the appearance with low-phosphorousization cobalt and be unfavorable for Morphological control, in addition transition is golden
The price for belonging to simple substance cobalt valuableness is unfavorable for preparing on a large scale, therefore finds cheap method and synthesize four high-purity phosphatization cobalts simultaneously
Regulate and control its pattern to have great importance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the four phosphatization cobalt of transition metal phosphide of rich phosphorus, this method behaviour
Work is simple, is easily-synthesized, cheap and morphology controllable.
To achieve the above object, the step of the technical solution adopted in the present invention is:
A kind of preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape, comprising the following steps: will not similar shape
The cobalt-based predecessor and phosphorus source of looks are mixed according to atomic ratio 1:4.5~1:5.5 of cobalt, phosphorus, are packaged in by high vacuum
It is 5 × 10 in 1100~1200K of temperature, vacuum degree in quartz ampoule-5~5 × 10-4High-temperature high-voltage reaction 6 under conditions of Pa~
10h overcomes four phosphatization cobalts under usual terms to synthesize the chemical potential being unable to reach, then uses CS2It is extra to remove to gained sample treatment
Phosphorus can be obtained.
Further, commercially available commodity can be used in the cobalt-based predecessor, can also pass through hydro-thermal, solvent heat, sol-gel
The methods of be prepared, in particular to cobalt-based predecessor hollow nanospheres piece, cobaltosic oxide powder, cobalt-based predecessor nanometer
Line, cobalt-based predecessor nanometer sheet or cobalt-based predecessor nanosphere.
The synthesis temperature is 1100~1200K, and heating rate is 2~4K/min.
Further, the specific preparation process of cobalt-based predecessor hollow nanospheres piece is as follows:
(1) jar agitation for 25mL isopropanol and 7mL glycerine being poured into 50mL is uniform, and six water nitric acid of 0.582g is then added
Cobalt, stirring and dissolving；
(2) solution of step (1) is poured into 180 DEG C of hydro-thermal reaction 6h in the ptfe autoclave liner of 50mL, it is natural
It is down to room temperature, by sediment centrifugation, washing, drying；
(3) powder that step (2) obtain is dispersed into 32mL ultrapure water, then in 180 DEG C of hydro-thermal reaction 6h, to be down to naturally
Room temperature, by sediment centrifugation, washing, it is dry to get.
Further, the specific preparation process of the cobaltosic oxide powder is as follows:
(1) cobalt nitrate solution that 6mL concentration is 0.26mol/L is poured into 40mL concentration is in the methylimidazole of 1.18mol/L
12h is stirred at normal temperature, is collected precipitating, 80 DEG C of dryings, is obtained cobalt-based presoma；
(2) cobalt-based presoma is made annealing treatment 5 hours in 300 DEG C of air, obtains the cobaltosic oxide powder of black.
Wherein, the specific preparation process of cobalt-based predecessor nano wire are as follows:
(1) first carbon cloth is impregnated 2 hours in the dust technology that mass fraction is 20%, takes out carbon cloth, washing, drying, it is spare；
(2) 0.582g cobalt nitrate hexahydrate, 0.186g ammonium fluoride and 0.6g urea are successively dissolved in water, stirring at normal temperature 30 is divided
Clock obtains solution；
(3) solution is transferred in 50mL ptfe autoclave liner, and washed drying carbon cloth is put into reaction kettle vertically
In liner, seal reaction kettle, in 120 DEG C of hydro-thermal reaction 6h, take out carbon cloth, cleaning, air drying to get.
Wherein, the specific preparation process of cobalt-based predecessor nanometer sheet is as follows:
(1) first carbon cloth is impregnated 2 hours in the dust technology that mass fraction is 20%, takes out carbon cloth, washing, drying, it is spare；
(2) 2.328g cobalt nitrate hexahydrate, 0.106g ammonium fluoride and 1.2g urea are successively dissolved in 40mL water, stirring at normal temperature 60
Minute, obtain homogeneous solution；
(3) homogeneous solution is transferred in 50mL ptfe autoclave liner, and washed drying carbon cloth is put into instead vertically
Answer in kettle liner, seal reaction kettle, in 120 DEG C of hydro-thermal reaction 22h, take out carbon cloth, cleaning, air drying to get.
