CN100372968C - NiP amorphous alloy and prep. thereof - Google Patents
NiP amorphous alloy and prep. thereof Download PDFInfo
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- CN100372968C CN100372968C CNB031090621A CN03109062A CN100372968C CN 100372968 C CN100372968 C CN 100372968C CN B031090621 A CNB031090621 A CN B031090621A CN 03109062 A CN03109062 A CN 03109062A CN 100372968 C CN100372968 C CN 100372968C
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Abstract
The present invention relates to the preparation of a superfine NiP amorphous alloy. The alloy is prepared from the following molar compositions: 40 to 70 of Ni and 60 to 30 of P. The particle diameter of the alloy is from 10 nm to 120 nm, and the specific surface area S<BET> is from 150m<2>/g to 400m<2>/g. In the preparation, hypophosphorous acids are used as a reducing agent, and the pH value of the system is regulated by a mixture of tripropyl amines and tetramethyl ammonium hydroxides or a mixture of the tripropyl amines and ammonia water; the NiP amorphous alloy is prepared by reducing nickel salt. When the temperature is from 0 DEG C to 100 DEG C, the pH value is from 5 to 10, the molar ratio of the hypophosphorous acids to the nickel salt is 1.5 to 8, and the concentration of the nickel salt is from 0.5 mol/L to 2.5 mol/L, the superfine NiP amorphous alloy with high specific surface area can be prepared. The NiP amorphous alloy of the present invention has the advantages of loose structure and higher thermal stability; compared with NiP amorphous alloys preparing prepared by a traditional preparation method, the NiP amorphous alloy of the present invention has greater superiority to be used as a catalyst material; the preparation method of the NiP amorphous alloy has the advantages of simple production process and higher output rate.
Description
Affiliated technical field
The present invention relates to the preparation of NiP amorphous alloy.
Technical background
Amorphous alloy is that a class has the unordered and material of shot-range ordered structure characteristics of atomic arrangement long-range.Since nineteen sixty, Duwez etc. have prepared amorphous alloy first by melting quench method.After this develop more economic, simple and direct chemical reduction method, can prepare ultrafine amorphous attitude alloy in this way.Amorphous alloy has isotropy, active sites is evenly distributed, the coordination of active atomic height is unsaturated and unique characteristics such as electronic state, thereby in a lot of catalyzed reactions, unique high reactivity and highly selective have been demonstrated, especially have excellent catalytic performance aspect the hydrogenation reaction of unsaturated compound especially, be expected to replace traditional skeletal nickel catalyst and be applied in the industrial production.
The classical pathway that chemical reduction method prepares the NiP amorphous alloy is, reduces nickel salt with sodium hypophosphite in the aqueous solution, and the pH value of solution uses sodium hydroxide solution to regulate.The prepared NiP amorphous alloy median size of classical pathway is generally at 70nm ~ 400nm, and specific surface area is generally at 1-20m
2/ g, specific surface area surpasses 20m
2The NiP amorphous alloy of/g seldom.Require catalyzer should have higher specific surface area as catalystic material, the effect of specific surface area high-activity component just can be not fully exerted.The NiP amorphous alloy grain diameter prepared owing to traditional method is big, specific surface area is little, and its application on catalyzed reaction is restricted.
Summary of the invention
The purpose of this invention is to provide a kind of NiP amorphous alloy and preparation method thereof, can overcome the shortcoming of prior art, the present invention is the NiP amorphous alloy that has than small particle size, high specific surface area.Its preparation method technology is simple.
Mole of the present invention consists of: Ni (40-70)-P (60-30), particle diameter be at 10nm-120nm, specific surface area S
BET=150m
2/ g-400m
2/ g.
The preparation method of NiP amorphous alloy comprises the steps:
1) nickel salt solution and Hypophosporous Acid, 50 solution are mixed, use Tri-n-Propylamine or tetramethyl-oxyammonia, or the mixture of Tri-n-Propylamine and ammoniacal liquor is transferred the pH value of solution, at pH value 5-10 (preferred 7-10), the POTASSIUM BOROHYDRIDE of 0 ℃-100 ℃ (preferred 0-40 ℃) and trace causes down, and fully stirring reaction is 2.5 hours; The mol ratio of described Hypophosporous Acid, 50 and nickel salt is from 1.5-8.Described nickel salt concentration all can be prepared the ultra-fine NiP amorphous alloy with high-specific surface area in the 0.5mol/L-2.5mol/L scope, promptly have better amorphous performance.Described nickel salt is nickelous nitrate, single nickel salt, nickelous chloride or nickelous acetate.
