CN105016319A - Three-dimensional porous urchin-like cobalt phosphide as well as preparation method and application thereof - Google Patents
Three-dimensional porous urchin-like cobalt phosphide as well as preparation method and application thereof Download PDFInfo
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- CN105016319A CN105016319A CN201510470946.9A CN201510470946A CN105016319A CN 105016319 A CN105016319 A CN 105016319A CN 201510470946 A CN201510470946 A CN 201510470946A CN 105016319 A CN105016319 A CN 105016319A
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses three-dimensional porous urchin-like cobalt phosphide as well as a preparation method and an application thereof. The preparation method comprises the steps of: uniformly mixing a cobalt salt and an amino compound in a neutral-polarity solvent to have hydrothermal reaction to prepare a three-dimensional urchin-like hydrated basic cobalt carbonate precursor mainly formed by assembly of nanowires; and annealing the hydrated basic cobalt carbonate precursor and hypophosphite at a high temperature to obtain the three-dimensional urchin-like cobalt phosphide. By preparing the three-dimensional urchin-like hydrated basic cobalt carbonate precursor by a simple hydrothermal process and obtaining the three-dimensional urchin-like cobalt phosphide through high temperature phosphorization, not only is the process simple and controllable, the source of raw material wide and the cost low, but also the yield is relatively high, and the mass production is realized. The prepared product is uniform in size, has an urchin-like porous structure, maintains more catalytic active sites, has high activity and excellent stability and is wide in application prospect in the field of electric catalysis.
Description
Technical field
The present invention relates to a kind of metal phosphide material and preparation method thereof, particularly relate to a kind of three-dimensional porous sea urchin shape phosphatization cobalt and preparation method thereof and application, belong to material science.
Background technology
The energy dilemma brought along with fossil energy and environmental pollution increasingly sharpen, and people are new for can physical efficiency source in the urgent need to what find a kind of clean, efficient, rich reserves.Hydrogen is a kind of desirable new for can physical efficiency source just.Water electrolysis hydrogen production is one of silicol process of greatest concern at present, and its core technology is catalyzer, and known optimal catalyzer is platinum, however due to platinum reserves low and expensive, make it apply and be extremely restricted.
At present, phosphatization cobalt because of rich reserves, and has excellent electrocatalytic hydrogen evolution reactivity worth, is considered to one of most probable material substituting platinum catalyst.In recent years, the phosphatization cobalt of synthesis different-shape, nano wire, the nano particle of such as phosphatization cobalt, become the focus of people's research.But these phosphatization cobalt nanowires, nano particle are easily reunited in use, cause the sharply minimizing of avtive spot, electro catalytic activity declines, and stability extreme difference, is therefore unsuitable for carrying out practical application.
Summary of the invention
Main purpose of the present invention is to provide a kind of three-dimensional porous sea urchin shape phosphatization cobalt and preparation method thereof, to overcome deficiency of the prior art.
For achieving the above object, the technical solution used in the present invention comprises:
A preparation method for three-dimensional porous sea urchin shape phosphatization cobalt, it comprises:
Get cobalt salt and aminocompound Homogeneous phase mixing carry out hydro-thermal reaction, the obtained three-dimensional sea urchin shape hydrated basic cobaltous carbonate presoma formed primarily of nano wire assembling in polar neutral solvent;
By described hydrated basic cobaltous carbonate presoma and hypophosphite high temperature annealing, obtain three-dimensional porous sea urchin shape phosphatization cobalt.
Among some comparatively preferred embodiments, described preparation method can comprise: get cobalt salt that mass ratio is 1 ~ 5:1 ~ 5 and aminocompound is dissolved in polar neutral solvent and carries out hydro-thermal reaction at 100 ~ 150 DEG C, obtains described three-dimensional sea urchin shape hydrated basic cobaltous carbonate presoma after reaction 1 ~ 24h.
Among some comparatively preferred embodiments, described preparation method can comprise: by described hydrated basic cobaltous carbonate presoma and hypophosphite in 200 ~ 400 DEG C of 2 ~ 10h that anneal, obtain three-dimensional porous sea urchin shape phosphatization cobalt.
