CN104118852B - A kind of transition metal phosphide Co 2the preparation method of P - Google Patents
A kind of transition metal phosphide Co 2the preparation method of P Download PDFInfo
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Abstract
The present invention relates to a kind of transition metal phosphide Co
2the preparation method of P, belongs to transition metal phosphide synthesis technical field.Preparation method of the present invention, using Tong – phosphorus alloy as phosphorus source, using Tong – cobalt-base alloy or cobalt as cobalt source, is first smelted into ingot metal by cobalt source and phosphorus source vacuum arc melting furnace; Then the process of ingot metal ferric chloride Solution is overflowed to bubble-free, Co
2p.Phosphorus source of the present invention is nontoxic, stable in properties, cheap, easily and the melting of cobalt source; Required for abundant melting, the time is short; Stable, the easy control of melting process, safety.Carry out melting with vacuum arc melting furnace, by i.e. temperature controllable of adjusting frequency, make the adjustable easy control of melting process, ensure that productive rate reaches 98.7-100% simultaneously; Adopt ferric chloride Solution to process, make product purity up to 99.3-100%, and ensure Co simultaneously
2p is vesicular structure, Kong Duo, little and evenly, specific surface area is large, active high.
Description
Technical field
The present invention relates to a kind of transition metal phosphide Co
2the preparation method of P, belongs to transition metal phosphide synthesis technical field.
Background technology
Transition metal phosphide (TM – P) is the general name of the binary that formed of transition metal and phosphorus or multi-element compounds, has metal and characteristic of semiconductor concurrently, because of its structure and have significant characteristic day by day receive publicity in electricity, mechanics and erosion resistance etc.Meanwhile, it is widely used in hydrogenating desulfurization, denitrogenation aspect as a kind of good catalyzer, to succeed application at chemical fields such as refining of petroleum.Co – P is as the Typical Representative of transition metal phosphide, have supraconductivity, ferromegnetism, magnetic heat inserts with magnetoresistance effect, photocatalysis performance and lithium ion/serial physical and the chemical property such as release capacity, be widely used in the fields such as opto-electronic device, magnetic memory device, magnetic refrigerating system, Industrial Catalysis and lithium ion battery material.
The tradition preparation of transition metal phosphide comprises: prepared by metal simple-substance and the direct chemical combination of red phosphorus; Dehalogenation silane reaction; Liquid phase replacement(metathesis)reaction; The thermolysis in organic solvent of single source precursor; Phosphoric acid salt reduces; Solvent thermal reaction.The many needs of above-mentioned preparation process carry out under the severe condition such as High Temperature High Pressure, and reaction is mainly with red phosphorus, hypertoxic PH
3as phosphorus source, cause process wayward, and produce more by product.
The stoichiometric ratio of phosphatization cobalt is very abundant, and the chemical property of cobalt element is very active, and phosphonium ion is unstable in aqueous systems, and these bring very large difficulty and challenge all to the work of preparation phosphatization cobalt.Therefore, relative to the preparation of other phosphides, the preparation method of phosphatization cobalt also seldom.As, Yuan Feifei adopts water and ethanol to make reaction solvent, and cobalt chloride and white phosphorus are as initial reactant, and Sodium dodecylbenzene sulfonate is tensio-active agent, and vulkacit H is pH adjusting agent, react 800min and prepare nano bar-shape Co at 170 DEG C
2p.In reaction process, require to use autoclave, the reaction times reaches more than 10h, and the follow-up drying of powder need be carried out under vacuum; White phosphorus high toxicity and inflammable, thus this preparation method exist potential safety hazard (Yuan Feifei. the synthesis of phosphatization cobalt nano material, sign and performance study thereof. Anhui Normal University, master thesis).The Yellow River adopts hydrothermal method to prepare Co
2p nano-powder, first adopt mortar, autoclave, constant temperature oven to carry out hydrothermal treatment consists to red phosphorus, this process needs 24h.Adopt Co (NO again
3)
26H
2content, as cobalt source, to be carried out vacuum filtration, distilled water flushing, vacuum-drying and finally obtain Co in autoclave, 180 – 200 DEG C, reaction by O after tens hours
2p nano particle.The Co/P proportional range adopted in this method is 1:4,1:10,1:12, phosphorus efficient relatively low (the Yellow River. transition metal phosphide Co
2p and Fe
2p nano particle Hydrothermal Synthesis and sign. Chinese Marine University, master thesis).Application number is that the Chinese patent of 200410006721.X reports and dissolves mixing by a certain percentage by metal-salt and Secondary ammonium phosphate, dry (120 DEG C, 6 – 12h), roasting (400 – 600 DEG C, 2 – 8h), and the method preparing transition metal phosphide in a hydrogen atmosphere under heating reduction (300 – 750 DEG C) and certain oxygen concentration under the multi-step process flow process such as passivation.In this preparation method, it dry just need reach 6-12 hour, and maturing temperature is 400-600 DEG C, and required time is 2-8 hour, follow-uply also needs the process such as reduction, passivation, and operation is loaded down with trivial details.Adopt metal simple-substance and phosphorus direct reaction, need carry out in high temperature, autoclave, and need protective atmosphere in preparation process, should not manipulate; There is inflammable and explosive danger.Finding cheap, low toxicity, high reactivity phosphorus source, simplify synthesis path further, Reaction time shorten, and the form realizing product is controlled, and then promote phosphide throughput rate, is the subject matter needing to solve.
