CN106006588A - Method for modulating Ni-P compound structure crystal form - Google Patents
Method for modulating Ni-P compound structure crystal form Download PDFInfo
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- CN106006588A CN106006588A CN201610321351.1A CN201610321351A CN106006588A CN 106006588 A CN106006588 A CN 106006588A CN 201610321351 A CN201610321351 A CN 201610321351A CN 106006588 A CN106006588 A CN 106006588A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention discloses a method for modulating the Ni-P compound structure crystal form. The method comprises the following steps that soluble nickel salt is dissolved into deionized water; a surfactant is added according to the nickel phosphide crystal form structure finally needing to be synthesized, and stirring is conducted until the surfactant is completely dissolved; simple substance phosphorus is added to form turbid liquid, and stirring is conducted for 20 min at room temperature; the turbid liquid is transferred into a polytetrafluoroethylene lining of a high-pressure reaction kettle, then the polytetrafluoroethylene lining is placed in a stainless steel mold to be sealed, the temperature is increased to 200 DEG C through heating, a hydrothermal reaction is conducted for 12 h, and the temperature is naturally decreased to room temperature; obtained grey black particles are collected through a magnet and then washed multiple times with absolute ethyl alcohol and deionized water separately; the washed product is placed in a vacuum drying oven to be dried, and then micro-nano nickel phosphide is obtained. According to the method, transformation from Ni2P in the hexagonal crystal form to Ni12P5 in the tetragonal crystal form is achieved under the action of the surfactant, the reaction temperature is low, the reaction time is short, and environmental friendliness is achieved.
Description
Technical field
The present invention relates to structure crystal polymorph control technical field, a kind of method of modulation Ni-P compound structure crystal formation, achieve by hexagonal structure Ni by adding surfactant polyethylene2P is to tetragonal structure Ni12P5Transformation.
Background technology
Transition metal phosphide is the hottest and electric conductor, and there is high rigidity and high intensity and high heat stability and chemical stability, in fields such as catalysis, electricity, data storage device, magnetic refrigerating systems, there is potential application, can be as the succedaneum of noble metal catalyst.
Nickel phosphide is a kind of important transition metal phosphide, has Ni2P、Ni12P5、Ni3The multiple phase such as P, wherein with Ni2P、Ni12P5Performance the most prominent, relative to other nanocrystals, there is higher specific heat and the coefficient of expansion, therefore there is preferable plasticity and toughness.Nickel phosphide has the characteristic similar with covalent compound and metal simultaneously, such as wear resistence, the high rigid and excellent stability that shows in catalytic reaction, by hydrodesulfurization, hydrodenitrogeneration catalytic performance and the selectivity of its excellence, the research of nickel phosphide becomes the another important topic in catalyticing research field.At present, the method preparing nickel phosphide is a lot, including: metal and elemental phosphorous direct chemical combination under (1) high temperature and protective atmosphere；(2) metal halide reacts with the solid displacement of phosphine；(3) metal halide and the reaction of hydrogen phosphide；(4) decomposition of organo-metallic compound；(5) electrolysis of fuse salt；(6) liquid phase parco-lubrizing；(7) reduction of metal phosphate；(8) transition metal hypophosphites thermal decomposition；(9) water/solvent-thermal method etc..Wherein, solvent-thermal method because have simple to operate, yield is high and low cost, can synthesize and a series of extraordinary is situated between steady crystal and product degree of crystallinity is high and the feature such as easily controllable crystal size, has caused extensive concern.It addition, solvent-thermal method can also increase the specific surface area of bulk phase catalyst, divided active component, so that the catalytic performance of metal phosphide is preferably played.
The performance of nano material and the pattern of themselves, especially crystal formation are correlated with.In phosphide forming process, transition metal atoms forms construction unit (usually triangular prism structure) in the surrounding of phosphorus atoms, then these unit form the lattice with regular shape the most in various ways, and P atom is then filled in the center gap of basic structural unit.In transition metal nitride forming process, owing to non-metallic atom is less relative to metallic atomic radius, according to Hagg rule: when the radius ratio of non-metallic atom and metallic atom is less than 0.59, fill compound and then take such as hcp, the crystal formation of the simple in construction such as fcc, hex.In transition metal phosphide, the radius of phosphorus atoms is bigger, and it is difficult to form octahedral structure when entering the internal basic structural unit of metal lattice, and bond energy is relatively low, it is impossible to form metastable crystalline structure, will form the clearance type phosphide of multiple lattice structure.
