CN105016319B - Three-dimensional porous sea urchin shape phosphatization cobalt and preparation method and application - Google Patents
Three-dimensional porous sea urchin shape phosphatization cobalt and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of three-dimensional porous sea urchin shape phosphatization cobalt and preparation method and application.The preparation method includes：Take cobalt salt uniformly to mix water-filling thermal response of going forward side by side in polar neutral solvent with amino-compound, be made and the three-dimensional sea urchin shape hydrated basic carbonic acid cobalt precursor formed is mainly assembled by nano wire；By the hydrated basic carbonic acid cobalt precursor and hypophosphites high annealing, three-dimensional porous sea urchin shape phosphatization cobalt is obtained.The present invention first passes through simple hydro-thermal method and prepares three-dimensional sea urchin shape hydrated basic cobalt carbonate, three-dimensional porous sea urchin shape phosphatization cobalt then is obtained by the method for high temperature phosphorization, not only technique is simply controllable, and raw material sources are extensive, it is with low cost, and yield is higher, suitable for large-scale production, while obtained product size uniformity, with sea urchin shape three-dimensional porous structure, active site retains many, with high activity and superior stability, has wide application prospects in electro-catalysis field.
Description
Technical field
The present invention relates to a kind of metal phosphide material and preparation method thereof, more particularly to a kind of three-dimensional porous sea urchin shape phosphorus
Change cobalt and preparation method and application, belong to material science.
Background technology
The energy crisis and environmental pollution brought with fossil energy are increasingly sharpened, and people are a kind of clear in the urgent need to finding
Clean, efficient, rich reserves the new sources of the physical efficiency containing energy.Exactly a kind of preferable new source of the physical efficiency containing energy of hydrogen.Water electrolysis hydrogen production
It is one of silicol process of greatest concern at present, its core technology is catalyst, it is known that optimal catalyst is platinum, yet with
Platinum reserves are low and expensive, are extremely restricted its application.
At present, phosphatization cobalt is because of rich reserves, and possesses excellent electrocatalytic hydrogen evolution reactivity worth, it is considered to be most probable
Substitute one of material of platinum catalyst.In recent years, the phosphatization cobalt of different-shape, such as nano wire of phosphatization cobalt, nanometer are synthesized
Grain, has become the focus of people's research.But these phosphatization cobalt nanowire, nano particles are easily reunited when in use, are caused
The drastically reduction of avtive spot, electro catalytic activity declines, stability extreme difference, therefore is unsuitable for carrying out practical application.
The content of the invention
It is existing to overcome it is a primary object of the present invention to provide a kind of three-dimensional porous sea urchin shape phosphatization cobalt and preparation method thereof
There is the deficiency in technology.
For achieving the above object, the technical solution adopted by the present invention includes：
A kind of preparation method of three-dimensional porous sea urchin shape phosphatization cobalt, it includes：
Take cobalt salt uniformly to mix water-filling thermal response of going forward side by side in polar neutral solvent with amino-compound, be made main by receiving
Rice noodles assemble the three-dimensional sea urchin shape hydrated basic carbonic acid cobalt precursor to be formed；
By the hydrated basic carbonic acid cobalt precursor and hypophosphites high annealing, three-dimensional porous sea urchin shape phosphatization is obtained
Cobalt.
Among some more preferred embodiment, the preparation method can include：It is 1~5 to take mass ratio：1~5
Cobalt salt and amino-compound be dissolved in polar neutral solvent and obtained after hydro-thermal reactions, 1~24h of reaction are carried out at 100~150 DEG C
The three-dimensional sea urchin shape hydrated basic carbonic acid cobalt precursor.
Among some more preferred embodiment, the preparation method can include：By the hydrated basic carbonic acid
Cobalt precursor, in 200~400 DEG C of 2~10h of annealing, obtains three-dimensional porous sea urchin shape phosphatization cobalt with hypophosphites.
It is more highly preferred to, the mass ratio of the hypophosphites and cobalt salt is 2~5：1~5.
Further, the cobalt salt may include cobalt chloride hexahydrate, six hydration cobaltous bromides, cabaltous nitrate hexahydrate, four hydrations
Any one in cobalt acetate, Cobalt monosulfate heptahydrate, acetylacetone cobalt (II), acetylacetone cobalt (III) or two or more groups
Close, but not limited to this.
