CN102031506A - Preparation method and application of Ni-P micro-nanometer material - Google Patents
Preparation method and application of Ni-P micro-nanometer material Download PDFInfo
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- CN102031506A CN102031506A CN 201010534489 CN201010534489A CN102031506A CN 102031506 A CN102031506 A CN 102031506A CN 201010534489 CN201010534489 CN 201010534489 CN 201010534489 A CN201010534489 A CN 201010534489A CN 102031506 A CN102031506 A CN 102031506A
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- 229910018104 Ni-P Inorganic materials 0.000 title claims abstract description 28
- 229910018536 Ni—P Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title abstract description 12
- 150000002815 nickel Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 239000002086 nanomaterial Substances 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 18
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 6
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 12
- 241000257465 Echinoidea Species 0.000 description 9
- 239000002594 sorbent Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000080590 Niso Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a Ni-P micro-nanometer material. The method comprises the following steps of: dissolving a soluble nickel salt and a phosphorus source with water, adding N,N-dimethylformamide, evenly stirring at room temperature and placing in a reaction kettle, raising the temperature, reacting for 8-48h at 110-160 DEG C, cooling to the room temperature, washing the product with deionized water for many times, vacuum drying at 60 DEG C to constant weight to obtain the Ni-P micro-nanometer material, wherein the molar concentration ratio of the nickel salt to the phosphorus source is 1:(0.25-1) and the volume ratio of water to the N,N-dimethylformamide is 1:(0.5-5). Compared with the prior art, the invention ensures that the reaction condition is temperate and the prepared echinus-like Ni-P micro-nanometer material has the characteristics of large specific surface area, capability of selectively absorbing heavy metal ions, strong absorption ability and easy separation from an absorbed solution; besides, the recovered adsorbent can be easily regenerated and reused.
Description
Technical field
The present invention relates to the preparation method and the application thereof of micro Nano material, particularly the preparation method of Ni-P micro Nano material and application thereof.
Background technology
Mostly traditional preparation Ni-P micro Nano material is to utilize electrodip process, and its synthetic particulate state, bar-shaped, wire, tubulose micro Nano material are used for the growth of catalyzed carbon nanofiber more.(J.Phys.Chem.B 2005,109,24361-24368) wait and synthesized the Ni-P nanometer ball under the condition of hydro-thermal, but need do the pH regulator agent simultaneously at highly purified N with highly basic for Xie
2Carry out under the protection, so the condition harshness.Bernardi (J.Mater.Sci2008,43,469-474) wait and to have synthesized Ni-P hollow micron ball, but this method will be under the acting in conjunction of NaOH and surfactant SDS with chemical reduction method, so complicated condition.Simultaneously, the syringe method is arranged, microwave method, thermal decomposition method, hydrothermal method etc. preparations nickel phosphide micro Nano material, but its reaction multiselect is with deleterious or expensive phosphorus source, and the while temperature of reaction generally is higher than 180 ℃, and the synthetic material is used on the organic catalysis mostly.
Chinese patent CN1200955A has introduced a kind of preparation method of Ni-P amorphous alloy catalyst.This Preparation of catalysts is by Ni-B amorphous alloy porous support and contains H
2PO
2 -And Ni
2+Ionic mixing solutions contact and reaction makes.This preparation process needs porous material as its operation more complicated of carrier.It is the surface chemical plating Ni-P process of main salt with single nickel salt that Chinese patent CN101187020A introduces a kind of, and its technological process is: ultrasonic cleaning-alkali cleaning-pickling-activation-chemical nickel phosphorus plating.As seen its technology more complicated.
Summary of the invention
The 1st technical problem to be solved by this invention provides a kind of preparation method and application of simple Ni-P micro Nano material.
The 2nd technical problem to be solved by this invention is the application of above-mentioned micro Nano material.
The technical scheme of the technical problem that the present invention solves is: a kind of preparation method of Ni-P micro Nano material:
Elder generation is with the nickel salt and the phosphorus source water dissolution of solubility, add N again, dinethylformamide (DMF), stirring under room temperature is placed in the reactor, heats up, and reacts 8～48 hours down in 110～160 ℃, be cooled to room temperature, with the deionized water wash product for several times,, get final product to constant weight in 60 ℃ of following vacuum-dryings; Nickel salt and phosphorus source molar concentration rate are 1: 0.25-1; Water and N, the volume ratio of dinethylformamide is 1: 0.5-2.