More preferred, the mass ratio of described hypophosphite and cobalt salt is 2 ~ 5:1 ~ 5.
Further, described cobalt salt can comprise cobalt chloride hexahydrate, six hydration cobaltous bromides, Cobaltous nitrate hexahydrate, four acetate hydrate cobalts, Cobalt monosulfate heptahydrate, acetylacetone cobalt (II), any one or two or more combinations in acetylacetone cobalt (III), but be not limited thereto.
Further, described polar neutral solvent can comprise water, methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, any one or two or more combinations in DMF, but is not limited thereto.
Further, described aminocompound can comprise urea, ammonium formiate, ammonium acetate, ammonium carbamate, volatile salt, any one or two or more combinations in bicarbonate of ammonia, but is not limited thereto.
Further, described hypophosphite can comprise calcium propionate, sodium hypophosphite, hypo-aluminum orthophosphate, magnesium hypophosphite, potassium hypophosphite, manganous hypophosphite, ammonium hypophosphite, nickelous hypophosphite, ferric hypophosphite, any one or two or more combinations in zinc hypophosphite, but is not limited thereto.
Among some more specifically preferred embodiment, described preparation method specifically comprises the steps:
I, ultrasonic dispersed after getting cobalt salt and polar neutral solvent;
II, to the final mixing solutions that obtains of step I add aminocompound and blending dispersion evenly after, then react 1 ~ 24h in 100 ~ 150 DEG C;
III, isolate by step II hydro-thermal reaction products therefrom, and clean, dry;
IV, by step III products therefrom and hypophosphite at 200 ~ 400 DEG C of 2 ~ 10h that anneal, obtain described three-dimensional porous sea urchin shape phosphatization cobalt.
The three-dimensional porous sea urchin shape phosphatization cobalt prepared by any one method aforementioned, it has three-dimensional porous structure, and diameter is 1 ~ 20 μm, is 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 comprises: get metal-salt and aminocompound Homogeneous phase mixing carry out hydro-thermal reaction in polar neutral solvent, the obtained three-dimensional sea urchin shape hydrated basic carbonate precursor formed primarily of nano wire assembling, and, by described hydrated basic carbonate precursor and hypophosphite high temperature annealing, obtain three-dimensional porous sea urchin shape metal phosphide.
Wherein, described metal-salt is at least selected from transition metal salt, such as manganese salt, molysite, nickel salt and mantoquita.
Additionally provide the three-dimensional porous sea urchin shape metal phosphide prepared by preceding method among some embodiments of the present invention, comprise phosphatization manganese, iron phosphide, nickel phosphide, phosphorized copper etc.
The purposes of described three-dimensional porous sea urchin shape metal phosphide is additionally provided, such as, in the purposes in electrocatalysis field among some embodiments of the present invention.
Such as, among some embodiments, provide a kind of electrocatalysis material or device, it comprises described three-dimensional porous sea urchin shape metal phosphide, such as described three-dimensional porous sea urchin shape phosphatization cobalt.
Described electrocatalysis material or device can be electrocatalytic hydrogen evolution material or device, and oxygen material or device are analysed in electrocatalysis, electrocatalytic oxidation reducing material or device etc., and are not limited thereto.
The present invention passes through metal-salt, particularly transition metal salt, such as cobalt salt mixes with aminocompound, certain hour is reacted under the condition of hydro-thermal reaction, define three-dimensional sea urchin shape hydrated basic carbonate precursor, then hydrated basic carbonate precursor obtained for this Hydrothermal Synthesis and hypophosphite high temperature annealing a few hours in tube furnace can be obtained three-dimensional porous sea urchin shape metal phosphide.Wherein, aminocompound decomposes the carbanion produced, and can grow to more complicated three-dimensional structure by induced product; And still keep three-dimensional sea urchin shape structure while of making metal phosphide have vesicular structure by high temperature annealing.
Compare to prior art, advantage of the present invention comprises:
(1) precursor power process of the present invention is hydro-thermal reaction, and step is simple, and experiment condition is controlled, and use reagent simple and easy to get, and high temperature phosphorization process subsequently can produce a large amount of vesicular structures, 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 has vesicular structure, makes its application in electrocatalysis can keep high reactivity and superior stability;
(4) preparation technology of the present invention also can be extended to the preparation technology of the phosphide of other three-dimensional porous structure, and productive rate is higher, is easy to iodine scale.