2) with ammoniacal liquor with the oxyhydroxide flush away in the above-mentioned precipitated product, wash precipitation again with water and reach till the neutrality to the water that washing is come out for several times, product places ethanol to preserve.
The prepared NiP amorphous alloy particle of the present invention is less, and median size is at 10nm～120nm, short texture, specific surface area height (150m
2/ g～400m
2/ g), thermostability is higher, and the NiP amorphous alloy of preparing than traditional preparation process method as catalystic material has bigger advantage, and its preparation method technology is simple, and productive rate is higher.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of NiP amorphous alloy.A is sample embodiment 9 among the figure, and B is embodiment 1, and C is embodiment 14.
Fig. 2 is the selected area electron diffraction figure (SAED) of sample embodiment 1.
Fig. 3 is the transmission electron microscope picture (TEM) of sample embodiment 1.
Fig. 4 is the transmission electron microscope picture (TEM) of sample embodiment 2.
Fig. 5 is the differential calorimetric curve (DSC) of sample.Wherein, curve 1 is embodiment 4, and curve 2 is embodiment 7, and curve 3 is embodiment 5, and curve 4 is embodiment 3.
Fig. 6 is the transmission electron microscope picture (TEM) of preparation sample under the differing temps, and A is sample embodiment four among the figure, and B is embodiment 11, and C is embodiment 12.
Fig. 7 is the transmission electron microscope picture (TEM) of sample embodiment 7.
Fig. 8 is the transmission electron microscope picture (TEM) of sample embodiment 8.
Embodiment
Under 0 ℃, single nickel salt and the 0.1mol Hypophosporous Acid, 50 of 0.05mol dissolved in the 70ml deionized water.After stirring, the pH value that adds the Tri-n-Propylamine regulator solution is 5.The KBH that adds 0.1ml
4Solution (2mol/l) causes reduction reaction.After being stirred to the reaction end, product is centrifugal,, wash with water more for several times the oxyhydroxide flush away in the above-mentioned precipitated product with ammoniacal liquor, be 7 until the pH value of washing the water that comes out, place ethanol to preserve product then.
The productive rate of product NiP is 50%, and mole consists of: Ni
61.0P
39.0Its X-ray diffraction (XRD) is illustrated in accompanying drawing 1B.Have only a fuzzy dispersion ring among the selected area electron diffraction figure (SAED, accompanying drawing 2), this is the feature diffraction pattern of non-crystalline state material.Transmission electron microscope picture (TEM) is shown in the accompanying drawing 3, shows among the figure that NiP is a spheroidal particle, and median size is about 30nm, and these particles are to be assembled by the small-particle of＜5nm and floss to form.It is 160.3m that the BET method records its specific surface area
2/ g.
Under 10 ℃, single nickel salt and the 0.1mol Hypophosporous Acid, 50 of 0.05mol dissolved in the 40ml deionized water.After stirring, add volume ratio and be 1/1 the Tri-n-Propylamine and the mixed solution of ammoniacal liquor, the pH value of regulator solution is 10.The KBH that adds 0.1ml
4Solution (2mol/l) causes reduction reaction.After being stirred to the reaction end, product is centrifugal,, wash with water more for several times the oxyhydroxide flush away in the above-mentioned precipitated product with ammoniacal liquor, be 7 until the pH value of washing the water that comes out, place ethanol to preserve product then.
The mole of product NiP consists of: Ni
60.7P
39.3Productive rate is 55%.Transmission electron microscope picture (TEM) is shown in the accompanying drawing 4, shows among the figure that the NiP granular size is about 10nm.
Under 20 ℃, single nickel salt and the 0.075mol Hypophosporous Acid, 50 of 0.05mol dissolved in the 50ml deionized water.After stirring, add the mixed solution of Tri-n-Propylamine and ammoniacal liquor, the pH value of regulator solution is 8.The KBH that adds 0.1ml
4Solution (2mol/l) causes reduction reaction.After being stirred to the reaction end, product is centrifugal,, wash with water more for several times the oxyhydroxide flush away in the above-mentioned precipitated product with ammoniacal liquor, be 7 until the pH value of washing the water that comes out, place ethanol to preserve product then.