Wherein, the specific preparation process of cobalt-based predecessor nanosphere is as follows:
(1) first carbon cloth is impregnated 2 hours in the dust technology that mass fraction is 20%, takes out carbon cloth, washing, drying, it is spare；
(2) 1.455g cobalt nitrate hexahydrate and 0.2g ammonium nitrate are successively dissolved in 40mL ultrapure water, stirring at normal temperature 60 minutes, are obtained
To homogeneous solution, then the above-mentioned solution of ammonium hydroxide addition that 5mL mass fraction is 25wt% is stirred 30 minutes and obtains homogeneous solution；
(3) homogeneous solution is transferred in 25mL ptfe autoclave liner, and washed drying carbon cloth is put into instead vertically
Answer in kettle liner, seal reaction kettle, in 90 DEG C of hydro-thermal reaction 14h, take out carbon cloth, cleaning, air drying to get.
Further, phosphorus source is one or both of sodium hypophosphite, potassium hypophosphite, hypophosphorous acid, white phosphorus and red phosphorus
The mixture of any of the above ratio.
Advantages of the present invention:
The present invention is with the cobalt-based predecessor (cobalt oxide, cobalt hydroxide, cobalt-based organic-inorganic presoma etc.) and phosphorus source of different-shape
For four phosphatization cobalts of Material synthesis different-shape, raw material are cheap, synthesis is simple and convenient to operate, morphology controllable, are suitable for advising greatly
The preparation and application of mould.Desulfurization-hydrogenation of the four phosphatization cobalt of rich phosphorus of preparation in petroleum coal, electrocatalytic decomposition water, battery cathode material
Material and thermoelectric material etc. all have a good application prospect.
Detailed description of the invention
Fig. 1 is the CoP prepared in embodiment 14The XRD and SEM of hollow nanospheres piece scheme；
Fig. 2 is the CoP prepared in embodiment 24The XRD and SEM of nanometer polyhedral scheme；
Fig. 3 is the CoP prepared on carbon cloth in embodiment 34The XRD and SEM of nano-wire array scheme；
Fig. 4 is the CoP prepared on carbon cloth in embodiment 44The XRD and SEM of nano-chip arrays scheme；
Fig. 5 is the CoP prepared on carbon cloth in embodiment 54XRD and the SEM figure of nanometer ball array；
Fig. 6 is the CoP prepared in comparative example 14The XRD and SEM of particle scheme；
Fig. 7 is the XRD diagram of the CoP prepared in comparative example 2.
Specific embodiment
The synthesis of four phosphatization cobalt of different-shape of the invention is described further below in conjunction with specific example, but not structure
At any limitation of the invention.
Flexibility carbon cloth used in text is all bought in the gloomy Electrical Appliances Co., Ltd in upper Haihe River, model are as follows: HCP330N(is hydrophilic
Type).
Embodiment 1
The preparation method of four phosphatization cobalt hollow nanospheres pieces of rich phosphorus in the present embodiment, comprising the following steps:
Step 1: the jar agitation that 25mL isopropanol and 7mL glycerine are poured into 50mL is uniform, then by six water nitric acid of 0.582g
Cobalt is dissolved in formation purple clear solution in above-mentioned mixed solution.
Step 2: by previous step obtain purple clear solution pour into the ptfe autoclave liner of 50mL
Sediment is centrifuged by 180 DEG C of hydro-thermal reaction 6h to be down to room temperature naturally, and dehydrated alcohol washs three times, and air drying obtains powder
Body.
Step 3: the powder that previous step obtains is dispersed into 32mL ultrapure water, then in 180 DEG C of hydro-thermal reaction 6h, to
Naturally it is down to room temperature, three times by sediment centrifugation, washing, air drying obtains cobalt-based predecessor hollow nanospheres piece.
Step 4: 100mg cobalt-based predecessor hollow nanospheres piece obtained in the previous step and 200mg red phosphorus are mixed, true
Pneumatics power is 5 × 10-5It is sealed in quartz ampoule under the conditions of Pa, the conformal phosphatization of 1150K high temperature 8 hours, takes out, be immersed in pure CS2
Middle processing 30min, which removes extra phosphorus surface and becomes ater, can be obtained four phosphatization cobalt hollow nanospheres pieces of rich phosphorus, SEM
Photo and XRD diagram are shown in Fig. 1, from SEM and XRD(Fig. 1 of four phosphatization cobalt hollow nanospheres pieces) as can be seen that embodiment 1 has succeeded
Synthesize high-purity and crystallinity four phosphatization cobalt hollow nanospheres pieces, further analysis finds that four phosphatization cobalts of synthesis are hollow to be received
Rice ball piece be by with a thickness of several nanometers sheet accumulation into 800nm it is spherical, size is very small, unique hollow nanometer
Structure has very big specific surface area, and adding in electrocatalytic decomposition elutriation hydrogen and petroleum coal desulfurization can expose more in hydrogen
Active site has very wide application prospect.