Described soluble nickel salt is nickelous chloride, nickelous nitrate, single nickel salt, nickel acetate, and its chemical formula is respectively NiCl
2, Ni (NO
3)
2, NiSO
4, Ni (CH
3COO)
2
Described phosphorus source is a metal phosphinate, preferred sodium hypophosphite and potassium hypophosphite, and its chemical formula is NaH
2PO
2, KH
2PO
2
The made micro Nano material of the present invention is used in containing the trade effluent of heavy metal ion.
Can selective adsorption contain Pb especially
2+, Cd
2+The ionic heavy metal solution.
The pattern that the present invention recently controls the magnetic micro Nano material by the nickel salt and the hypophosphite volumetric molar concentration of solubility obtains the sea urchin shape microballoon of size homogeneous; It has very big specific surface area.In the process of using,, therefore after having adsorbed heavy metal,, this micro Nano material is separated with waste water by externally-applied magnetic field because the gained micro Nano material is magnetic.
In the mixed solvent of the water of certain temperature, suitable proportion and DMF, the nickel salt of solubility and hypophosphite generation redox reaction generate the Ni-P micro Nano material.Owing to contain water-wet side and hydrophobic side in the DMF molecule, thus DMF in reaction not only as solvent but also playing the part of the effect of tensio-active agent, form coordination between N nuclear power in its hydrophilic radical and the nickel simultaneously.When reaction takes place,, thereby finally obtained sea urchin shape Ni-P micro Nano material because the sterically hindered effect of DMF molecule forces the Ni-P micro Nano material to form along specific direction.In addition, excessive hypophosphite can change the pH value of system significantly, thereby is unfavorable for the formation of sea urchin shape Ni-P micro Nano material.
The present invention compared with prior art, the reaction conditions gentleness, the Ni-P micro Nano material of made sea urchin shape, have specific surface area big, can the selective adsorption heavy metal ion and high adsorption capacity, be easy to isolating characteristics from adsorbed solution; Simultaneously, the sorbent material of recovery can easily regenerate and reuse.
Description of drawings
Fig. 1 is the X-ray powder diffraction pattern of embodiment 1 gained nano material.
Fig. 2 is scanning electronic microscope (SEM) photo of embodiment 1 gained micro Nano material.
Fig. 3 is transmission electron microscope (TEM) photo of embodiment 1 gained micro materials.
Fig. 4 is the room temperature magnetic hysteresis loop of embodiment 1 micro materials.
Fig. 5 is the N of embodiment 1 gained micro materials
2Adsorption isothermal line and graph of pore diameter distribution are conciliate in absorption.
Fig. 6 is the Pb that contains of embodiment 1 gained micro materials
2+The adsorption curve of solution.
Fig. 7 is the Cd that contains of embodiment 1 gained micro materials
2+The adsorption curve of solution.
Fig. 8 is the Pb that contains of embodiment 1 gained micro materials
2+, Cd
2+The time adsorption curve of solution.
Fig. 9 is the Pb that contains of embodiment 1 gained micro materials
2+, Cd
2+The isothermal adsorption curve of solution.
Figure 10 is the Pb that contains of embodiment 1 gained micro materials
2+, Cd
2+The solution weight attached curve of reverting to take drugs.
Embodiment
Below in conjunction with embodiment the present invention is done detailed explanation.
Embodiment 1:
1, sea urchin shape magnetic Ni-P nano material preparation process:
With 2mmol NiCl
26H
2O with 1mmol NaH
2PO
2H
2O is dissolved in the 10ml deionized water, adds 10ml N then, dinethylformamide (DMF).With this mixed solution under the room temperature on magnetic stirring apparatus vigorous stirring 20 minutes, then this mixed solution is poured in the polytetrafluoroethyllining lining that volume is the 25ml stainless steel autoclave, reactor is put into thermostatic drying chamber, 160 ℃ of reactions 16 hours down.After reaction finished, question response still temperature was reduced to room temperature, opens reactor, and liquid in the still is poured in the clean beaker, can see that black solid generates.With the deionized water wash product for several times, 60 ℃ of following vacuum-dryings 6 hours, promptly get black powder shape product.
With day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument to implementing product (the Cu K alpha-ray of experiment 1, λ=0.154060nm, sweep velocity 0.02o/s) carry out the thing identification of phases, as shown in fig. 1, can only see that about 44.6 degree individual amorphous bag is arranged, illustrate that the product crystallinity is very poor.When product 500 ℃ of thermal treatments after 2 hours, Ni and Ni
3(Fig. 1) appears in the P diffraction peak.Fig. 2 Fig. 3 shows that products therefrom has sea urchin shape structure.Fig. 4 confirms that the product of gained has magnetic.Fig. 5 illustrates that products therefrom has bigger specific surface area (425m
2/ g).
