CN101973537A - Method for preparing transition metal phosphide - Google Patents
Method for preparing transition metal phosphide Download PDFInfo
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- CN101973537A CN101973537A CN 201010521225 CN201010521225A CN101973537A CN 101973537 A CN101973537 A CN 101973537A CN 201010521225 CN201010521225 CN 201010521225 CN 201010521225 A CN201010521225 A CN 201010521225A CN 101973537 A CN101973537 A CN 101973537A
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- transition metal
- metal phosphide
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Abstract
The invention discloses a method for preparing transition metal phosphide, which comprises the following steps: adding ethylene glycol and water in a preset volume ratio, and then mixing the ethylene glycol and the water evenly; adding nickel salt into the obtained mixture, then stirring the obtained solution until the solution is transparent; adding yellow phosphorus into the transparent solution, then heating the obtained mixture from room temperature under an airtight condition so as to carry out reaction on the obtained mixture for 12h at a temperature of 140 to 180 DEG C; after the reaction is completed, cooling the obtained product to room temperature with a reacting furnace, then filtering the obtained product so as to obtain coarse products; washing the obtained coarse products sequentially by benzene, ethanol and distilled water; putting the washed products in a vacuum drying oven to carry out vacuum drying at a temperature of 50 DEG C, then obtaining the transition metal phosphide. In the invention, because of adopting a method for carrying out liquid solid chemical reaction in a solvent thermal system, the preparation of the transition metal phosphide can be realized by conventional equipment at a low temperature; and the water and the ethylene glycol are used as solvent, which reduces the production cost, simplifies the production process, avoids the pollution caused by toxic by-products, and raises the yield; and meanwhile, the application of toxic and difficultly-synthesized metal organic compounds and expensive raw materials is also avoided.
Description
Technical field
The invention belongs to the thermal synthesis production method of solvent field, especially a kind of technology of preparing that relates to the transition metal phosphide of two kinds of compositions.
Background technology
Transition metal phosphide is another new catalytic material that occurs after transition metal carbide, nitride, because physical properties and excellent hydrogenating desulfurization, the activity and the selectivity of denitrogenation that it is similar with nitride to carbide, thereby become a focus of new catalytic material research field, and be successfully applied to chemical fields such as refining of petroleum.Nickel phosphide is extraordinary anti-oxidant, anticorrosive and high-abrasive material, be high reactivity, high stability and the new catalytic material with anti-sulfur poisonous performance and luminescent device and materials of electronic components, thereby its application prospect is boundless.
At present, the preparation method of nickel phosphide mainly contains: the direct chemical combination of simple substance under the high temperature protection gas; The solid-state displacement reaction of nickelous chloride and phosphine; The reaction of nickelous chloride and phosphuret-(t)ed hydrogen; The decomposition of organometallic compound; The reduction of nickelous phosphate; Nickelous chloride and sodium hypophosphite prepared in reaction etc.In all these preparation methods, what have needs high temperature, the raw material that the needs that have are very expensive, and perhaps the by product of Sheng Chenging can cause the phosphide pollution.It is that the salt (as nickelous nitrate) with metal and the oxide compound of ammonium phosphate salt are presoma that the method for temperature programmed reduction(TPR) prepares phosphide, at H
2In the atmosphere, heating reduction and making progressively.But, adopt this method except preparation temperature higher (being higher than 550 ℃), slowly temperature rise rate in scale operation difficult the realization, for fear of the oxidizing reaction of fierceness, the fresh phosphide for preparing need just can be exposed in the air through after the surface passivation.It is solvent with n-octyl phosphine (TOP) or n-octyl phosphine oxide that Park etc. have reported a kind of, prepares transition metal phosphine thing with transition metal carbonyl compound generation liquid phase reaction.But still there are some problems in this method, and is higher as the TOP price, and only can be used for preparing the transition metal phosphide of non-loading type.Solvent thermal also can prepare transition metal phosphide, but the phosphide that the solvent-thermal method of reporting at present obtains mostly is random particle.
Summary of the invention
The objective of the invention is to overcome in the existing production technique deficiencies such as starting material and equipment cost costliness or product particle are irregular, a kind of preparation method of transition metal phosphide is provided, this method not only production technique is simple, and productive rate height, nontoxicity by-product contamination.