Embodiment 2
The preparation method of four phosphatization cobalt nanometer polyhedrals of rich phosphorus, includes the following steps in the present embodiment
Step 1: the cobalt nitrate solution that 6mL concentration is 0.26mol/L is poured into the dimethyl miaow that 40mL concentration is 1.18mol/L
12h is persistently stirred in azoles at normal temperature, the violet precipitate of acquisition is collected, 80 DEG C of dry 8 ~ 10h obtain cobalt-based presoma.
Step 2: cobalt-based presoma is annealed five hours in 300 DEG C of air, the cobaltosic oxide powder of black is obtained.
Step 3: it is 5 × 10 that the red phosphorus of the black cobaltosic oxide powder of 100mg and 200mg, which are mixed vacuum pressure,-5Pa item
It is sealed in quartz ampoule under part, the conformal phosphatization of 1150K high temperature 8 hours, takes out, be immersed in pure CS2Middle processing 30min removal is extra
Phosphorus, surface, which becomes ater, can be obtained four phosphatization cobalt nanometer polyhedrals of rich phosphorus, and SEM and XRD diagram are detailed in Fig. 2, from four
The SEM and XRD diagram of phosphatization cobalt nanometer polyhedral can be seen that embodiment 2 and successfully synthesized high-purity and crystallinity four phosphatizations
Cobalt nanometer polyhedral, further analysis find, the sizes of four phosphatization cobalt nanometer polyhedrals of synthesis in 300-600 ran,
In addition the presoma is organic matter meeting self-assembling formation carbon load in annealing parkerizing process, can be further improved electric conductivity,
There is important application in lithium, sodium-ion battery.
Embodiment 3
Self-supporting grows the preparation method of four phosphatization cobalt nanowires on carbon cloth in the present embodiment, includes the following steps
Step 1: flexible carbon cloth is first impregnated two hours in the dust technology that mass fraction is 20%, it is protonated,
Then take out flexible carbon cloth water, dehydrated alcohol successively washs drying for standby three times.
Step 2: 0.582g cobalt nitrate hexahydrate, 0.186g ammonium fluoride and 0.6g urea are successively dissolved in 40mL ultrapure water
In, stirring at normal temperature 30 minutes, obtain homogeneous solution.
Step 3: homogeneous solution is transferred in 50mL ptfe autoclave liner, and washed drying for standby is soft
Property carbon cloth be put into reaction kettle liner vertically, reaction kettle is sealed, in 120 DEG C of hydro-thermal reaction 6h, takes out carbon cloth, with water, anhydrous
Ethyl alcohol clean the surface, air drying obtains the cobalt-based predecessor nano wire grown on carbon cloth, spare.
It is 5 × 10 in vacuum pressure step 4: the dried carbon cloth of previous step and 70mg red phosphorus are mixed-5It is close under the conditions of Pa
It is enclosed in quartz ampoule, then the conformal phosphatization of 1100K high temperature 6 hours, takes out, be immersed in pure CS2It is extra that middle processing 30min is removed
Phosphorus, surface, which becomes ater, can be obtained the four phosphatization cobalt nanowire arrays that self-supporting is grown on carbon cloth, SEM and XRD diagram
It is detailed in Fig. 3.From SEM and XRD(Fig. 3 of four phosphatization cobalt nanowire arrays) as can be seen that the present embodiment successfully synthesized it is high-purity
With four phosphatization cobalt nanowire arrays of crystallinity, further analysis finds that four phosphatization cobalt nanowires of synthesis are equably grown in
On carbon cloth, each nano wire about 20nm is thick, 1 μm long, and the flexible electrode of this self-supporting can directly do the cathode material of battery
Material and electrocatalysis material, avoid powder body material and do the cumbersome of electrode.
Embodiment 4:
Self-supporting grows the preparation method of four phosphatization cobalt nanometer sheets on carbon cloth in the present embodiment, includes the following steps
Step 1: flexible carbon cloth is first impregnated two hours in the dust technology that mass fraction is 20%, it is protonated,
Then take out flexible carbon cloth water, dehydrated alcohol successively washs drying for standby three times.
Step 2: 2.328g cobalt nitrate hexahydrate, 0.106g ammonium fluoride and 1.2g urea are successively dissolved in 40mL water, often
Temperature stirring 60 minutes, obtains homogeneous solution.