Embodiment 2:
The Pb that 10mg embodiment 1 products therefrom is added 50 milliliters of 10mg/L
2+In the solion, whip attachment 10 minutes adopts the ICP Atomic Emission SpectrometerAES to measure Pb
2+Ionic concn drops to 2.2mg/L (shown in Figure 6) by the preceding 10mg/L of absorption.As calculated, sorbent material is at the Pb of 10mg/L
2+Absorption Pb in the solion
2+Ability be 39.0mg/g.
Embodiment 3:
The Cd that 10mg embodiment 1 products therefrom is added 50 milliliters of 10mg/L
2+In the solion, whip attachment 30 minutes adopts the ICP Atomic Emission SpectrometerAES to measure, i.e. Cd
2+Ionic concn drops to 1.86mg/L (as shown in Figure 7) by the preceding 10mg/L of absorption, and as calculated, sorbent material is at the Cd of 10mg/L
2+Adsorb Cd in the solion
2+Ability be 40.7mg/g.
Embodiment 4:
The Cu that 10mg embodiment 1 products therefrom is added 50 milliliters of 10mg/L
2+In the solion, whip attachment 10 minutes adopts the ICP Atomic Emission SpectrometerAES to measure, and the result shows Cu
2+Ionic concn is constant.
Embodiment 5:
Embodiment 6:
Embodiment 7:
The Hg that 10mg embodiment 1 products therefrom is added 50 milliliters of 10mg/L
2+In the solion, whip attachment 10 minutes adopts the ICP Atomic Emission SpectrometerAES to measure, and the result shows Hg
2+Ionic concn is constant.
Above presentation of results, sea urchin shape magnetic Ni-P nano material adsorbent for heavy metal has the selection absorption property, to Pb
2+, Cd
2+But active adsorption, and to heavy metal ion Cu
2+, As (V), Cr (VI) and Hg
2+Ionic absorption to no effect.
Embodiment 8:
The Pb that 10mg embodiment 1 products therefrom is added 50 milliliters of 10mg/L respectively
2+, Cd
2+In the solion, the whip attachment different time adopts the ICP Atomic Emission SpectrometerAES to measure, the result be presented at absorption after 50 minutes sorbent material to Pb
2+, Cd
2+Absorption reach capacity, its adsorption effect is～75% and～80% (as Fig. 8).
Embodiment 9:
At room temperature, the Pb that 10mg embodiment 1 products therefrom is added 50 milliliters of different concns respectively
2+, Cd
2+In the solion, whip attachment 10 minutes adopts the ICP Atomic Emission SpectrometerAES to measure, after the result shows that sorbent material reaches capacity, to Pb
2+, Cd
2+Adsorptive power be～170mg/g and～110mg/g.
Embodiment 10:
The sorbent material that absorption is reached capacity separates with waste water by externally-applied magnetic field, and the sorbent material after the separation is put into the deionized water of 50ml, and supersound washing is removed the heavy metal ion of surface adsorption for several times.Figure 10 is 5 recycling absorption of sorbent material Pb
2+, Cd
2+Absorption figure.The result shows: sorbent material still has adsorption effect preferably after repeating 5 times.
Embodiment 11: sea urchin shape magnetic Ni-P nano material preparation process:
With NaH among the embodiment 1
2PO
2H
2O KH
2PO
2H
2O substitutes, under the same conditions, and gained pattern and thing same instance 1.
Embodiment 12: sea urchin shape magnetic Ni-P nano material preparation process:
With the NiCl among the embodiment 1
26H
2O Ni (NO
3)
2.6H
2O substitutes, under the same conditions, and gained pattern and thing same instance 1.
Claims (6)
1. the preparation method of a Ni-P micro Nano material: it is characterized in that:
Elder generation is with the nickel salt and the phosphorus source water dissolution of solubility, add N again, dinethylformamide, stirring under room temperature is placed in the reactor, heats up, and reacts 8～48 hours down in 110～160 ℃, be cooled to room temperature, with the deionized water wash product for several times,, get final product to constant weight in 60 ℃ of following vacuum-dryings; Nickel salt and phosphorus source molar concentration rate are 1: 0.25-1; Water and N, the volume ratio of dinethylformamide is 1: 0.5-2.
2. the preparation method of a kind of Ni-P micro Nano material according to claim 1: it is characterized in that: described soluble nickel salt is nickelous chloride, nickelous nitrate, single nickel salt, nickel acetate.