The mole of product NiP amorphous alloy consists of: Ni
58.4P
41.6Productive rate is 45%.Have only an exothermic peak in the differential calorimetric curve of product (accompanying drawing 5, curve 4), show that the inner classes atoms metal of product distributes comparatively even.The summit temperature of exothermic peak is 365.0 ℃, and the structure that shows product is in this temperature crystallization or partially-crystallized.
Embodiment 4
Under 20 ℃, the nickelous nitrate of 0.05mol and the Hypophosporous Acid, 50 of 0.175mol are dissolved in the 40ml deionized water.After stirring, the pH value that adds the Tri-n-Propylamine regulator solution is 7.The KBH that adds 0.1ml
4Solution (2mol/l) causes reduction reaction.After being stirred to the reaction end, product is centrifugal,, wash with water more for several times the oxyhydroxide flush away in the above-mentioned precipitated product with ammoniacal liquor, be 7 until the pH value of washing the water that comes out, place ethanol to preserve product then.
The mole of product NiP amorphous alloy consists of: Ni
59.9P
40.1Productive rate is 78%.Transmission electron microscope picture (TEM) is shown among the accompanying drawing 6A, shows among the figure that the NiP granular size is at 60nm-100nm.The BET method records its specific surface area: 296.8m
2/ g.Have only an exothermic peak in the differential calorimetric curve of product (accompanying drawing 5, curve 1), show that the inner classes atoms metal of product distributes comparatively even.The summit temperature of exothermic peak is 408.9 ℃, shows that the thermostability of product is higher.
Embodiment 5
Under 25 ℃, the nickelous chloride of 0.05mol and the Hypophosporous Acid, 50 of 0.2mol are dissolved in the 71ml deionized water.After stirring, the pH value that adds the Tri-n-Propylamine regulator solution is 8.The KBH that adds 0.1ml
4Solution (2mol/l) causes reduction reaction.After being stirred to the reaction end, product is centrifugal,, wash with water more for several times the oxyhydroxide flush away in the above-mentioned precipitated product with ammoniacal liquor, be 7 until the pH value of washing the water that comes out, place ethanol to preserve product then.
The mole of product NiP amorphous alloy consists of: Ni
60.7P
39.3Productive rate is 81%.Have only an exothermic peak in the differential calorimetric curve of product (accompanying drawing 5, curve 3), summit temperature is 400 ℃, better heat stability.
Embodiment 6
Under 30 ℃, nickel acetate and the 0.175mol Hypophosporous Acid, 50 of 0.05mol dissolved in the 40ml deionized water.After stirring, the pH that adds tetramethyl-oxyammonia regulator solution is 6.The KBH that adds 0.1ml
4Solution (2mol/l) causes the carrying out of reduction reaction.After being stirred to reaction and finishing, product is centrifugal, with the nickel hydroxide in the ammoniacal liquor flush away precipitation, wash with water more for several times earlier, reach neutrality to washings till.Product places ethanol to preserve.
The mole of product NiP amorphous alloy consists of: Ni
48.0P
52.0, productive rate is 70%.
Embodiment 7
Under 30 ℃, the nickelous chloride of 0.05mol and the Hypophosporous Acid, 50 of 0.175mol are dissolved in the 40ml deionized water.After stirring, the pH value that adds tetramethyl-oxyammonia regulator solution is 10.The KBH that adds 0.1ml
4Solution (2mol/l) causes reduction reaction.After being stirred to the reaction end, product is centrifugal,, wash with water more for several times the oxyhydroxide flush away in the above-mentioned precipitated product with ammoniacal liquor, be 7 until the pH value of washing the water that comes out, place ethanol to preserve product then.
The mole of product NiP amorphous alloy consists of: Ni
59.1P
40.9Have only an exothermic peak in the differential calorimetric curve of product (accompanying drawing 5, curve 2), summit temperature is 406 ℃, better heat stability.Transmission electron microscope picture (TEM) is shown in the accompanying drawing 7, show the NiP granular size among the figure about 10nm, and majority is the reunion attitude.
Embodiment 8
Under 30 ℃, the nickelous chloride of 0.05mol and the Hypophosporous Acid, 50 of 0.175mol are dissolved in the 40ml deionized water.After stirring, the pH value that adds the Tri-n-Propylamine regulator solution is 5.The KBH that adds 0.1ml
4Solution (2mol/l) causes reduction reaction.After being stirred to the reaction end, product is centrifugal,, wash with water more for several times the oxyhydroxide flush away in the above-mentioned precipitated product with ammoniacal liquor, be 7 until the pH value of washing the water that comes out, place ethanol to preserve product then.