Further, the polar neutral solvent may include water, methanol, ethanol, propyl alcohol, butanol, ethylene glycol, N, N- diformazans
Any one in base formamide or two or more combinations, but not limited to this.
Further, the amino-compound may include urea, ammonium formate, ammonium acetate, aminoquinoxaline, ammonium carbonate, carbon
Any one in sour hydrogen ammonium or two or more combinations, but not limited to this.
Further, the hypophosphites may include calcium hypophosphite, sodium hypophosphite, hypo-aluminum orthophosphate, magnesium hypophosphite, hypophosphorous acid
Any one in potassium, manganese hypophosphite, ammonium hypophosphite, nickelous hypophosphite, ferric hypophosphite, zinc hypophosphite or two or more combinations,
But not limited to this.
Among some more specifically preferred embodiment, the preparation method specifically includes following steps：
Ith, take cobalt salt ultrasonic dispersed after being mixed with polar neutral solvent；
IIth, to step I after finally obtained mixed solution adds amino-compound and mixes and be uniformly dispersed, then at 100~150
DEG C reaction 1~24h；
IIIth, isolate by step II hydro-thermal reaction products therefrom, and clean, dry；
IV, anneal step III products therefrom and hypophosphites at 200~400 DEG C 2~10h, obtains described three-dimensional porous
Sea urchin shape phosphatization cobalt.
The three-dimensional porous sea urchin shape phosphatization cobalt prepared by foregoing any method, it has three-dimensional porous structure, and diameter
For 1~20 μm, preferably 5~10 μm.
A kind of preparation method of three-dimensional porous sea urchin shape metal phosphide is additionally provided among some embodiments of the present invention,
It includes：Take metal salt uniformly to mix water-filling thermal response of going forward side by side in polar neutral solvent with amino-compound, be made it is main by
Nano wire assembles the three-dimensional sea urchin shape hydrated basic carbonate precursor to be formed, and, by the hydrated basic carbonic acid salt precursor
Body and hypophosphites high annealing, obtain three-dimensional porous sea urchin shape metal phosphide.
Wherein, the metal salt is at least selected from transition metal salt, such as manganese salt, molysite, nickel salt and mantoquita.
The three-dimensional porous sea urchin shape metal phosphorizing prepared by preceding method is additionally provided among some embodiments of the present invention
Thing, including phosphatization manganese, iron phosphide, nickel phosphide, phosphorized copper etc..
The purposes of the three-dimensional porous sea urchin shape metal phosphide is additionally provided among some embodiments of the present invention, for example
Purposes in electro-catalysis field.
For example, providing a kind of electrocatalysis material or device among some embodiments, it is comprising described three-dimensional porous
Sea urchin shape metal phosphide, example three-dimensional porous sea urchin shape phosphatization cobalt as mentioned.
Described electrocatalysis material or device can be electrocatalytic hydrogen evolution material or device, and oxygen material or dress are analysed in electro-catalysis
Put, electrocatalytic oxidation reducing material or device etc., and not limited to this.
Such as the present invention is by the way that by metal salt, particularly transition metal salt, cobalt salt is mixed with amino-compound, anti-in hydro-thermal
Certain time is reacted under conditions of answering, three-dimensional sea urchin shape hydrated basic carbonate precursor is formd, then by the Hydrothermal Synthesiss
Obtained hydrated basic carbonate precursor and hypophosphites be in tube furnace high temperature annealing a few hours can obtain it is three-dimensional porous
Sea urchin shape metal phosphide.Wherein, amino-compound decomposes the carbanion produced, can induce product to increasingly complex three
Tie up structure growth；And cause metal phosphide that there is loose structure while still keeping three-dimensional sea urchin shape structure by high annealing.
Compared to prior art, advantages of the present invention includes：
(1) forerunner's production procedure of the invention is hydro-thermal reaction, and step is simple, and experiment condition is controllable, and is used
Reagent is simple and easy to get, and subsequent high temperature phosphorization process can produce substantial amounts of loose structure, is conducive to the reservation of avtive spot；
(2) the three-dimensional porous sea urchin shape phosphatization cobalt prepared by the present invention is three-dimensional sea urchin shape, even size distribution, and is had
Loose structure so that its application in terms of electro-catalysis can keep high activity and superior stability；
(4) preparation technology of the invention can also be extended to the preparation technology of the phosphide of other three-dimensional porous structures, and production
Rate is higher, it is easy to iodine scale.