Accompanying drawing explanation
Fig. 1 a-Fig. 1 b is electron scanning micrograph and the transmission electron microscope photo of three-dimensional sea urchin shape hydrated basic cobaltous carbonate presoma in the embodiment of the present invention 1 respectively;
Fig. 2 a-Fig. 2 b is electron scanning micrograph and the transmission electron microscope photo of three-dimensional porous sea urchin shape phosphatization cobalt in the embodiment of the present invention 1 respectively;
Fig. 3 a-Fig. 3 b is 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 in the embodiment of the present invention 1, three-dimensional porous sea urchin shape phosphatization cobalt is used as the polarization curve that electrode materials carries out electrocatalytic hydrogen evolution.
Embodiment
As previously mentioned, in view of the phosphatization cobalt nano-particle, nano wire etc. of existing zero dimension or one dimension exist the defect of easily reuniting and cannot meet practical application request, inventor is through studying for a long period of time and finding after practice in a large number: aminocompound decomposes the carbanion produced the hydrated basic cobaltous carbonate self-assembly of inductive formation can form three-dimensional sea urchin shape structure in hydro-thermal reaction, and hydrated basic cobaltous carbonate pattern after high temperature phosphorization is substantially constant produces a large amount of vesicular structure simultaneously.Find based on this, inventor is proposed technical scheme of the present invention, and it does more detailed explanation by it as mentioned before below.
Among some embodiments, the method preparing described three-dimensional porous sea urchin shape phosphatization cobalt comprises: get cobalt salt and aminocompound is dissolved in a polar neutral solvent, obtainedly after reaction in hydro-thermal reaction system assembles by nano wire the three-dimensional sea urchin shape hydrated basic cobaltous carbonate presoma formed; Then presoma obtained for this Hydrothermal Synthesis and hypophosphite can be obtained three-dimensional porous sea urchin shape phosphatization cobalt in high temperature annealing a few hours.
Among some more specifically embodiment, this preparation method comprises the steps:
I, get cobalt salt and polar neutral solvent, then ultrasonic disperse is even;
II, to the mixing solutions after step I process add aminocompound and blending dispersion evenly after, at 100 ~ 150 DEG C of reaction 1 ~ 24h;
III, after reaction terminates, centrifugation goes out the product after by step II gained hydro-thermal reaction, then cleans this product, and by this product in 60 DEG C of oven dry;
IV, by the product of step III gained and hypophosphite at 200 ~ 400 DEG C of 2 ~ 10h that anneal, obtain target product.
Aforementioned cobalt salt, aminocompound, state hypophosphite and polar neutral solvent etc. and can be selected from but be not limited only to listed kind above.
Further, among an exemplary embodiments, described preparation method can comprise: first that Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is soluble in water, adds urea ultrasonic disperse evenly, after stirring 30min, be placed in autoclave, 100 ~ 150 DEG C reaction 1 ~ 24h, centrifugation afterwards collect product, and with sodium hypophosphite 300 DEG C of 2h that anneal in tube furnace, wash again, dry, obtain target product.
The product that the present invention obtains is three-dimensional porous sea urchin shape phosphatization cobalt, and it has three-dimensional porous structure, effectively remains avtive spot, improves the easy agglomeration traits of material in electrocatalysis process, makes it keep superior stability.
Further, the diameter about 1 ~ 20 μm of described three-dimensional porous sea urchin shape phosphatization cobalt, preferably about 5 ~ 10 μm, size uniformity, and can prepare in a large number.
The present invention first prepares three-dimensional sea urchin shape hydrated basic cobaltous carbonate by simple hydrothermal method, method then through high temperature phosphorization obtains three-dimensional porous sea urchin shape phosphatization cobalt, products therefrom size uniformity, its three-dimensional porous structure is that it keeps superior chemical property to provide prerequisite.
In addition, preparation method of the present invention can also be generalized to other transition metal phosphide of preparation as phosphatization manganese, iron phosphide, nickel phosphide, phosphorized copper etc.