The mole of product NiP amorphous alloy consists of: Ni
53.3P
46.7Productive rate is 70%.Transmission electron microscope picture (TEM) is shown in the accompanying drawing 8, shows among the figure that the NiP granular size is about 30nm.
Embodiment 9
Under 30 ℃, the nickelous nitrate of 0.05mol and the Hypophosporous Acid, 50 of 0.225mol are dissolved in the 28ml deionized water.After stirring, the pH value that adds the Tri-n-Propylamine regulator solution is 7.The KBH that adds 0.1ml
4Solution (2mol/l) causes reduction reaction.After being stirred to the reaction end, product is centrifugal,, wash with water more for several times the oxyhydroxide flush away in the above-mentioned precipitated product with ammoniacal liquor, be 7 until the pH value of washing the water that comes out, place ethanol to preserve product then.
The mole of product NiP amorphous alloy consists of: Ni
50.9P
49.1Productive rate is 85%.Its X-ray diffraction (XRD) is illustrated in accompanying drawing 1A.
Embodiment 10
Under 30 ℃, the nickelous nitrate of 0.05mol and the Hypophosporous Acid, 50 of 0.32mol are dissolved in the 24ml deionized water.After stirring, the pH value that adds the Tri-n-Propylamine regulator solution is 7.The KBH that adds 0.1ml
4Solution (2mol/l) causes reduction reaction.After being stirred to the reaction end, product is centrifugal,, wash with water more for several times the oxyhydroxide flush away in the above-mentioned precipitated product with ammoniacal liquor, be 7 until the pH value of washing the water that comes out, place ethanol to preserve product then.
The mole of product NiP amorphous alloy consists of: Ni
59.2P
40.8Productive rate is 90%.
Embodiment 11
Under 40 ℃, the nickelous nitrate of 0.05mol and the Hypophosporous Acid, 50 of 0.175mol are dissolved in the 40ml deionized water.After stirring, the pH value that adds the Tri-n-Propylamine regulator solution is 7.The KBH that adds 0.1ml
4Solution (2mol/l) causes the carrying out of reduction reaction.After being stirred to the reaction end,, washing with water more for several times the oxyhydroxide flush away in the above-mentioned precipitated product with ammoniacal liquor, is 7 until the pH value of washing the water that comes out, and places ethanol to preserve product then.
The mole of product NiP amorphous alloy consists of: Ni
36.8P
63.2Productive rate is 79%.Transmission electron microscope picture (TEM) is shown among the accompanying drawing 6B, shows among the figure that the NiP granular size is at 80nm-120nm.The BET method records its specific surface area: 251.3m
2/ g.
Embodiment 12
Under 60 ℃, the nickelous nitrate of 0.05mol and the Hypophosporous Acid, 50 of 0.175mol are dissolved in the 40ml deionized water.After stirring, the pH value that adds the Tri-n-Propylamine regulator solution is 7.The KBH that adds 0.1ml
4Solution (2mol/l) causes the carrying out of reduction reaction.After being stirred to the reaction end,, washing with water more for several times the oxyhydroxide flush away in the above-mentioned precipitated product with ammoniacal liquor, is 7 until the pH value of washing the water that comes out, and places ethanol to preserve product then.
The mole of product NiP amorphous alloy consists of: Ni
41.1P
58.9Productive rate is 76%.Transmission electron microscope picture (TEM) is shown among the accompanying drawing 6C, shows among the figure that the NiP granular size is at 10nm-50nm.The BET method records its specific surface area: 356.6m
2/ g.
Embodiment 13
Under 80 ℃, nickel acetate and the 0.175mol Hypophosporous Acid, 50 of 0.05mol dissolved in 40 deionized waters.After stirring, the pH that adds tetramethyl-oxyammonia regulator solution is 8.The KBH that adds 0.1ml
4Solution (2mol/l) causes the carrying out of reduction reaction.After being stirred to reaction and finishing, product is centrifugal, with the nickel hydroxide in the ammoniacal liquor flush away precipitation, wash with water more for several times earlier, reach neutrality to washings till.Product places ethanol to preserve.