Brief description of the drawings
Fig. 1 a- Fig. 1 b are the scanning electricity of three-dimensional sea urchin shape hydrated basic carbonic acid cobalt precursor in the embodiment of the present invention 1 respectively
Sub- microphotograph and transmission electron microscope photo；
Fig. 2 a- Fig. 2 b are that the SEM of three-dimensional porous sea urchin shape phosphatization cobalt in the embodiment of the present invention 1 is shone respectively
Piece and transmission electron microscope photo；
Fig. 3 a- Fig. 3 b are the powder x-ray diffraction collection of illustrative plates of three-dimensional porous sea urchin shape phosphatization cobalt in the embodiment of the present invention 1.
Fig. 4 is that three-dimensional porous sea urchin shape phosphatization cobalt is used as electrode material and carries out electrocatalytic hydrogen evolution in the embodiment of the present invention 1
Polarization curve.
Embodiment
As it was previously stated, in view of existing zero dimension or one-dimensional phosphatization cobalt nano-particle, nano wire etc. are in the presence of easily reunion
The defect of practical application request can not be met, inventor has found after studying for a long period of time and largely putting into practice：Amino-compound point
Solve the carbanion produced hydrated basic cobalt carbonate of inducible generation in hydro-thermal reaction and be self-assembly of three-dimensional sea urchin shape
Structure, and hydrated basic cobalt carbonate pass through high temperature phosphorization after pattern be basically unchanged while producing a large amount of loose structures.It is based on
This finds that inventor is able to propose technical scheme, and it to it as it was noted above, will make more detailed below
Explain.
Among some embodiments, a kind of method for preparing the three-dimensional porous sea urchin shape phosphatization cobalt includes：Take cobalt salt
Polar neutral solvent is dissolved in amino-compound, the three-dimensional for being assembled and being formed by nano wire is made after being reacted in hydro-thermal reaction system
Sea urchin shape hydrated basic carbonic acid cobalt precursor；Then by presoma made from the Hydrothermal Synthesiss and hypophosphites in high annealing number
Hour can obtain three-dimensional porous sea urchin shape phosphatization cobalt.
Among some more specifically embodiment, the preparation method comprises the following steps：
Ith, cobalt salt and polar neutral solvent is taken to mix, then ultrasonic disperse is uniform；
IIth, to after being handled through step I after mixed solution addition amino-compound and mixing is uniformly dispersed, 100~150
DEG C reaction 1~24h；
IIIth, after reaction terminates, centrifuge out by the product after hydro-thermal reaction obtained by step II, then clean the product,
And by the product in 60 DEG C of drying；
IV, anneal the product obtained by step III and hypophosphites at 200~400 DEG C 2~10h, acquisition target product.
Foregoing cobalt salt, amino-compound, state hypophosphites and polar neutral solvent etc. and may be selected from but be not limited only to institute above
The species of row.
Further, among an exemplary embodiments, the preparation method can include：Cobalt nitrate is dissolved in water first
In, add urea ultrasonic disperse uniformly, after stirring 30min, be placed in autoclave, 100~150 DEG C of 1~24h of reaction, it
Afterwards centrifuge collect product, and with sodium hypophosphite in tube furnace 300 DEG C annealing 2h, then wash, dry, obtain target production
Thing.
The product that the present invention is obtained is three-dimensional porous sea urchin shape phosphatization cobalt, and it has three-dimensional porous structure, effectively retained
Avtive spot, improves easy agglomeration traits of the material during electro-catalysis, it is kept superior stability.
Further, about 1~20 μm of the diameter of the three-dimensional porous sea urchin shape phosphatization cobalt, preferably from about 5~10 μm, size is equal
One, and can largely prepare.
The present invention first passes through simple hydro-thermal method and prepares three-dimensional sea urchin shape hydrated basic cobalt carbonate, then by high temperature phosphorous
The method of change obtains three-dimensional porous sea urchin shape phosphatization cobalt, products therefrom size uniformity, and its three-dimensional porous structure is that its holding is superior
Chemical property provide necessary condition.
