CN106006588B - A kind of method of modulation Ni-P compound structure crystal forms - Google Patents
A kind of method of modulation Ni-P compound structure crystal forms Download PDFInfo
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- CN106006588B CN106006588B CN201610321351.1A CN201610321351A CN106006588B CN 106006588 B CN106006588 B CN 106006588B CN 201610321351 A CN201610321351 A CN 201610321351A CN 106006588 B CN106006588 B CN 106006588B
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- 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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- C—CHEMISTRY; METALLURGY
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- 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 kind of method of modulation Ni P-compounds structure crystal form, comprise the following steps：Soluble nickel salt is dissolved in deionized water；According to the nickel phosphide crystalline structure for finally needing to synthesize, surfactant is added, stirring is to being completely dissolved；Add it is elemental phosphorous, formed suspension, 20min is stirred at room temperature；Then suspension is transferred in the polytetrafluoroethyllining lining of autoclave, is subsequently placed into stainless steel mould and seals, be heated to 200 DEG C, hydro-thermal reaction 12h, cooled to room temperature；The greyish black coloured particles of gained are collected with magnet, are washed for several times with absolute ethyl alcohol and deionized water respectively；Product after washing is placed in drying in vacuum drying chamber, that is, obtains micro-nano nickel phosphide.The present invention realizes hexagonal structure Ni under the action of surfactant2P is to tetragonal structure Ni12P5Transformation.Reaction temperature of the present invention is low, and the reaction time is shorter, environmentally friendly.
Description
Technical field
The present invention relates to structure crystal polymorph control technical field, is specifically a kind of side of modulation Ni-P compound structure crystal forms
Method, is realized by hexagonal structure Ni by adding surfactant polyethylene2P is to tetragonal structure Ni12P5Transformation.
Background technology
Transition metal phosphide is good heat and electric conductor, and has high rigidity and high intensity and high heat endurance
And chemical stability, there is potential application in fields such as catalysis, electricity, data storage device, magnetic refrigerating systems, can be used as expensive
The substitute of metallic catalyst.
Nickel phosphide is a kind of important transition metal phosphide, has Ni2P、Ni12P5、Ni3A variety of phases such as P, wherein with
Ni2P、Ni12P5Performance it is more prominent, relative to other nanocrystals, there is the specific heat and the coefficient of expansion of higher, therefore have
Preferable plasticity and toughness.Nickel phosphide has the characteristic similar with covalent compound and metal at the same time, as wear resistence, it is high rigid with
And the excellent stability shown in catalytic reaction, by its excellent hydrodesulfurization, hydrodenitrogeneration catalytic performance and
Selectivity, the research of nickel phosphide become the another important topic in catalyticing research field.At present, the method for preparing nickel phosphide is very much,
Including:(1) metal and elemental phosphorous direct chemical combination under high temperature and protective atmosphere；(2) solid displacement of metal halide and phosphine is reacted；
(3) reaction of metal halide and hydrogen phosphide；(4) decomposition of organo-metallic compound；(5) electrolysis of fuse salt；(6) liquid phase phosphorus
Change method；(7) reduction of metal phosphate；(8) transition metal hypophosphites thermally decomposes；(9) water/solvent-thermal method etc..Wherein, solvent
Easy to operate, yield is high and cost is low, can synthesize a series of extraordinary steady crystal and product crystallinity of being situated between because having for hot method
The features such as high and easily controllable crystal size, extensive concern is caused.In addition, solvent-thermal method can also increase bulk phase catalyst
Specific surface area, 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 form are related.In phosphide forming process, transition
Metallic atom forms construction unit (being usually triangular prism structure) in the surrounding of phosphorus atoms, and then these units are then according to a variety of sides
Formula forms the lattice with regular shape, and P atoms are then filled in the center gap of basic structural unit.In transitional metal nitride
In thing forming process, since non-metallic atom is smaller relative to metallic atomic radius, according to Hagg rules：Non-metallic atom and gold
When belonging to the radius ratio of atom and being less than 0.59, fill compound and then take crystal form as simple in structure such as hcp, fcc, hex etc..In transition
The radius of phosphorus atoms is bigger in metal phosphide, it is difficult to form octahedra knot when entering basic structural unit inside metal lattice
Structure, bond energy are relatively low, it is impossible to form metastable crystalline structure, will form the clearance type phosphide of a variety of lattice structures.