Summary of the invention
For the problems referred to above preparing transition metal phosphide existence, the invention provides the transition metal phosphide Co that a kind of step is simple, productive rate is high, purity is high, product morphology is good
2the preparation method of P.
For solving the problems of the technologies described above, the technical solution used in the present invention:
A kind of transition metal phosphide Co
2the preparation method of P, the steps include:
(1) is using Tong – phosphorus alloy as phosphorus source, using Tong – cobalt-base alloy or cobalt as cobalt source, be smelted into ingot metal by cobalt source and phosphorus source vacuum arc melting furnace;
(2) ingot metal is used ferric chloride Solution process, overflow to bubble-free; Gained solid is Co
2p.
In above-mentioned preparation method, described phosphorus source, cobalt source are obtainable any phosphorus content Tong – phosphorus alloy, arbitrarily cobalt contents Tong – cobalt-base alloy.And the usage ratio in phosphorus source and cobalt source, according to the content of phosphorus in Tong – phosphorus alloy Ji in Tong – cobalt-base alloy the content of cobalt adjust, to reach the requirement of mol ratio for 2:1 of cobalt contents and phosphorus content.Smelting temperature adjusts according to the fusing point in selected cobalt source and phosphorus source, is the arbitrary temp that cobalt source and phosphorus source can be made fully to melt.Described ferric chloride Solution, its concentration is obtainable any concentration.
Above-mentioned preparation method, can use as raw material to make the copper – phosphorus alloy of obtainable any phosphorus content, arbitrarily the copper – cobalt-base alloy of cobalt contents, and reduce the comprehensive cost (raw materials cost, time cost, energy cost etc.) of reaction to a certain extent, adopt copper as conditioning agent in step (1), to regulate the mol ratio of Co, P.
Above-mentioned preparation method, preferably, Yong Tong – cobalt-base alloy is as cobalt source.Now, required melt temperature is lower, and the fusion time is shorter, the Co obtained
2the granularity of P evenly.
Above-mentioned preparation method, preferably, copper 13.85-19.90%, Tong – cobalt-base alloy 28.60-51.50%, Tong – phosphorus alloy 28.60-57.10%; Wherein, Tong – phosphorus alloy used, the mass percent of its component is: phosphorus 3.0 – 14.5%, and surplus is copper; Tong – cobalt-base alloy used, the mass percent of its component is: cobalt 5.0 – 30.0%, and surplus is copper.Now, phosphorus and cobalt complete reaction, the comprehensive cost (raw materials cost, time cost, energy cost etc.) of reaction is minimum.
Above-mentioned preparation method, preferably, ingot metal, with before ferric chloride Solution process, revolves with vacuum list roller the system of quenching and to revolve it and quench.Now, the treatment time required for step (2) shortens more than 50%, and the purity of product is higher, prepared Co
2the size of P particulate is less.Concrete operations are: ingot metal is cut into strip and be placed on high vacuum single roller and revolve in the system of quenching, and heating 1 –, to set single roller speed range after 3 minutes be that 1000 – 2500 revs/min carries out revolving process of quenching; Now, the treatment time required for step (2) is 15-24 hour, and the purity of product is higher, prepared Co
2the size of P particulate is less (4-5 μm).
Above-mentioned preparation method, in order to improve productive rate and the purity of product further; To prepared ingot metal vacuum arc melting furnace melt back 3 – 5 times; The now high purity more than 98.7% of product.
Above-mentioned preparation method, in order to a nearlyer step improves Co
2the purity of P, is handled as follows step (2) gained powder; Adopt distilled water or dehydrated alcohol to gained powder carry out ultrasonic cleaning 2 times, centrifugal 3 times, drying treatment 1 – 3 hours; Centrifuge speed is 8000 – 15000 revs/min; Loft drier temperature range is 50 – 90 DEG C; Now high purity 100%.