For make the practicality of substantive distinguishing features of the present invention and institute's tool thereof be easier to understand, below just by reference to the accompanying drawings and preferred embodiment technical scheme of the present invention is described in further detail.But the following description about embodiment and explanation do not constitute any limitation scope.
The Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 0.5mmol is dissolved in 30mL water by embodiment 1; ultrasonic disperse is even; then, add 1.5mmol urea, continue stirring after 30 minutes; solution is transferred in 50mL reactor; 120 DEG C are reacted 12 hours, after cooling, and three-dimensional sea urchin shape hydrated basic cobaltous carbonate presoma (its pattern refers to Fig. 1 a-Fig. 1 b) of collected by centrifugation product; and anneal 2 hours in lower 300 DEG C of nitrogen protection with the sodium hypophosphite of 0.25g, three-dimensional porous sea urchin shape phosphatization cobalt can be obtained.
As can be seen from Fig. 2 a-Fig. 2 b, the phosphatization cobalt Product size of the present embodiment is homogeneous, diameter about 5 μm, and has three-dimensional porous sea urchin shape structure.Referring to Fig. 3 a-Fig. 3 b again, is rhombic system phosphatization cobalt by X-ray powder diffraction determination product.
The Ketjen black getting phosphatization cobalt that 5mg obtains and 1mg is dissolved in the mixing solutions of the Nafion solution (massfraction is 5%) of 32 μ L, the ethanol of 200 μ L and the deionized water of 768 μ L, ultrasonic at least 30 minutes, makes catalyst ink.Getting 4 μ L catalyst inks drips on the platinum carbon dioxide process carbon electrode that diameter is 3mm, obtained working electrode.Electrocatalytic hydrogen evolution reactivity worth uses traditional three-electrode system to measure, above-mentioned platinum carbon dioxide process carbon electrode is as working electrode, silver/silver chloride electrode is as reference electrode, platinum plate electrode is as to electrode, and the linear sweep voltammetry curve recorded with 5 millivolts of sweep velocitys per second is to characterize its electrocatalysis characteristic.In Fig. 4, current potential has carried out ohm compensation and has converted the current potential relative to reversible hydrogen electrode to.
The cobalt chloride of 1mmol is dissolved in 30mL ethanol by embodiment 2; ultrasonic disperse is even; then, add 5mmol urea, continue stirring after 30 minutes; solution is transferred in 50mL reactor; 100 DEG C are reacted 10 hours, after cooling, and collected by centrifugation product; and anneal 4 hours in lower 400 DEG C of argon shield with the potassium hypophosphite of 0.25g, three-dimensional porous sea urchin shape phosphatization cobalt can be obtained.
In addition, inventor also utilizes the various raw material in the alternate embodiment 1-2 such as other listed raw material and other processing condition and corresponding processing condition to carry out corresponding test above, to obtain the pattern, performance etc. of three-dimensional porous sea urchin shape phosphatization cobalt also ideal, basic similar to embodiment 1-2 product.
The present invention first prepares three-dimensional sea urchin shape hydrated basic cobaltous carbonate by simple hydrothermal method, method then through high temperature phosphorization obtains three-dimensional porous sea urchin shape phosphatization cobalt, and not only technique is simply controlled, and raw material sources are extensive, with low cost, and productive rate is higher, be suitable for scale operation, simultaneously obtained product size uniformity, there is sea urchin shape three-dimensional porous structure, active site retains many, has high reactivity and superior stability, has wide application prospects in electrocatalytic hydrogen evolution field.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all make in spirit of the present invention any amendment, supplement or similar fashion substitute etc., all should be included within protection scope of the present invention.
Claims (14)
1. a preparation method for three-dimensional porous sea urchin shape phosphatization cobalt, is characterized in that comprising:
Get cobalt salt and aminocompound Homogeneous phase mixing carry out hydro-thermal reaction, the obtained three-dimensional sea urchin shape hydrated basic cobaltous carbonate presoma formed primarily of nano wire assembling in polar neutral solvent;
By described hydrated basic cobaltous carbonate presoma and hypophosphite high temperature annealing, obtain three-dimensional porous sea urchin shape phosphatization cobalt.