The stoichiometric proportion of nickel phosphide is the abundantest, and P3 OneIon is unstable in aqueous systems; these bring the biggest challenge all to the solvent/water thermal synthesis work of nickel phosphide micro Nano material; nickel phosphide has multiple crystalline structure; at present; synthesize the nickel phosphide of pure phase single crystal form be all by modulation raw material in the middle of nickel phosphorus ratio; operating process requires strict, and the product obtained often is mixed with other crystalline structures.Therefore, find a kind of simple method and carry out the crystalline structure of modulation nickel phosphide, thus it is significant to realize the controllable growth between nickel phosphide micro Nano material structure crystal formation.
Summary of the invention
A kind of method that it is an object of the invention to provide modulation Ni-P compound structure crystal formation, to realize the nickel phosphide controlledly synthesis of multiple stoichiometric proportion, make to prepare raw material more environmental protection, reaction condition is the gentleest, operation is the easiest, by adding surfactant polyethylene, it is achieved the controllable growth of nickel phosphide structure crystal formation.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of modulation Ni-P compound structure crystal formation, comprises the following steps:
(1) adding deionized water in beaker, soluble nickel salt added in deionized water, stirring is to dissolving；
(2) according to the final nickel phosphide crystalline structure needing synthesis, adding surfactant, stirring is to being completely dissolved；
(3) add in the solution that step (2) obtains elemental phosphorous, formed suspension, be stirred at room temperature 20min；
(4) then the suspension that step (3) obtains is transferred in the polytetrafluoroethyllining lining of autoclave, subsequently the polytetrafluoroethyllining lining being contained within suspension is put in the stainless steel mould of autoclave, put into after sealing in baking oven, begun to warm up by room temperature and be warming up to 200 DEG C, hydro-thermal reaction 12h, naturally cools to room temperature；
(5) the grey black granule of gained Magnet is collected, use dehydrated alcohol and deionized water wash for several times respectively；
(6) being placed in vacuum drying oven by the product after washing, be vacuum dried 6h in 60 DEG C, i.e. obtain micro-nano nickel phosphide, its crystalline phase constitutional chemistry formula is Ni2P or Ni12P5。
Preferably, in step (1), described soluble nickel salt is as nickel source；In step (3), described is elemental phosphorous as phosphorus source.
Preferably, described soluble nickel salt is 1:10 with the mass ratio of elemental phosphorous addition.
Preferably, in step (2), described surfactant is Polyethylene Glycol.
Preferably, in step (2), the described final nickel phosphide of synthesis is 1:0-1:5 with the mass ratio of Polyethylene Glycol.
Preferably, when described nickel phosphide and Polyethylene Glycol mass ratio are 1:0, product is hexagonal structure Ni2P；When mass ratio is 1:0.5-1:1, product is hexagonal structure Ni2P and tetragonal structure Ni12P5Mixed crystal；When mass ratio is 1:2-1:5, product is tetragonal structure Ni12P5。
Beneficial effect: compared with prior art, advantage and the effect of nickel phosphide preparation method of the present invention are, use simple hydrothermal synthesis method, with elemental phosphorous as phosphorus source, with soluble nickel salt as nickel source, under the effect of surfactant polyethylene, realize the controlledly synthesis of nickel phosphide different structure crystal formation.Reaction temperature of the present invention is low, and the response time is shorter, environmentally friendly.
Accompanying drawing explanation
Fig. 1 is that the XRD of nickel phosphide characterizes.
Detailed description of the invention
The detailed description of the invention of the present invention is described in detail below in conjunction with embodiment.
The reactor that following embodiment is used is made up of polytetrafluoroethyllining lining and stainless steel outer sleeve.
Embodiment 1
In beaker, add the deionized water of 60ml, add the stirring of 1.426g Nickel dichloride. to dissolving；Adding 0.223g Polyethylene Glycol, stirring is to being completely dissolved formation green transparent solution；In this solution, add 1.858g elemental phosphorous, form suspension, be stirred at room temperature 20min；Then suspension is transferred in autoclave polytetrafluoroethyllining lining, add until the amount of filling out reaches 60%, subsequently the polytetrafluoroethyllining lining being contained within suspension is put in the stainless steel mould of autoclave, put into after sealing in baking oven, begun to warm up by room temperature and be warming up to 200 DEG C, hydro-thermal reaction 12h, naturally cools to room temperature.Collect grey black granule with Magnet, use dehydrated alcohol and deionized water wash for several times respectively；Product after washing is placed in vacuum drying oven, is vacuum dried 6h in 60 DEG C, i.e. obtains micro-nano nickel phosphide, as it is shown in figure 1, its crystalline phase constitutional chemistry formula is Ni2P and Ni12P5, what stain indicated is Ni12P5Characteristic peak.
Embodiment 2
In beaker, add the deionized water of 60ml, add the stirring of 1.426g Nickel dichloride. to dissolving；Adding 0.445g Polyethylene Glycol, stirring is to being completely dissolved formation green transparent solution, and subsequent operation, with embodiment 1, i.e. obtains micro-nano nickel phosphide, as it is shown in figure 1, its crystalline phase constitutional chemistry formula is Ni2P and Ni12P5, characteristic peak is more sharp-pointed, and sample crystallinity is preferable.