Above-mentioned preparation method, ferric chloride Solution volumetric molar concentration used is preferably 1.5 – 5mol/L; Now, etching time is 12 – 48 hours; The Co obtained
2the pore of P particulate is less and even.
Beneficial effect
Compared with the preparation method of the direct chemical combination of metal simple-substance and red phosphorus, method of the present invention possesses following advantage:
(1) using Tong – phosphorus alloy as phosphorus source, nontoxic, stable in properties, be easy to get, cheap, can and easily forms the Transition-metal Alloys ingot containing Gu – phosphorus with the abundant melting in cobalt source, be prepare Co
2p provides condition; Time required for abundant melting is only 40-70s, thus reduces preparation requirement, shortens preparation time;
(2) be melting process between phosphorus source and cobalt source, process stabilization, easily control, safety; Use conventional apparatus for melting metal, do not need autoclave, avoid the reaction conditions of the harshnesses such as high pressure;
(3) carry out melting with vacuum arc melting furnace, by i.e. temperature controllable of adjusting frequency, make the adjustable easy control of melting process; Ensure that the productive rate of product is up to 98.7-100% simultaneously;
(4) adopt ferric chloride Solution to process, product purity can be made up to 99.3-100% while guarantee high yield, and ensure Co simultaneously
2p is vesicular structure, Kong Duo, little and evenly, specific surface area is large, active high;
(5) as long as products therefrom carries out ultrasonic cleaning, centrifugal, drying, without the need to other subsequent disposal, technique is simple.
Accompanying drawing explanation
Fig. 1 is Co prepared by the present invention
2the XRD diffractogram of P powder;
Fig. 2 is Co prepared by the present invention
2the scanning electron microscopic picture of P powder;
Fig. 3 is the EDS figure of Fig. 2 corresponding point position (+1), and according to this figure, this thing is elementary composition by cobalt, two kinds, phosphorus, and the atomic ratio of two kinds of elements meets Co
2p-compound.
Embodiment
embodiment 1
(1) raw material is taken by the mass percent of industrial pure copper 19.90%, Tong – cobalt-base alloy 51.50%, Tong – phosphorus alloy 28.60%.Wherein in Tong – cobalt-base alloy, the mass percent of copper is 70.3%, and the mass percent of cobalt is 29.7%; In Tong – phosphorus alloy, the mass percent of copper is 86.0%, and the mass percent of phosphorus is 14.0%;
(2) in vacuum arc melting furnace, Tong – Gu – phosphorus alloy ingot is founded.Concrete steps are as follows: be placed in the copper crucible of electric arc furnace by the raw material prepared, be adjusted to intermediate frequency, and utilize arc-over to produce high temperature, control heat-up time is 60s, and melting obtains female ingot.At this, melt back 5 times is even to ensure melting.All female for alloy ingot to be removed surface oxide layer after each melting
(3) the female ingot of Suo get Tong – Gu – phosphorus alloy carries out the process of high vacuum melt spinning method and makes strip.Treat alloy female ingot fusing post-heating 2.5 minutes, utilize high pressure gas to be blown and cast onto on high speed rotating copper roller, copper roller speed setting is 2500 revs/min.
(4) Suo get Tong – Gu – phosphorus alloy strip being placed in the ferric chloride Solution of 4.5mol/L, freely corroding 24 hours (at the end of guaranteeing corrosion, bubble-free is overflowed, and as also having bubble, can supplement ferric chloride Solution).Utilize distilled water, dehydrated alcohol to carry out ultrasonic cleaning in gained powder subsequently, utilize supercentrifuge to carry out thing and be separated, centrifuge speed is set as 8000 revs/min, gained powder is placed in the loft drier 2.5 hours of 80 DEG C, obtains Co
2p powder.This Co
2p is rhombic system crystalline structure; Bar-shaped or porous is irregular spherical in porous; Relative to the particle of identical pattern, equal particle diameter, its specific surface area improves 65.7%.Co
2p can quick catalysis NaBH
4reduction p-NP generates p-aminophenol, is added to p-NP and NaBH
4in, along with the reaction times extends to 7 minutes, by observing ultra-violet absorption spectrum, the generation of p-aminophenol just can be found.
embodiment 2
(1) raw material is taken by the mass percent of industrial pure copper 13.85%, Tong – cobalt-base alloy 50.00%, Tong – phosphorus alloy 36.15%.Wherein in Tong – cobalt-base alloy, the mass percent of copper is 80.0%, and the mass percent of cobalt is 20.0%; In Tong – phosphorus alloy, the mass percent of copper is 91.7%, and the mass percent of phosphorus is 8.3%.