In addition, the preparation method of the present invention can also be generalized to and prepare other transition metal phosphides such as phosphatization manganese, phosphatization
Iron, nickel phosphide, phosphorized copper etc..
To make the substantive distinguishing features and its practicality that has of the present invention it is more readily appreciated that below just with reference to accompanying drawing and preferably
Embodiment is described in further detail to technical scheme.But the description and explanation below in relation to embodiment are to this hair
Bright protection domain is not limited in any way.
0.5mmol cobalt nitrate is dissolved in 30mL water by embodiment 1, and ultrasonic disperse is uniform, then, adds 1.5mmol urine
Element, continues after stirring 30 minutes, transfers the solution into 50mL reactors, and 120 DEG C are reacted 12 hours, after cooling, are collected by centrifugation
Product three-dimensional sea urchin shape hydrated basic carbonic acid cobalt precursor (its pattern refers to Fig. 1 a- Fig. 1 b), and with 0.25g sodium hypophosphite
Annealed 2 hours for lower 300 DEG C in nitrogen protection, you can obtain three-dimensional porous sea urchin shape phosphatization cobalt.
As can be seen that the phosphatization cobalt Product size of the present embodiment is homogeneous from Fig. 2 a- Fig. 2 b, about 5 μm of diameter, and with three
The porous sea urchin shape structure of dimension.Fig. 3 a- Fig. 3 b are referred to again, determine that product is rhombic system phosphatization by X-ray powder diffraction
Cobalt.
The Ketjen black of phosphatization cobalt and 1mg made from 5mg is taken to be dissolved in 32 μ L Nafion solution (mass fraction is 5%), 200
In the mixed solution of μ L ethanol and 768 μ L deionized water, catalyst ink is made in ultrasound at least 30 minutes.4 μ L are taken to be catalyzed
Agent ink is dripped on a diameter of 3mm platinum carbon electrode, and working electrode is made.Electrocatalytic hydrogen evolution reactivity worth uses three traditional electricity
Electrode systems are measured, and above-mentioned platinum carbon electrode is made as working electrode, silver/silver chloride electrode as reference electrode, platinum plate electrode
For to electrode, the linear sweep voltammetry curve measured with 5 millivolts of sweep speeds per second characterizes its electrocatalysis characteristic.In Fig. 4
Current potential has carried out ohm compensation and has been converted into current potential relative to reversible hydrogen electrode.
1mmol cobalt chloride is dissolved in 30mL ethanol by embodiment 2, and ultrasonic disperse is uniform, then, adds 5mmol urea,
Continue after stirring 30 minutes, transfer the solution into 50mL reactors, 100 DEG C are reacted 10 hours, and after cooling, production is collected by centrifugation
Thing, and annealed 4 hours for lower 400 DEG C in argon gas protection with 0.25g potassium hypophosphite, you can obtain three-dimensional porous sea urchin shape phosphatization
Cobalt.
In addition, inventor also utilizes the alternate embodiment such as listed other raw materials and other process conditions above
Various raw materials and corresponding process conditions in 1-2 have carried out corresponding experiment, obtain pattern, the property of three-dimensional porous sea urchin shape phosphatization cobalt
Energy waits also ideal, substantially similar to embodiment 1-2 products.
The present invention first passes through simple hydro-thermal method and prepares three-dimensional sea urchin shape hydrated basic cobalt carbonate, then by high temperature phosphorous
The method of change obtains three-dimensional porous sea urchin shape phosphatization cobalt, and not only technique is simply controllable, and raw material sources are extensively, with low cost, and production
Rate is higher, suitable for mass producing, while obtained product size uniformity, with sea urchin shape three-dimensional porous structure, catalytic active site
Point retains many, with high activity and superior stability, has wide application prospects in electrocatalytic hydrogen evolution field.