Embodiment 3
In beaker, add the deionized water of 60ml, add the stirring of 1.426g Nickel dichloride. to dissolving；Adding 0.89g Polyethylene Glycol, stirring is to being completely dissolved formation green transparent solution, and subsequent operation, with embodiment 1, i.e. obtains micro-nano nickel phosphide, as it is shown in figure 1, its crystalline phase constitutional chemistry formula is Ni12P5, characteristic peak is more sharp-pointed, and sample crystallinity is preferable.
Embodiment 4
In beaker, add the deionized water of 60ml, add the stirring of 1.426g Nickel dichloride. to dissolving；Adding 1.335g Polyethylene Glycol, stirring is to being completely dissolved formation green transparent solution, and subsequent operation is with embodiment 1, as it is shown in figure 1, its crystalline phase constitutional chemistry formula is Ni12P5, characteristic peak is more sharp-pointed, and sample crystallinity is preferable.
Embodiment 5
In beaker, add the deionized water of 60ml, add the stirring of 1.426g Nickel dichloride. to dissolving；Adding 1.78g Polyethylene Glycol, stirring is to being completely dissolved formation green transparent solution, and subsequent operation is with embodiment 1, as it is shown in figure 1, its crystalline phase constitutional chemistry formula is Ni12P5, characteristic peak is more sharp-pointed, and sample crystallinity is preferable.
Embodiment 6
In beaker, add the deionized water of 60ml, add the stirring of 1.426g Nickel dichloride. to dissolving；Adding 2.225g Polyethylene Glycol, stirring is to being completely dissolved formation green transparent solution, and subsequent operation is with embodiment 1, as it is shown in figure 1, its crystalline phase constitutional chemistry formula is Ni12P5, characteristic peak is more sharp-pointed, and sample crystallinity is preferable.
Comparative example 1
In beaker, add the deionized water of 60ml, add the stirring of 1.426g Nickel dichloride. to dissolving formation green transparent solution；In this solution, add 1.858g elemental phosphorous, form suspension, be stirred at room temperature 20min；Then it is transferred in autoclave polytetrafluoroethyllining lining, add until the amount of filling out reaches 60%, subsequently polytetrafluoroethyllining lining is put in the stainless steel mould of autoclave, put into after sealing in baking oven, begun to warm up by room temperature and be warming up to 200 DEG C, hydro-thermal reaction 12h, naturally cools to room temperature.Collect grey black granule with Magnet, use dehydrated alcohol and deionized water wash for several times respectively；Product after washing is placed in vacuum drying oven, is vacuum dried 6h in 60 DEG C, i.e. obtains micro-nano nickel phosphide, as it is shown in figure 1, its crystalline phase constitutional chemistry formula is Ni2P。
Comparative example 2
In beaker, add the deionized water of 60ml, add the stirring of 1.426g Nickel dichloride. to dissolving formation green transparent solution；Add 4.5g urotropine, elemental phosphorous with this solution backward adds 1.858g, form suspension, be stirred at room temperature 20min；Then it is transferred in autoclave polytetrafluoroethyllining lining, add until the amount of filling out reaches 60%, subsequently polytetrafluoroethyllining lining is put in the stainless steel mould of autoclave, put into after sealing in baking oven, begun to warm up by room temperature and be warming up to 200 DEG C, hydro-thermal reaction 12h, naturally cools to room temperature.Collect grey black granule with Magnet, use dehydrated alcohol and deionized water wash for several times respectively；Product after washing is placed in vacuum drying oven, is vacuum dried 6h in 60 DEG C, i.e. obtains micro-nano nickel phosphide, as it is shown in figure 1, its crystalline phase constitutional chemistry formula is Ni12P5。
Can be seen that from embodiment 1-6 and comparative example 1-2, when nickel phosphide and Polyethylene Glycol mass ratio are 1:0, product is hexagonal structure Ni2P；When mass ratio is 1:0.5-1:1, product is hexagonal structure Ni2P and tetragonal structure Ni12P5Mixed crystal；When mass ratio is 1:2-1:5, product is tetragonal structure Ni12P5.Under the effect of Polyethylene Glycol, it is achieved that the modulation of nickel phosphide structure crystal formation.
The present invention is not restricted to particular embodiments described above, and any those skilled in the art are changed possibly also with the technology contents that the present invention discloses or retrofit.But, every without departing from the present invention program content, according to the technical characterstic of the present invention to any simple modification of above example or equivalent variations, still fall within protection scope of the present invention.