The mole of product NiP amorphous alloy consists of: Ni
60.9P
39.1Productive rate is 76%.
Embodiment 14
Under 100 ℃, nickel acetate and the 0.075mol Hypophosporous Acid, 50 of 0.05mol dissolved in the 100ml deionized water.After stirring, the pH that adds tetramethyl-oxyammonia regulator solution is 8.The KBH that adds 0.1ml
4Solution (2mol/l) causes the carrying out of reduction reaction.After being stirred to reaction and finishing, product is centrifugal, with the nickel hydroxide in the ammoniacal liquor flush away precipitation, wash with water more for several times earlier, reach neutrality to washings till.Product places ethanol to preserve.
The mole of product NiP amorphous alloy consists of: Ni
68.4P
31.6Productive rate is 45%.The XRD figure of product is listed in accompanying drawing 1C.
Claims (6)
1. NiP amorphous alloy is characterized in that its mole consists of:
Ni?40-70
P 30-60；
Particle diameter 10-120nm, specific surface area S
BET=150-400m
2/ g.
2. the preparation method of the described NiP amorphous alloy of claim 1 is characterized in that it comprises the steps:
1) nickel salt solution and Hypophosporous Acid, 50 solution are mixed, use the mixture of organic amine or organic amine and ammoniacal liquor to transfer pH, at pH value 5-10,0 ℃-100 ℃, adding 0.1ml concentration is the solution of potassium borohydride of 2mol/l, and fully stirring reaction is 2.5 hours; Described nickel salt is nickelous nitrate, single nickel salt, nickelous chloride or nickelous acetate; Described organic amine is Tri-n-Propylamine or tetramethyl-oxyammonia;
2) with ammoniacal liquor with the oxyhydroxide flush away in the above-mentioned precipitated product, wash precipitation then with water for several times, to the pH value of the water that washs out be 7, product places ethanol to preserve.
3. according to the preparation method of the NiP amorphous alloy described in the claim 2, it is characterized in that described nickel salt concentration: 0.5-2.5mol/L.
4. according to the preparation method of the NiP amorphous alloy described in the claim 2, it is characterized in that the mol ratio of described Hypophosporous Acid, 50 and nickel salt: 1.5-8.
5. according to the preparation method of the NiP amorphous alloy described in the claim 2, it is characterized in that the described pH value of step 1) is 7-10.
6. according to the preparation method of the NiP amorphous alloy described in the claim 2, it is characterized in that the described reaction of step 1) is to carry out under 0 ℃-40 ℃.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430135C (en) * | 2006-10-19 | 2008-11-05 | 安徽师范大学 | Catalyst of phosphatizing nickel, and preparation method |
| CN100448533C (en) * | 2006-12-29 | 2009-01-07 | 南开大学 | Catalyst for preparing elemental phosphorus, its preparation and application |
| JP5327582B2 (en) * | 2007-10-18 | 2013-10-30 | 日立金属株式会社 | Reduction precipitation type spherical NiP fine particles and method for producing the same |
| CN100503094C (en) * | 2007-11-22 | 2009-06-24 | 同济大学 | A method for preparing Co-Ni-Cu architecture amorphous alloy monodispersity nanometer particle |
| CN101327439B (en) * | 2008-08-01 | 2012-01-04 | 南开大学 | Hypophosphite precursor heat decomposition method for preparing Ni2P catalyst |
| CN102877009B (en) * | 2012-10-23 | 2014-03-19 | 河北工业大学 | Method for preparing porous nickel-based amorphous alloy material |
| CN104651410B (en) * | 2015-02-27 | 2018-04-13 | 福建师范大学 | A kind of preparation method of High color values red yeast rice |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073726A (en) * | 1991-12-24 | 1993-06-30 | 中国石油化工总公司石油化工科学研究院 | Large specific surface amorphous alloy and preparation thereof |
| CN1403619A (en) * | 2001-09-13 | 2003-03-19 | 中国科学院金属研究所 | Multicomponent titanium-base alloy to form amorphous structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1073726A (en) * | 1991-12-24 | 1993-06-30 | 中国石油化工总公司石油化工科学研究院 | Large specific surface amorphous alloy and preparation thereof |
| CN1403619A (en) * | 2001-09-13 | 2003-03-19 | 中国科学院金属研究所 | Multicomponent titanium-base alloy to form amorphous structure |
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