The objective of the invention is to solve by the following technical programs:
The preparation method of this kind transition metal phosphide of the present invention may further comprise the steps:
1) adding volume ratio in autoclave is 1: the ethylene glycol of (1～4) and water, and mixing and stirring solution adds the nickel salt of 0.01～0.03g in every ml soln, stir and dissolve, form clear solution fully until solid;
2) clear solution is changed in the polytetrafluoroethyllining lining, the yellow phosphorus that in every milliliter of clear solution, adds 0.005～0.02g, then polytetrafluoroethyllining lining is sealed in the stainless steel mould, in confined conditions by room temperature begin the heating and at 140-180 ℃ of reacting by heating 12h;
3) after reaction was finished, furnace cooling was used the fast quantification filter paper filtering then to room temperature, promptly gets crude product;
4) with benzene, ethanol and distilled water crude product is washed successively;
5) product after will washing is inserted in the vacuum drying oven, in 50 ℃ of following vacuum-drying 4h, obtains described transition metal phosphide.
Further, above-mentioned steps 1) in nickel salt be single nickel salt, nickelous chloride or nickelous nitrate.
The present invention has following beneficial effect:
The present invention adopts the method for carrying out solid-liquid reaction in the solvent thermal system, thereby can be under lower temperature, use conventional equipment to realize the preparation of metal phosphide catalytic material, and water and ethylene glycol is as reaction solvent, reduced production cost, simplified production technique, avoided toxic by-products pollution, improved productive rate.Also avoided poisonous simultaneously, be difficult to the use of synthetic organometallics and expensive raw materials.
Description of drawings
Fig. 1 is the product Ni of the present invention's preparation
2P carries out the style that XRD analysis obtained;
Fig. 2 is the product Ni of the present invention's preparation
12P
5Carry out the style that XRD analysis obtained;
Fig. 3 (A) is product Ni of the present invention
2P microballoon photo; (B) be product Ni of the present invention
2The photo of the dendritic crystallite of P; (C) be product Ni of the present invention
12P
5The photo of microballoon;
Fig. 4 is product Ni of the present invention
2The process of growth of the dendritic crystallite of P;
Fig. 5 is the Ni of embodiment 4 preparations
2The thing phasor of P powder;
Fig. 6 is the Ni of embodiment 5 preparations
2The thing phasor of P powder;
Fig. 7 is the Ni of embodiment 6 preparations
2The thing phasor of P powder;
Fig. 8 is the Ni of embodiment 7 preparations
2The thing phasor of P powder.
Embodiment
Below in conjunction with accompanying drawing the present invention is done and to describe in further detail:
Embodiment 1
The preparation method of the transition metal phosphide of present embodiment carries out according to following steps:
1) adding volume ratio in autoclave is 1: 1 ethylene glycol and water, and mixing and stirring solution adds the nickel salt of 0.01g in every ml soln, stir and dissolve, form clear solution fully until solid; Wherein nickel salt is selected single nickel salt for use;
2) clear solution is changed in the polytetrafluoroethyllining lining of 50mL, this teflon-lined compactedness is 80%, the yellow phosphorus that in every milliliter of clear solution, adds 0.005g, then polytetrafluoroethyllining lining is sealed in the stainless steel mould, in confined conditions by room temperature begin the heating and at 140 ℃ of reacting by heating 12h;
3) after reaction was finished, furnace cooling was used the fast quantification filter paper filtering then to room temperature, promptly gets crude product;
4) with benzene, ethanol and distilled water crude product is washed 2 times successively;
5) product after will washing is inserted in the vacuum drying oven, in 50 ℃ of following vacuum-drying 4h, obtains described transition metal phosphide.
The preparation method of the transition metal phosphide of present embodiment carries out according to following steps:
1) adding volume ratio in autoclave is 1: 3 ethylene glycol and water, and mixing and stirring solution adds the nickel salt of 0.03g in every ml soln, stir and dissolve, form clear solution fully until solid; Wherein nickel salt is selected nickelous chloride for use;
2) clear solution is changed in the polytetrafluoroethyllining lining of 50mL, this teflon-lined compactedness is 80%, the yellow phosphorus that in every milliliter of clear solution, adds 0.02g, then polytetrafluoroethyllining lining is sealed in the stainless steel mould, in confined conditions by room temperature begin the heating and at 180 ℃ of reacting by heating 12h;
3) after reaction was finished, furnace cooling was used the fast quantification filter paper filtering then to room temperature, promptly gets crude product;
4) with benzene, ethanol and distilled water crude product is washed 3 times successively;
5) product after will washing is inserted in the vacuum drying oven, in 50 ℃ of following vacuum-drying 4h, obtains described transition metal phosphide.