Claims (6)
1. the method for a modulation Ni-P compound structure crystal formation, it is characterised in that: comprise the following steps:
(1) adding deionized water in beaker, soluble nickel salt added in deionized water, stirring is to dissolving；
(2) according to the final nickel phosphide crystalline structure needing synthesis, adding surfactant, stirring is to completely
Dissolve；
(3) add in the solution that step (2) obtains elemental phosphorous, formed suspension, be stirred at room temperature
20min；
(4) then the suspension that step (3) obtains is transferred to the polytetrafluoroethyllining lining of autoclave
In, subsequently the polytetrafluoroethyllining lining being contained within suspension is put into the stainless steel mould of autoclave
In, put into after sealing in baking oven, room temperature begin to warm up and be warming up to 200 DEG C, hydro-thermal reaction 12h, from
So it is cooled to room temperature；
(5) the grey black granule of gained Magnet is collected, respectively with dehydrated alcohol and deionized water wash number
Secondary；
(6) product after washing is placed in vacuum drying oven, is vacuum dried 6h in 60 DEG C, i.e. obtains micro-
Nano nickel phosphide, its crystalline phase constitutional chemistry formula is Ni2P or Ni12P5。
The method of modulation Ni-P compound structure crystal formation the most according to claim 1, it is characterised in that:
In step (1), described soluble nickel salt is the nickel source of reaction；In step (3), described list
Matter phosphorus is phosphorus source.
The method of modulation Ni-P compound structure crystal formation the most according to claim 2, it is characterised in that:
Described soluble nickel salt is 1:10 with the mass ratio of elemental phosphorous addition.
The method of modulation Ni-P compound structure crystal formation the most according to claim 1, it is characterised in that:
In step (2), described surfactant is Polyethylene Glycol.
The method of modulation Ni-P compound structure crystal formation the most according to claim 4, it is characterised in that:
In step (2), the addition of described surfactant polyethylene is the theoretical product according to nickel phosphide
Amount is added, and nickel phosphide is 1:0-1:5 with the mass ratio of Polyethylene Glycol.
The method of modulation Ni-P compound structure crystal formation the most according to claim 5, it is characterised in that:
When described nickel phosphide and Polyethylene Glycol mass ratio are 1:0, product is hexagonal structure Ni2P；Mass ratio
During for 1:0.5-1:1, product is hexagonal structure Ni2P and tetragonal structure Ni12P5Mixed crystal；Mass ratio is
During 1:2-1:5, product is tetragonal structure Ni12P5。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160500A (en) * | 2018-09-28 | 2019-01-08 | 常州大学 | A method of control synthesis different phase nano nickel phosphide |
| CN111186826A (en) * | 2019-12-27 | 2020-05-22 | 宿州学院 | Ni2P nanosphere and preparation method thereof |
| 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 |
| CN116273098A (en) * | 2023-03-20 | 2023-06-23 | 东南大学 | Interfacial activity composite photocatalyst and preparation method and application thereof |
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| CN101659403A (en) * | 2009-09-18 | 2010-03-03 | 中国海洋大学 | Hydro-thermal synthesis process of phosphide |
| CN102040203A (en) * | 2010-11-19 | 2011-05-04 | 安徽师范大学 | Preparation method and application of nano nickel phosphide |
| CN104944396A (en) * | 2015-06-09 | 2015-09-30 | 辽宁科技学院 | Controllable synthesis method of nickel phosphide micro-nano material |
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2016
- 2016-05-13 CN CN201610321351.1A patent/CN106006588B/en active Active
Patent Citations (3)
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| CN101659403A (en) * | 2009-09-18 | 2010-03-03 | 中国海洋大学 | Hydro-thermal synthesis process of phosphide |
| CN102040203A (en) * | 2010-11-19 | 2011-05-04 | 安徽师范大学 | Preparation method and application of nano nickel phosphide |
| CN104944396A (en) * | 2015-06-09 | 2015-09-30 | 辽宁科技学院 | Controllable synthesis method of nickel phosphide micro-nano material |
Non-Patent Citations (1)
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| YONGHONG NI ET AL.: "Phase-controllable synthesis of nanosized nickel phosphides and comparison of photocatalytic degradation ability", 《NANOSCALE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160500A (en) * | 2018-09-28 | 2019-01-08 | 常州大学 | A method of control synthesis different phase nano nickel phosphide |
| CN111186826A (en) * | 2019-12-27 | 2020-05-22 | 宿州学院 | Ni2P nanosphere and preparation method thereof |
| 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 |
| CN116273098A (en) * | 2023-03-20 | 2023-06-23 | 东南大学 | Interfacial activity composite photocatalyst and preparation method and application thereof |
| CN116273098B (en) * | 2023-03-20 | 2024-07-02 | 东南大学 | Interfacial activity composite photocatalyst and preparation method and application thereof |
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