The stoichiometric ratio of nickel phosphide is very abundant, and P3 oneIon is unstable in aqueous systems, these are all micro- to nickel phosphide
The solvent/water thermal synthesis work of nano material brings very big challenge, and nickel phosphide has a variety of crystalline structures, at present, synthesis
The nickel phosphide of pure phase single crystal form is all that operating process requirement is stringent, and obtained production by the nickel phosphorus ratio among modulation raw material
Product are often mixed with other crystalline structures.Therefore, the crystalline structure that a kind of simple and practicable method carrys out modulation nickel phosphide is found, so that
Realize that the controllable growth between nickel phosphide micro Nano material structure crystal form is of great significance.
The content of the invention
The object of the present invention is to provide a kind of method of modulation Ni-P compound structure crystal forms, to realize a variety of stoichiometries
The nickel phosphide controlledly synthesis of ratio so that preparing raw material is more environmentally friendly, reaction condition is more gentle, operation is more easy, by adding
Add surfactant polyethylene, realize the controllable growth of nickel phosphide structure crystal form.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of method of modulation Ni-P compound structure crystal forms, comprises the following steps：
(1) deionized water is added in beaker, soluble nickel salt is added in deionized water, stirring to dissolving；
(2) according to finally needing the nickel phosphide crystalline structure that synthesizes, addition surfactant, is stirred to being completely dissolved；
(3) added in the solution obtained to step (2) it is elemental phosphorous, formed suspension, 20min is stirred at room temperature；
(4) and then by step (3) suspension obtained is transferred in the polytetrafluoroethyllining lining of autoclave, then will
The interior polytetrafluoroethyllining lining containing suspension is put into the stainless steel mould of autoclave, is put into after sealing in baking oven, by
Room temperature, which is begun to warm up, is warming up to 200 DEG C, hydro-thermal reaction 12h, cooled to room temperature；
(5) the greyish black coloured particles of gained are collected with magnet, is washed for several times with absolute ethyl alcohol and deionized water respectively；
(6) product after washing is placed in vacuum drying chamber, is dried in vacuo 6h in 60 DEG C, that is, obtains micro-nano phosphatization
Nickel, its crystalline phase constitutional chemistry formula are Ni2P or Ni12P5。
Preferably, in step (1), the soluble nickel salt is as nickel source；In step (3), the elemental phosphorous conduct
Phosphorus source.
Preferably, the mass ratio of the soluble nickel salt and elemental phosphorous additive amount is 1：10.
Preferably, in step (2), the surfactant is polyethylene glycol.
Preferably, in step (2), the mass ratio of the nickel phosphide finally synthesized and polyethylene glycol is 1：0-1：5.
Preferably, the nickel phosphide and polyethylene glycol mass ratio are 1:When 0, product is hexagonal structure Ni2P；Mass ratio
For 1:0.5-1:When 1, product is hexagonal structure Ni2P and tetragonal structure Ni12P5Mixed crystal；Mass ratio is 1:2-1:When 5, product
For tetragonal structure Ni12P5。
Beneficial effect：Compared with prior art, the advantages of phosphatization method for preparing nickel of the present invention and effect is, use
Simple hydrothermal synthesis method, with elemental phosphorous for phosphorus source, using soluble nickel salt as nickel source, in the effect of surfactant polyethylene
Under, realize the controlledly synthesis of nickel phosphide different structure crystal form.Reaction temperature of the present invention is low, and the reaction time is shorter, environmentally friendly.
Brief description of the drawings
Fig. 1 is the XRD characterization of nickel phosphide.
Embodiment
Describe the embodiment of the present invention in detail with reference to embodiments.
Reaction kettle used in following embodiments is made of polytetrafluoroethyllining lining and stainless steel outer sleeve.
Embodiment 1
The deionized water of 60ml is added in beaker, 1.426g nickel chlorides is added and stirs to dissolving；Add the poly- second of 0.223g
Glycol, stirring to form green transparent solution to being completely dissolved；It is elemental phosphorous that 1.858g is added into the solution, forms suspension,
20min is stirred at room temperature；Then suspension is transferred in autoclave polytetrafluoroethyllining lining, addition is until the amount of filling out reaches
60%, then the interior polytetrafluoroethyllining lining containing suspension is put into the stainless steel mould of autoclave, is put after sealing
Enter in baking oven, begun to warm up by room temperature and be warming up to 200 DEG C, hydro-thermal reaction 12h, cooled to room temperature.Collected with magnet greyish black
Coloured particles, are washed for several times with absolute ethyl alcohol and deionized water respectively；Product after washing is placed in vacuum drying chamber, in 60 DEG C
6h is dried in vacuo, that is, micro-nano nickel phosphide is obtained, as shown in Figure 1, its crystalline phase constitutional chemistry formula is Ni2P and Ni12P5, stain mark
That show is Ni12P5Characteristic peak.