Technical scheme is described in detail embodiment described above, it should be understood that the above is only
For the specific embodiment of the present invention, it is not intended to limit the invention, all any modifications made in the spirit of the present invention,
Supplement or similar fashion replacement etc., should be included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of three-dimensional porous sea urchin shape phosphatization cobalt, it is characterised in that including：
Take cobalt salt uniformly to mix water-filling thermal response of going forward side by side in polar neutral solvent with amino-compound, be made main by nano wire
The three-dimensional sea urchin shape hydrated basic carbonic acid cobalt precursor formed is assembled, the amino-compound includes urea, ammonium formate, acetic acid
Any one in ammonium, aminoquinoxaline, ammonium carbonate, ammonium hydrogen carbonate or two or more combinations；
By the hydrated basic carbonic acid cobalt precursor and hypophosphites high annealing, three-dimensional porous sea urchin shape phosphatization cobalt is obtained.
2. the preparation method of three-dimensional porous sea urchin shape phosphatization cobalt according to claim 1, it is characterised in that including：Take quality
Than for 1~5：1~5 cobalt salt is dissolved in polar neutral solvent with amino-compound and carries out hydro-thermal reaction at 100~150 DEG C, instead
Answer and obtained after 1~24h the three-dimensional sea urchin shape hydrated basic carbonic acid cobalt precursor.
3. the preparation method of three-dimensional porous sea urchin shape phosphatization cobalt according to claim 1, it is characterised in that including：Will be described
Hydrated basic carbonic acid cobalt precursor, in 200~400 DEG C of 2~10h of annealing, obtains three-dimensional porous sea urchin shape phosphatization with hypophosphites
Cobalt.
4. the preparation method of three-dimensional porous sea urchin shape phosphatization cobalt according to claim 3, it is characterised in that the hypophosphorous acid
The mass ratio of salt and cobalt salt is 2~5：1~5.
5. the preparation method of the three-dimensional porous sea urchin shape phosphatization cobalt according to any one of claim 1-3, it is characterised in that
The cobalt salt include cobalt chloride hexahydrate, six hydration cobaltous bromides, cabaltous nitrate hexahydrate, four acetate hydrate cobalts, Cobalt monosulfate heptahydrate,
Any one in acetylacetone cobalt (II), acetylacetone cobalt (III) or two or more combinations.
6. the preparation method of three-dimensional porous sea urchin shape phosphatization cobalt according to claim 1 or 2, it is characterised in that the neutrality
Polar solvent includes any one or two kinds in water, methanol, ethanol, propyl alcohol, butanol, ethylene glycol, DMF
Combination above.
7. the preparation method of the three-dimensional porous sea urchin shape phosphatization cobalt according to any one of claim 1-4, it is characterised in that
The hypophosphites includes calcium hypophosphite, sodium hypophosphite, hypo-aluminum orthophosphate, magnesium hypophosphite, potassium hypophosphite, manganese hypophosphite, hypophosphorous acid
Any one in ammonium, nickelous hypophosphite, ferric hypophosphite, zinc hypophosphite or two or more combinations.
8. the preparation method of the three-dimensional porous sea urchin shape phosphatization cobalt according to any one of claim 1-4, it is characterised in that
Specifically include：
Ith, take cobalt salt ultrasonic dispersed after being mixed with polar neutral solvent；
IIth, it is anti-then at 100~150 DEG C to step I after finally obtained mixed solution adds amino-compound and mixes and be uniformly dispersed
Answer 1~24h；
IIIth, isolate by step II hydro-thermal reaction products therefrom, and clean, dry；
IV, anneal step III products therefrom and hypophosphites at 200~400 DEG C 2~10h, obtains the three-dimensional porous sea urchin
Shape phosphatization cobalt.
9. a kind of preparation method of three-dimensional porous sea urchin shape metal phosphide, it is characterised in that including：Take metal salt and amination
Compound is uniform in polar neutral solvent to mix water-filling thermal response of going forward side by side, and is made and the three-dimensional sea urchin formed is mainly assembled by nano wire
Shape hydrated basic carbonate precursor, and, the hydrated basic carbonate precursor and hypophosphites high annealing are obtained
Three-dimensional porous sea urchin shape metal phosphide；Wherein, the metal salt is at least selected from manganese salt, molysite, nickel salt and mantoquita, the amino
Compound includes urea, ammonium formate, ammonium acetate, aminoquinoxaline, ammonium carbonate, in ammonium hydrogen carbonate any one or it is two or more
Combination.
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