Step 3: homogeneous solution is transferred in 50mL ptfe autoclave liner, and washed drying for standby is soft
Property carbon cloth be put into reaction kettle liner vertically, reaction kettle is sealed, in 120 DEG C of hydro-thermal reaction 22h, takes out carbon cloth, with water, ethyl alcohol
Clean the surface, air drying obtains the cobalt-based predecessor nanometer sheet grown on carbon cloth, spare.
Step 4: it is 5 × 10 that the dried carbon cloth of previous step and 70mg red phosphorus, which are mixed vacuum pressure,-5It is sealed under the conditions of Pa
In quartz ampoule, then the conformal phosphatization of 1100K high temperature 7 hours, takes out, is immersed in pure CS2Middle processing 30min removes extra phosphorus,
Surface, which becomes ater, can be obtained the four phosphatization cobalt nano-chip arrays that self-supporting is grown on carbon cloth, and SEM and XRD diagram are detailed in
Fig. 4.From SEM and XRD(Fig. 4 of four phosphatization cobalt nano-chip arrays) as can be seen that the present embodiment has successfully synthesized high-purity and knot
Four phosphatization cobalt nano-chip arrays of brilliant degree, further analysis find that four phosphatization cobalt nanometer sheets of synthesis are equably grown in carbon cloth
On, each nanometer sheet thickness about 10nm, the flexible electrode of this self-supporting can directly do the negative electrode material and electro-catalysis of battery
Material avoids powder body material and does the cumbersome of electrode.
Embodiment 5:
Self-supporting grows the preparation method of four phosphatization cobalt nanospheres on carbon cloth in the present embodiment, comprising the following steps:
Step 1: flexible carbon cloth is first impregnated two hours in the dust technology that mass fraction is 20%, it is protonated,
Then take out flexible carbon cloth water, ethyl alcohol successively washs drying for standby three times.
Step 2: 1.455g cobalt nitrate hexahydrate and 0.2g ammonium nitrate are successively dissolved in 15mL ultrapure water, stirring at normal temperature
60 minutes, homogeneous solution is obtained, then the above-mentioned solution of ammonium hydroxide addition that 5ml mass fraction is 25wt% is stirred 30 minutes and is obtained
Homogeneous solution.
Step 3: the homogeneous solution of previous step is transferred in 25mL ptfe autoclave liner, and washed is done
Dry spare flexible carbon cloth is put into vertically in reaction kettle liner, and reaction kettle is sealed, in 90 DEG C of hydro-thermal reaction 14h, takes out carbon cloth, uses
Water, washes of absolute alcohol surface, the cobalt-based predecessor nanosphere air drying that air drying obtains growing on carbon cloth are spare.
Step 4: it is 5 × 10 that the dried carbon cloth of previous step and 70mg red phosphorus, which are mixed vacuum pressure,-5It is sealed under the conditions of Pa
In quartz ampoule, then the conformal phosphatization of 1200K high temperature 10 hours, takes out, is immersed in pure CS2Middle processing 30min removes extra phosphorus,
Surface, which becomes ater, can be obtained the four phosphatization cobalt nanometer ball arrays that self-supporting is grown on carbon cloth, and SEM and XRD diagram are detailed in
Fig. 5.From SEM and XRD(Fig. 5 of four phosphatization cobalt nanometer ball arrays) as can be seen that the present embodiment has successfully synthesized high-purity and knot
Four phosphatization cobalt nanometer ball arrays of brilliant degree, further analysis find that four phosphatization cobalt nanospheres of synthesis are equably grown in carbon cloth
On, the flexible electrode of each nanometer of bulb diameter about 400nm, this self-supporting can directly do the negative electrode material of battery and electricity is urged
Change material, avoids powder body material and do the cumbersome of electrode.
Comparative example 1
In this comparative example four phosphatization cobalts the preparation method comprises the following steps:
According to synthetic methods such as Ronald A. Munson in 1967 by 750 DEG C of high temperature sinterings 10 of the metal cobalt powder of purchase and red phosphorus
Hour obtains four phosphatization cobalts, and SEM and XRD diagram are detailed in Fig. 6, it will be appreciated from fig. 6 that the four phosphatization cobalt patterns that this method is synthesized are not
Rule, in the micron-scale, specific surface area is small for size, and cobalt powder is expensive is unfavorable for preparation of industrialization and application.