Embodiment 2
The deionized water of 60ml is added in beaker, 1.426g nickel chlorides is added and stirs to dissolving；Add the poly- second of 0.445g
Glycol, stirring to form green transparent solution to being completely dissolved, subsequent operation obtains micro-nano nickel phosphide, such as scheme with embodiment 1
Shown in 1, its crystalline phase constitutional chemistry formula is Ni2P and Ni12P5, characteristic peak is more sharp, and sample crystallinity is preferable.
Embodiment 3
The deionized water of 60ml is added in beaker, 1.426g nickel chlorides is added and stirs to dissolving；Add the poly- second two of 0.89g
Alcohol, stirring to form green transparent solution to being completely dissolved, subsequent operation obtains micro-nano nickel phosphide, such as Fig. 1 with embodiment 1
Shown, its crystalline phase constitutional chemistry formula is Ni12P5, characteristic peak is more sharp, and sample crystallinity is preferable.
Embodiment 4
The deionized water of 60ml is added in beaker, 1.426g nickel chlorides is added and stirs to dissolving；Add the poly- second of 1.335g
Glycol, stirring to form green transparent solution to being completely dissolved, and subsequent operation is with embodiment 1, as shown in Figure 1, its crystalline phase compositionization
Formula is Ni12P5, characteristic peak is more sharp, and sample crystallinity is preferable.
Embodiment 5
The deionized water of 60ml is added in beaker, 1.426g nickel chlorides is added and stirs to dissolving；Add the poly- second two of 1.78g
Alcohol, stirring to form green transparent solution to being completely dissolved, and subsequent operation is with embodiment 1, as shown in Figure 1, its crystalline phase constitutional chemistry
Formula is Ni12P5, characteristic peak is more sharp, and sample crystallinity is preferable.
Embodiment 6
The deionized water of 60ml is added in beaker, 1.426g nickel chlorides is added and stirs to dissolving；Add the poly- second of 2.225g
Glycol, stirring to form green transparent solution to being completely dissolved, and subsequent operation is with embodiment 1, as shown in Figure 1, its crystalline phase compositionization
Formula is Ni12P5, characteristic peak is more sharp, and sample crystallinity is preferable.
Comparative example 1
The deionized water of 60ml is added in beaker, 1.426g nickel chlorides is added and stirs to dissolving that to form green transparent molten
Liquid；It is elemental phosphorous that 1.858g is added into the solution, suspension is formed, 20min is stirred at room temperature；Then it is transferred to high pressure
In reaction kettle polytetrafluoroethyllining lining, addition reaches 60% up to the amount of filling out, and polytetrafluoroethyllining lining then is put into reaction under high pressure
In the stainless steel mould of kettle, it is put into after sealing in baking oven, is begun to warm up by room temperature and be warming up to 200 DEG C, hydro-thermal reaction 12h, nature
It is cooled to room temperature.Greyish black coloured particles are collected with magnet, are washed for several times with absolute ethyl alcohol and deionized water respectively；By the production after washing
Product are placed in vacuum drying chamber, are dried in vacuo 6h in 60 DEG C, that is, micro-nano nickel phosphide are obtained, as shown in Figure 1, its crystalline phase compositionization
Formula is Ni2P。
Comparative example 2
The deionized water of 60ml is added in beaker, 1.426g nickel chlorides is added and stirs to dissolving that to form green transparent molten
Liquid；4.5g urotropines are added, it is elemental phosphorous then to 1.858g is added in the solution, suspension is formed, at room temperature
Stir 20min；Then it is transferred in autoclave polytetrafluoroethyllining lining, addition is until the amount of filling out reaches 60%, then
Polytetrafluoroethyllining lining is put into the stainless steel mould of autoclave, is put into after sealing in baking oven, is begun to warm up by room temperature
200 DEG C, hydro-thermal reaction 12h are warming up to, cooled to room temperature.Collect greyish black coloured particles with magnet, respectively with absolute ethyl alcohol and
Deionized water is washed for several times；Product after washing is placed in vacuum drying chamber, 6h is dried in vacuo in 60 DEG C, that is, obtains micro-nano
Nickel phosphide, as shown in figure, its crystalline phase constitutional chemistry formula are Ni12P5。
It can be seen that from embodiment 1-6 and comparative example 1-2, nickel phosphide is 1 with polyethylene glycol mass ratio:When 0, product is six sides
Crystal form Ni2P；Mass ratio is 1:0.5-1:When 1, product is hexagonal structure Ni2P and tetragonal structure Ni12P5Mixed crystal；Mass ratio is
1:2-1:When 5, product is tetragonal structure Ni12P5.Under the action of polyethylene glycol, the modulation of nickel phosphide structure crystal form is realized.