2. the preparation method of three-dimensional porous sea urchin shape phosphatization cobalt according to claim 1, it is characterized in that comprising: get cobalt salt that mass ratio is 1 ~ 5:1 ~ 5 and aminocompound is dissolved in polar neutral solvent and carries out hydro-thermal reaction at 100 ~ 150 DEG C, after reaction 1 ~ 24h, obtain described three-dimensional sea urchin shape hydrated basic cobaltous carbonate presoma.
3. the preparation method of three-dimensional porous sea urchin shape phosphatization cobalt according to claim 1, is characterized in that comprising: by described hydrated basic cobaltous carbonate presoma and hypophosphite in 200 ~ 400 DEG C of 2 ~ 10h that anneal, obtain three-dimensional porous sea urchin shape phosphatization cobalt.
4. the preparation method of three-dimensional porous sea urchin shape phosphatization cobalt according to claim 3, is characterized in that the mass ratio of described hypophosphite 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 characterized in that described cobalt salt comprises cobalt chloride hexahydrate, six hydration cobaltous bromides, Cobaltous nitrate hexahydrate, four acetate hydrate cobalts, Cobalt monosulfate heptahydrate, acetylacetone cobalt (II), any one or two or more combinations in acetylacetone cobalt (III).
6. the preparation method of three-dimensional porous sea urchin shape phosphatization cobalt according to claim 1 and 2, it is characterized in that described polar neutral solvent comprises water, methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, any one or two or more combinations in DMF.
7. the preparation method of three-dimensional porous sea urchin shape phosphatization cobalt according to claim 1 and 2, is characterized in that described aminocompound comprises urea, ammonium formiate, ammonium acetate, ammonium carbamate, volatile salt, any one or two or more combinations in bicarbonate of ammonia.
8. the preparation method of the three-dimensional porous sea urchin shape phosphatization cobalt according to any one of claim 1-4, it is characterized in that described hypophosphite comprises calcium propionate, sodium hypophosphite, hypo-aluminum orthophosphate, magnesium hypophosphite, potassium hypophosphite, manganous hypophosphite, ammonium hypophosphite, nickelous hypophosphite, ferric hypophosphite, any one or two or more combinations in zinc hypophosphite.
9. the preparation method of the three-dimensional porous sea urchin shape phosphatization cobalt according to any one of claim 1-4, is characterized in that specifically comprising:
I, ultrasonic dispersed after getting cobalt salt and polar neutral solvent;
II, to the final mixing solutions that obtains of step I add aminocompound and blending dispersion evenly after, then react 1 ~ 24h in 100 ~ 150 DEG C;
III, isolate by step II hydro-thermal reaction products therefrom, and clean, dry;
IV, by step III products therefrom and hypophosphite at 200 ~ 400 DEG C of 2 ~ 10h that anneal, obtain described three-dimensional porous sea urchin shape phosphatization cobalt.
10. the three-dimensional porous sea urchin shape phosphatization cobalt that according to any one of claim 1-9 prepared by method, it has three-dimensional porous structure, and diameter is 1 ~ 20 μm, is preferably 5 ~ 10 μm.
The preparation method of 11. 1 kinds of three-dimensional porous sea urchin shape metal phosphides, it is characterized in that comprising: get metal-salt and aminocompound Homogeneous phase mixing carry out hydro-thermal reaction in polar neutral solvent, the obtained three-dimensional sea urchin shape hydrated basic carbonate precursor formed primarily of nano wire assembling, and, by described hydrated basic carbonate precursor and hypophosphite high temperature annealing, obtain three-dimensional porous sea urchin shape metal phosphide; Wherein, described metal-salt is at least selected from manganese salt, molysite, nickel salt and mantoquita.
The 12. three-dimensional porous sea urchin shape metal phosphides prepared by method described in claim 11.
13. three-dimensional porous sea urchin shape phosphatization cobalts as claimed in claim 10 or the application of three-dimensional porous sea urchin shape metal phosphide as claimed in claim 12 in electrocatalysis.
14. 1 kinds of electrocatalysis materials or device, is characterized in that comprising three-dimensional porous sea urchin shape phosphatization cobalt according to claim 10 or three-dimensional porous sea urchin shape metal phosphide according to claim 12.
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