Embodiment 3
The preparation method of the transition metal phosphide of present embodiment carries out according to following steps:
1) adding volume ratio in autoclave is 1: 2 ethylene glycol and water, and mixing and stirring solution adds the nickel salt of 0.02g in every ml soln, stir and dissolve, form clear solution fully until solid; Wherein nickel salt is selected nickelous nitrate for use;
2) clear solution is changed in the polytetrafluoroethyllining lining of 50mL, this teflon-lined compactedness is 80%, the yellow phosphorus that in every milliliter of clear solution, adds 0.01g, then polytetrafluoroethyllining lining is sealed in the stainless steel mould, in confined conditions by room temperature begin the heating and at 160 ℃ of reacting by heating 12h;
3) after reaction was finished, furnace cooling was used the fast quantification filter paper filtering then to room temperature, promptly gets crude product;
4) with benzene, ethanol and distilled water crude product is washed 3 times successively;
5) product after will washing is inserted in the vacuum drying oven, in 50 ℃ of following vacuum-drying 4h, obtains described transition metal phosphide.
Embodiment 4:
The preparation method of the transition metal phosphide that present embodiment proposes finishes according to following explanation:
The volume ratio of at first pressing 1: 4 is got ethylene glycol and water mixing and stirring 40mL and is added reactor, adds 0.525g single nickel salt (NiSO subsequently
46H
2O), stirred solution changes solution in the 50mL polytetrafluoroethyllining lining till bleach then; Then in clear solution, add excessive yellow phosphorus 0.31g, this liner is sealed in the stainless steel mould, rise to 160 ℃ by room temperature, and insulation 12h; Furnace cooling respectively washs the powder that obtains 2-3 time with ethanol, benzene and distilled water to room temperature then, insert in the vacuum drying oven, and 50 ℃ of vacuum-drying 4h, getting the product powder is transition metal phosphide of the present invention.
Ni by the present embodiment preparation
2The thing of P powder is mutually as Fig. 5, as seen from the figure gained Ni
2P powder thing is mutually pure.
Embodiment 5:
The volume ratio of at first pressing 1: 4 is got ethylene glycol and water mixing and stirring 40mL and is added reactor, adds 0.525g single nickel salt (NiSO subsequently
46H
2O), stirred solution changes solution in the 50mL polytetrafluoroethyllining lining till bleach then; Then in clear solution, add excessive yellow phosphorus 0.31g, this liner is sealed in the stainless steel mould, rise to 180 ℃ by room temperature, and insulation 12h; Furnace cooling respectively washs the powder that obtains 2-3 time with ethanol, benzene and distilled water to room temperature then, insert in the vacuum drying oven, and 50 ℃ of vacuum-drying 4h, getting the product powder is transition metal phosphide of the present invention.
Ni by the present embodiment preparation
2The thing of P powder is mutually as Fig. 6, as seen from the figure gained Ni
2P powder thing is mutually pure.
Embodiment 6:
The volume ratio of at first pressing 1: 1 is got water and ethylene glycol mixing and stirring 40mL and is added reactor, adds 1.051g single nickel salt (NiSO subsequently
46H
2O), stirred solution changes solution in the 50mL polytetrafluoroethyllining lining till bleach then; Then in clear solution, add excessive yellow phosphorus 0.31g, this liner is sealed in the stainless steel mould, rise to 140 ℃ by room temperature, and insulation 12h; Furnace cooling respectively washs the powder that obtains 2-3 time with ethanol, benzene and distilled water to room temperature then, inserts in the vacuum drying oven 50 ℃ of vacuum-drying 4h.Getting the product powder is transition metal phosphide of the present invention.
Ni by the present embodiment preparation
12P
5The thing of powder is mutually as Fig. 7, as seen from the figure gained Ni
12P
5The powder thing is mutually pure.
Embodiment 7:
The volume ratio of at first pressing 1: 1 is got water and ethylene glycol mixing and stirring 40mL and is added reactor, adds 0.525g single nickel salt (NiSO subsequently
46H
2O), stirred solution changes solution in the 50mL polytetrafluoroethyllining lining till bleach then; Then in clear solution, add excessive yellow phosphorus 0.31g, this liner is sealed in the stainless steel mould, rise to 160 ℃ by room temperature, and insulation 12h; Furnace cooling respectively washs the powder that obtains 2-3 time with ethanol, benzene and distilled water to room temperature then, inserts in the vacuum drying oven 50 ℃ of vacuum-drying 4h.Getting the product powder is transition metal phosphide of the present invention.
Ni by the present embodiment preparation
12P
5The thing of powder is mutually as Fig. 8, as seen from the figure gained Ni
12P
5The powder thing is mutually pure.