The present invention is not restricted to particular embodiments described above, any person skilled in the art possibly also with
The technology contents that the present invention discloses are changed or are retrofited.But it is every without departing from the present invention program content, according to the present invention's
Technical characterstic still falls within protection scope of the present invention to any simple modification of above example or equivalent variations.
Claims (3)
- A kind of 1. method of modulation Ni-P compound structure crystal forms, it is characterised in that：Comprise the following steps：（1）Deionized water is added in beaker, soluble nickel salt is added in deionized water, stirring to dissolving；（2）According to the nickel phosphide crystalline structure for finally needing to synthesize, surfactant is added, stirring is to being completely dissolved；Described Surfactant is polyethylene glycol；The additive amount of the surfactant polyethylene be according to the theoretical yield of nickel phosphide into Row addition, the mass ratio of nickel phosphide and polyethylene glycol is 1：0 or 1:0.5-1:1 or 1:2-1:5；The nickel phosphide and poly- second Glycol mass ratio is 1:When 0, product is hexagonal structure Ni2P；Mass ratio is 1:0.5-1:When 1, product is hexagonal structure Ni2P with Tetragonal structure Ni12P5Mixed crystal；Mass ratio is 1:2-1:When 5, product is tetragonal structure Ni12P5；（3）To step（2）Added in obtained solution it is elemental phosphorous, formed suspension, 20min is stirred at room temperature；（4）Then by step（3）Obtained suspension is transferred in the polytetrafluoroethyllining lining of autoclave, will then be included The polytetrafluoroethyllining lining for having suspension is put into the stainless steel mould of autoclave, is put into after sealing in baking oven, by room temperature Begin to warm up and be warming up to 200 DEG C, hydro-thermal reaction 12h, cooled to room temperature；（5）The greyish black coloured particles of gained are collected with magnet, are washed for several times with absolute ethyl alcohol and deionized water respectively；（6）Product after washing is placed in vacuum drying chamber, 6h is dried in vacuo in 60 DEG C, that is, obtains micro-nano nickel phosphide, its Crystalline phase constitutional chemistry formula is Ni2P、Ni2P and Ni12P5Or Ni12P5。
- 2. the method for modulation Ni-P compound structure crystal forms according to claim 1, it is characterised in that：Step（1）In, institute The soluble nickel salt stated is the nickel source of reaction；Step（3）In, it is described it is elemental phosphorous be phosphorus source.
- 3. the method for modulation Ni-P compound structure crystal forms according to claim 2, it is characterised in that：The solubility The mass ratio of nickel salt and elemental phosphorous additive amount is 1：10.
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| CN109160500B (en) * | 2018-09-28 | 2022-03-11 | 常州大学 | Method for controlling and synthesizing different-phase nano nickel phosphide |
| CN111186826A (en) * | 2019-12-27 | 2020-05-22 | 宿州学院 | Ni2P nanosphere and preparation method thereof |
| CN112619571B (en) * | 2020-11-18 | 2022-06-14 | 东南大学 | Method for regulating and controlling relative exposure strength of crystal face of transition metal phosphide |
| CN116273098B (en) * | 2023-03-20 | 2024-07-02 | 东南大学 | Interfacial activity composite photocatalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Title |
|---|
| Phase-controllable synthesis of nanosized nickel phosphides and comparison of photocatalytic degradation ability;Yonghong Ni et al.;《Nanoscale》;20111231;第3卷;196-200 * |
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