Comparative example 2
It will be sealed directly in quartz ampoule under the cobalt-based predecessor synthesized in embodiment 3 and 70mg red phosphorus normal pressure, directly in tubular type
350 DEG C of high temperature phosphorizations in furnace find that the material being synthesized is a phosphatization cobalt even if temperature is risen to 950 DEG C of phosphatizations 20 hours,
XRD is as shown in fig. 7, it can thus be seen that the synthesis of four phosphatization cobalts needs to overcome the chemistry for synthesizing and being unable to reach under usual terms
Gesture can just be synthesized, and not synthesize not come out under usual terms.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape, which is characterized in that including as follows
Step: different-shape cobalt-based predecessor and phosphorus source are mixed according to atomic ratio 1:4.5~1:5.5 of cobalt, phosphorus, in temperature
1100~1200K, vacuum degree are 5 × 10-5~5×10-4CS is used in 6~10h of reaction under confined conditions of Pa, taking-up again2To gained sample
Product processing removes extra phosphorus to obtain the final product.
2. the preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape according to claim 1, feature
It is, different-shape cobalt-based predecessor specifically refers to cobalt-based predecessor hollow nanospheres piece, cobaltosic oxide powder, cobalt-based forerunner
Object nano wire, cobalt-based predecessor nanometer sheet or cobalt-based predecessor nanosphere.
3. the preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape according to claim 2, feature
It is, the specific preparation process of cobalt-based predecessor hollow nanospheres piece is as follows:
(1) jar agitation for 25mL isopropanol and 7mL glycerine being poured into 50mL is uniform, and six water nitric acid of 0.582g is then added
Cobalt, stirring and dissolving；
(2) solution of step (1) is poured into 180 DEG C of hydro-thermal reaction 6h in the ptfe autoclave liner of 50mL, it is natural
It is down to room temperature, by sediment centrifugation, washing, drying；
(3) powder that step (2) obtain is dispersed into 32mL ultrapure water, then in 180 DEG C of hydro-thermal reaction 6h, to be down to naturally
Room temperature, by sediment centrifugation, washing, it is dry to get.
4. the preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape according to claim 2, feature
It is, the specific preparation process of the cobaltosic oxide powder is as follows:
(1) cobalt nitrate solution that 6mL concentration is 0.26mol/L is poured into 40mL concentration is in the methylimidazole of 1.18mol/L
12h is stirred at normal temperature, is collected precipitating, 80 DEG C of dryings, is obtained cobalt-based presoma；
(2) cobalt-based presoma is made annealing treatment 5 hours in 300 DEG C of air, obtains the cobaltosic oxide powder of black.
5. the preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape according to claim 2, feature
It is, the specific preparation process of cobalt-based predecessor nano wire are as follows:
(1) first carbon cloth is impregnated 2 hours in the dust technology that mass fraction is 20%, takes out carbon cloth, washing, drying, it is spare；
(2) 0.582g cobalt nitrate hexahydrate, 0.186g ammonium fluoride and 0.6g urea are successively dissolved in 40mL ultrapure water, room temperature stirs
It mixes 30 minutes, obtains solution；
(3) solution is transferred in 50mL ptfe autoclave liner, and washed drying carbon cloth is put into reaction kettle vertically
In liner, seal reaction kettle, in 120 DEG C of hydro-thermal reaction 6h, take out carbon cloth, cleaning, air drying to get.
6. the preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape according to claim 2, feature
It is, the specific preparation process of cobalt-based predecessor nanometer sheet is as follows:
(1) first carbon cloth is impregnated 2 hours in the dust technology that mass fraction is 20%, takes out carbon cloth, washing, drying, it is spare；
(2) 2.328g cobalt nitrate hexahydrate, 0.106g ammonium fluoride and 1.2g urea are successively dissolved in 40mL water, stirring at normal temperature 60
Minute, obtain homogeneous solution；
(3) homogeneous solution is transferred in 50mL ptfe autoclave liner, and washed drying carbon cloth is put into instead vertically
Answer in kettle liner, seal reaction kettle, in 120 DEG C of hydro-thermal reaction 22h, take out carbon cloth, cleaning, air drying to get.