3. the preparation method of a kind of Ni-P micro Nano material according to claim 1: it is characterized in that: described phosphorus source is a metal phosphinate.
4. the preparation method of a kind of Ni-P micro Nano material according to claim 3: it is characterized in that: described phosphorus source is sodium hypophosphite and potassium hypophosphite.
5. the described Ni-P micro Nano material of claim 1 is used at the trade effluent that contains heavy metal ion.
6. the described Ni-P micro Nano material of claim 1 is containing pb
2+, Cd
2+The ionic trade effluent is used.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105344892A CN102031506B (en) | 2010-11-08 | 2010-11-08 | Preparation method and application of Ni-P micro-nanometer material |
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|---|---|---|---|
| CN2010105344892A CN102031506B (en) | 2010-11-08 | 2010-11-08 | Preparation method and application of Ni-P micro-nanometer material |
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|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117372A (en) * | 2013-04-26 | 2014-10-29 | 中国石油天然气股份有限公司 | Hydrothermal preparation method of supported nickel phosphide catalyst taking nano red phosphorus as phosphorus source |
| CN106179140A (en) * | 2016-07-07 | 2016-12-07 | 江苏大学 | A kind of preparation method of nickel phosphide hollow nanospheres |
| CN107473189A (en) * | 2017-09-30 | 2017-12-15 | 合肥师范学院 | The preparation method of sea urchin shape nanometer lead telluride and the sea urchin shape nanometer lead telluride being prepared |
| CN109647459A (en) * | 2019-01-17 | 2019-04-19 | 淮北师范大学 | A kind of preparation method for the Ni-based phosphide that composition is controllable |
| CN112194107A (en) * | 2020-09-28 | 2021-01-08 | 银隆新能源股份有限公司 | Transition metal phosphide nanowire bundle, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5291725A (en) * | 1976-01-29 | 1977-08-02 | Tatsuko Takei | Producing method of high hardness alloy |
| CN1439741A (en) * | 2002-10-23 | 2003-09-03 | 沈阳黎明航空发动机(集团)有限责任公司 | Method for chemically electroplating thick nickle on titanium alloy |
-
2010
- 2010-11-08 CN CN2010105344892A patent/CN102031506B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5291725A (en) * | 1976-01-29 | 1977-08-02 | Tatsuko Takei | Producing method of high hardness alloy |
| CN1439741A (en) * | 2002-10-23 | 2003-09-03 | 沈阳黎明航空发动机(集团)有限责任公司 | Method for chemically electroplating thick nickle on titanium alloy |
Non-Patent Citations (1)
| Title |
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| 《Materials Chemistry and Physics》 20100516 Lina Jin etal Large-scale synthesis of Mn11(HPO3)8(OH)6 superstructures constructed by microrods via a mixed-solvothermal route 1-6 , 2 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117372A (en) * | 2013-04-26 | 2014-10-29 | 中国石油天然气股份有限公司 | Hydrothermal preparation method of supported nickel phosphide catalyst taking nano red phosphorus as phosphorus source |
| CN104117372B (en) * | 2013-04-26 | 2016-08-03 | 中国石油天然气股份有限公司 | Hydrothermal preparation method of supported nickel phosphide catalyst taking nano red phosphorus as phosphorus source |
| CN106179140A (en) * | 2016-07-07 | 2016-12-07 | 江苏大学 | A kind of preparation method of nickel phosphide hollow nanospheres |
| CN106179140B (en) * | 2016-07-07 | 2019-01-08 | 江苏大学 | A kind of preparation method of nickel phosphide hollow nanospheres |
| CN107473189A (en) * | 2017-09-30 | 2017-12-15 | 合肥师范学院 | The preparation method of sea urchin shape nanometer lead telluride and the sea urchin shape nanometer lead telluride being prepared |
| CN107473189B (en) * | 2017-09-30 | 2019-11-26 | 合肥师范学院 | The preparation method of sea urchin shape nanometer lead telluride and the sea urchin shape nanometer lead telluride being prepared |
| CN109647459A (en) * | 2019-01-17 | 2019-04-19 | 淮北师范大学 | A kind of preparation method for the Ni-based phosphide that composition is controllable |
| CN109647459B (en) * | 2019-01-17 | 2021-07-30 | 淮北师范大学 | Preparation method of nickel-based phosphide with controllable composition |
| CN112194107A (en) * | 2020-09-28 | 2021-01-08 | 银隆新能源股份有限公司 | Transition metal phosphide nanowire bundle, and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN102031506B (en) | 2012-06-06 |
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