In sum, preparation method of the present invention is simple, raw materials usedly extensively is easy to get, and can prepare two kinds of different the composition and the nickel phosphide of pattern: Ni at same solvent system
2P and Ni
12P
5, be the product Ni that the present invention prepares as Fig. 1
2P carries out the style that XRD analysis obtained, and the product Ni that Fig. 2 is the present invention to be prepared
12P
5Carry out the style that XRD analysis obtained; Fig. 3 (A) is product Ni of the present invention
2P microballoon photo; (B) be product Ni of the present invention
2The photo of the dendritic crystallite of P; (C) be product Ni of the present invention
12P
5The photo of microballoon; Its result proves: (ethylene glycol and water) can prepare nickel phosphide (Ni under 1: 4 solvent ratios
2P) crystallite is product Ni of the present invention as Fig. 4
2The process of growth of the dendritic crystallite of P.And can obtain hollow acanthosphere and two kinds of crystal of dendritic crystallite by adjusting differing temps (160-180 ℃); (ethylene glycol and water) can prepare hollow thorn globular nickel phosphide (Ni under 1: 1 solvent ratios
12P
5) microballoon; The content of ethylene glycol and water can be realized different composition nickel phosphide (Ni in add-on by adjusting single nickel salt and the mixed solvent
2P and Ni
12P
5) between the phase co-conversion.
Claims (2)
1. the preparation method of a transition metal phosphide is characterized in that, may further comprise the steps:
1) adding volume ratio in autoclave is 1: the ethylene glycol of (1～4) and water, and mixing and stirring solution adds the nickel salt of 0.01～0.03g in every ml soln, stir and dissolve, form clear solution fully until solid;
2) clear solution is changed in the polytetrafluoroethyllining lining, the yellow phosphorus that in every milliliter of clear solution, adds 0.005～0.02g, then polytetrafluoroethyllining lining is sealed in the stainless steel mould, in confined conditions by room temperature begin the heating and at 140-180 ℃ of reacting by heating 12h;
3) after reaction was finished, furnace cooling was used the fast quantification filter paper filtering then to room temperature, promptly gets crude product;
4) with benzene, ethanol and distilled water crude product is washed successively;
5) product after will washing is inserted in the vacuum drying oven, in 50 ℃ of following vacuum-drying 4h, obtains described transition metal phosphide.
2. the preparation method of transition metal phosphide according to claim 1 is characterized in that, described nickel salt is single nickel salt, nickelous chloride or nickelous nitrate.
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| CN 201010521225 CN101973537A (en) | 2010-10-27 | 2010-10-27 | Method for preparing transition metal phosphide |
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|---|---|---|---|
| CN 201010521225 CN101973537A (en) | 2010-10-27 | 2010-10-27 | Method for preparing transition metal phosphide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104555957A (en) * | 2014-12-29 | 2015-04-29 | 陕西科技大学 | Method for preparing hollow cobalt phosphide (Co2P) multi-level microspheres |
| CN106179434A (en) * | 2016-07-05 | 2016-12-07 | 济南大学 | A kind of porous Ni P based compound and preparation method thereof |
| CN107088432A (en) * | 2017-04-12 | 2017-08-25 | 南京师范大学 | A kind of two-dimentional Ru doping Ni2P plate-like nano flakes and its preparation method and application |
| CN112619571A (en) * | 2020-11-18 | 2021-04-09 | 东南大学 | Method for regulating and controlling relative exposure strength of crystal face of transition metal phosphide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391223A (en) * | 2007-09-19 | 2009-03-25 | 中国科学院大连化学物理研究所 | Preparation method of no-loaded nickel phosphide catalyst |
-
2010
- 2010-10-27 CN CN 201010521225 patent/CN101973537A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391223A (en) * | 2007-09-19 | 2009-03-25 | 中国科学院大连化学物理研究所 | Preparation method of no-loaded nickel phosphide catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 《Ceramics International》 20100104 Zongyi Liu et al. A simple mild hydrothermal route for the synthesis of nickel phosphide powders 第1155-1158页 1-2 第36卷, 第3期 2 * |
| 《中国博士学位论文全文数据库 工程科技I辑》 20070915 刘淑玲 过渡金属氮化物、磷化物和硫化物纳米晶的溶剂热合成与表征 第37-48页 1-2 , 第3期 2 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104555957A (en) * | 2014-12-29 | 2015-04-29 | 陕西科技大学 | Method for preparing hollow cobalt phosphide (Co2P) multi-level microspheres |
| CN106179434A (en) * | 2016-07-05 | 2016-12-07 | 济南大学 | A kind of porous Ni P based compound and preparation method thereof |
| CN107088432A (en) * | 2017-04-12 | 2017-08-25 | 南京师范大学 | A kind of two-dimentional Ru doping Ni2P plate-like nano flakes and its preparation method and application |
| CN107088432B (en) * | 2017-04-12 | 2019-09-06 | 南京师范大学 | A kind of two dimension Ru doping Ni2P plate-like nano flake and its preparation method and application |
| CN112619571A (en) * | 2020-11-18 | 2021-04-09 | 东南大学 | Method for regulating and controlling relative exposure strength of crystal face of transition metal phosphide |
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Application publication date: 20110216 |