7. the preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape according to claim 2, feature
It is, the specific preparation process of cobalt-based predecessor nanosphere is as follows:
(1) first carbon cloth is impregnated 2 hours in the dust technology that mass fraction is 20%, takes out carbon cloth, washing, drying, it is spare；
(2) 1.455g cobalt nitrate hexahydrate and 0.2g ammonium nitrate are successively dissolved in water, stirring at normal temperature 60 minutes, are obtained uniformly molten
Liquid, then the above-mentioned solution of ammonium hydroxide addition that 5mL mass fraction is 25wt% is stirred 30 minutes and obtains homogeneous solution；
(3) homogeneous solution is transferred in 25mL ptfe autoclave liner, and washed drying carbon cloth is put into instead vertically
Answer in kettle liner, seal reaction kettle, in 90 DEG C of hydro-thermal reaction 14h, take out carbon cloth, cleaning, air drying to get.
8. the preparation method of the four phosphatization cobalt of rich phosphorus transition metal phosphide of different-shape according to claim 1, feature
It is, phosphorus source is one or more of sodium hypophosphite, potassium hypophosphite, hypophosphorous acid, white phosphorus and red phosphorus arbitrary proportion
Mixture.
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Cited By (4)
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|---|---|---|---|---|
| CN112479170A (en) * | 2020-12-23 | 2021-03-12 | 河南大学 | Cobalt tetraphosphoride with core-shell structure and preparation method and application thereof |
| CN114284496A (en) * | 2021-11-16 | 2022-04-05 | 石家庄科林电气股份有限公司 | Preparation method of three-dimensional large-framework multi-level structure electrode material |
| CN114590844A (en) * | 2022-05-04 | 2022-06-07 | 台州学院 | Mesoporous Co3O4CoO/CoP and preparation method thereof |
| CN114956019A (en) * | 2022-01-14 | 2022-08-30 | 哈尔滨工业大学（深圳） | Method for one-step synthesis of cobalt phosphide by molten salt mediation and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660695A (en) * | 2004-02-26 | 2005-08-31 | 中国科学院大连化学物理研究所 | Method for preparing phosphide of transition metal |
| CN101475152A (en) * | 2009-01-20 | 2009-07-08 | 中国科学技术大学 | Method for preparing Co2P or/and CoP nano-rod |
| CN102181897A (en) * | 2011-04-13 | 2011-09-14 | 清华大学 | Method for preparing Co-P membrane |
| CN106672928A (en) * | 2017-01-12 | 2017-05-17 | 南京师范大学 | CoxPy porous nanometer sheet, and synthesis method and application thereof |
| CN107980072A (en) * | 2015-03-31 | 2018-05-01 | Inl-国际伊比利亚纳米技术实验室 | The manufacture method of porous electrode material |
-
2019
- 2019-05-05 CN CN201910368874.5A patent/CN110104623B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660695A (en) * | 2004-02-26 | 2005-08-31 | 中国科学院大连化学物理研究所 | Method for preparing phosphide of transition metal |
| CN101475152A (en) * | 2009-01-20 | 2009-07-08 | 中国科学技术大学 | Method for preparing Co2P or/and CoP nano-rod |
| CN102181897A (en) * | 2011-04-13 | 2011-09-14 | 清华大学 | Method for preparing Co-P membrane |
| CN107980072A (en) * | 2015-03-31 | 2018-05-01 | Inl-国际伊比利亚纳米技术实验室 | The manufacture method of porous electrode material |
| CN106672928A (en) * | 2017-01-12 | 2017-05-17 | 南京师范大学 | CoxPy porous nanometer sheet, and synthesis method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| K. ISHIDA，ET AL.: "The Co-P (Cobalt-Phosphorus) system", 《BULLETIN OF ALLOY PHASE DIAGRAMS》 * |
| R.A. MUNSON,ET AL.: "Formation of the skutterudite phase in the cobalt-phosephorus system", 《INORGANIC CHEMISTRY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112479170A (en) * | 2020-12-23 | 2021-03-12 | 河南大学 | Cobalt tetraphosphoride with core-shell structure and preparation method and application thereof |
| CN114284496A (en) * | 2021-11-16 | 2022-04-05 | 石家庄科林电气股份有限公司 | Preparation method of three-dimensional large-framework multi-level structure electrode material |
| CN114284496B (en) * | 2021-11-16 | 2023-07-25 | 石家庄科林电气股份有限公司 | Preparation method of three-dimensional large-framework multi-stage structure electrode material |
| CN114956019A (en) * | 2022-01-14 | 2022-08-30 | 哈尔滨工业大学（深圳） | Method for one-step synthesis of cobalt phosphide by molten salt mediation and application thereof |
| CN114590844A (en) * | 2022-05-04 | 2022-06-07 | 台州学院 | Mesoporous Co3O4CoO/CoP and preparation method thereof |
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