(2) in vacuum arc melting furnace, Tong – Gu – phosphorus alloy ingot is founded.Concrete steps are as follows: be placed in the copper crucible of electric arc furnace by the raw material prepared, be adjusted to intermediate frequency, and utilize arc-over to produce high temperature, control heat-up time is 50s, and melting obtains female ingot.At this, melt back 4 times is even to ensure melting.All female for alloy ingot to be removed surface oxide layer after each melting.
(3) the female ingot of Suo get Tong – Gu – phosphorus alloy carries out the process of high vacuum melt spinning method and makes strip.Treat alloy female ingot fusing post-heating 2 minutes, utilize high pressure gas to be blown and cast onto on high speed rotating copper roller, copper roller speed setting is 2200 revs/min.
(4) Suo get Tong – Gu – phosphorus alloy strip is placed in the ferric chloride Solution of 3.2mol/L, freely corrodes 20 hours.Utilize distilled water, dehydrated alcohol to carry out ultrasonic cleaning in gained powder subsequently, utilize supercentrifuge to carry out thing and be separated, centrifuge speed is set as 10000 revs/min, gained powder is placed in the loft drier 2 hours of 70 DEG C, obtains Co
2p powder.This Co
2p is rhombic system crystalline structure; Bar-shaped or porous is irregular spherical in porous; Relative to the particle of identical pattern, equal particle diameter, its specific surface area improves 69.3%; Be added to p-NP and NaBH
4in, along with the reaction times extends to 6 minutes, by observing ultra-violet absorption spectrum, the generation of p-aminophenol just can be found.
embodiment 3
(1) raw material is taken by the mass percent of industrial pure copper 14.30%, Tong – cobalt-base alloy 28.60%, Tong – phosphorus alloy 57.10%.Wherein in Tong – cobalt-base alloy, the mass percent of copper is 93.0%, and the mass percent of cobalt is 7.0%; In Tong – phosphorus alloy, the mass percent of copper is 93.0%, and the mass percent of phosphorus is 7.0%.
(2) in vacuum arc melting furnace, Tong – Gu – phosphorus alloy ingot is founded.Concrete steps are as follows: be placed in the copper crucible of electric arc furnace by the raw material prepared, be adjusted to intermediate frequency, and utilize arc-over to produce high temperature, control heat-up time is 45s, and melting obtains female ingot.At this, melt back 3 times is even to ensure melting.All female for alloy ingot to be removed surface oxide layer after each melting.
(3) Suo get Tong – Gu – phosphorus alloy carries out the process of high vacuum melt spinning method and makes strip.Treat that alloy melts female ingot post-heating 1 minute, utilize high pressure gas to be blown and cast onto on high speed rotating copper roller, copper roller speed setting is 1500 revs/min.
(4) Suo get Tong – Gu – phosphorus alloy strip is placed in the ferric chloride Solution of 2.5mol/L, freely corrodes 15 hours.Utilize distilled water, dehydrated alcohol to carry out ultrasonic cleaning in gained powder subsequently, utilize supercentrifuge to carry out thing and be separated, centrifuge speed is set as 12000 revs/min, gained powder is placed in the loft drier 1.5 hours of 60 DEG C, obtains Co
2p powder.This Co
2p is rhombic system crystalline structure; Bar-shaped or porous is irregular spherical in porous; Relative to the particle of identical pattern, equal particle diameter, its specific surface area improves 73.6%; Be added to p-NP and NaBH
4in, along with the reaction times extends to 5 minutes, by observing ultra-violet absorption spectrum, the generation of p-aminophenol just can be found.
embodiment 4
(1) raw material is taken by the mass percent of industrial pure copper 34.34%, cobalt metal 22.80%, Tong – phosphorus alloy 42.86%.Wherein in Tong – phosphorus alloy, the mass percent of copper is 86.0%, and the mass percent of phosphorus is 14.0%.
(2) in vacuum arc melting furnace, Tong – Gu – phosphorus alloy ingot is founded.Concrete steps are as follows: be placed in the copper crucible of electric arc furnace by the raw material prepared, be adjusted to intermediate frequency, and utilize arc-over to produce high temperature, control heat-up time is 70s, and melting obtains female ingot.At this, melt back 5 times is even to ensure melting.All female for alloy ingot to be removed surface oxide layer after each melting.
(3) the female ingot of Suo get Tong – Gu – phosphorus alloy carries out the process of high vacuum melt spinning method and makes strip.Treat alloy female ingot fusing post-heating 2 minutes, utilize high pressure gas to be blown and cast onto on high speed rotating copper roller, copper roller speed setting is 2500 revs/min.
(4) Suo get Tong – Gu – phosphorus alloy strip being placed in the ferric chloride Solution of 4.5mol/L, freely corroding 18 hours (at the end of guaranteeing corrosion, bubble-free is overflowed, and as also having bubble, can supplement ferric chloride Solution).Utilize distilled water, dehydrated alcohol to carry out ultrasonic cleaning in gained powder subsequently, utilize supercentrifuge to carry out thing and be separated, centrifuge speed is set as 8000 revs/min, gained powder is placed in the loft drier 2.5 hours of 80 DEG C, obtains Co
2p powder.This Co
2p is rhombic system crystalline structure; Bar-shaped or porous is irregular spherical in porous; Relative to the particle of identical pattern, equal particle diameter, its specific surface area improves 63.9%; Co
2p is added to p-NP and NaBH
4in, along with the reaction times extends to 7.5 minutes, by observing ultra-violet absorption spectrum, the generation of p-aminophenol just can be found.
comparative example 1
Tong – Gu – phosphorus alloy strip prepared by embodiment 3 and be placed in the salpeter solution of 3.2mol/L, the dilution heat of sulfuric acid of 1mol/L respectively, freely corrode, the former corrodes and is all corroded by strip for 15 hours, have no powdered product, the latter is corroded and the matrix copper in strip cannot be eroded for 48 hours, there is no pure Co
2p powdered product.
Claims (7)
1. a transition metal phosphide Co
2the preparation method of P, is characterized in that, the steps include:
(1) is using Tong – phosphorus alloy as phosphorus source, using Tong – cobalt-base alloy or cobalt as cobalt source, be smelted into ingot metal by cobalt source and phosphorus source vacuum arc melting furnace;
(2) ingot metal is used ferric chloride Solution process, overflow to bubble-free; Gained solid is Co
2p;
Copper 13.85-19.90%, Tong – cobalt-base alloy 28.60-51.50%, Tong – phosphorus alloy 28.60-57.10%; Wherein, Tong – phosphorus alloy used, the mass percent of its component is: phosphorus 3.0 – 14.5%, and surplus is copper; Tong – cobalt-base alloy used, the mass percent of its component is: cobalt 5.0 – 30.0%, and surplus is copper;
Ingot metal, with before ferric chloride Solution process, revolves with vacuum list roller the system of quenching and to revolve it and quench.
2. preparation method according to claim 1, is characterized in that, adopts copper as conditioning agent in step (1).
3. preparation method according to claim 1, is characterized in that, Yong Tong – cobalt-base alloy is as cobalt source.
4. preparation method according to claim 1, is characterized in that, ingot metal is cut into strip and is placed on high vacuum single roller and revolves in the system of quenching, and heating 1 –, to set single roller speed range after 3 minutes be that 1000 – 2500 revs/min carries out revolving process of quenching.
5. preparation method according to claim 1, is characterized in that, to prepared ingot metal vacuum arc melting furnace melt back 3 – 5 times.
6. preparation method according to claim 1, is characterized in that, is handled as follows step (2) gained powder; Adopt distilled water or dehydrated alcohol to gained powder carry out ultrasonic cleaning 2 times, centrifugal 3 times, drying treatment 1 – 3 hours; Centrifuge speed is 8000 – 15000 revs/min; Loft drier temperature range is 50 – 90 DEG C.
7. preparation method according to claim 1, is characterized in that, above-mentioned preparation method ferric chloride Solution volumetric molar concentration used is preferably 1.5 – 5mol/L.
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| EP1985583A2 (en) * | 2007-04-17 | 2008-10-29 | Samsung Electronics Co., Ltd. | Method for preparing metal phosphide nanocrystal from phosphite compound and method for passivating nanocrystal core with the same |
| 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 |
| CN101857207A (en) * | 2010-06-08 | 2010-10-13 | 南开大学 | Preparation method and application of transition metal phosphide Co2P |
| CN103193214A (en) * | 2013-03-29 | 2013-07-10 | 太原理工大学 | Preparation method of Co2P nanometer structure material |
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| CN100392505C (en) * | 2004-11-02 | 2008-06-04 | 株式会社神户制钢所 | Copper alloy thin films, copper alloy sputtering targets and flat panel displays |
| EP1985583A2 (en) * | 2007-04-17 | 2008-10-29 | Samsung Electronics Co., Ltd. | Method for preparing metal phosphide nanocrystal from phosphite compound and method for passivating nanocrystal core with the same |
| 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 |
| CN101857207A (en) * | 2010-06-08 | 2010-10-13 | 南开大学 | Preparation method and application of transition metal phosphide Co2P |
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