CN110523970A - A kind of carbon-coating nickel nano-particle and preparation method thereof - Google Patents
A kind of carbon-coating nickel nano-particle and preparation method thereof Download PDFInfo
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- CN110523970A CN110523970A CN201810510423.6A CN201810510423A CN110523970A CN 110523970 A CN110523970 A CN 110523970A CN 201810510423 A CN201810510423 A CN 201810510423A CN 110523970 A CN110523970 A CN 110523970A
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Abstract
The invention discloses a kind of carbon-coating nickel nano-particles, the nano particle contains metal state nickel and is coated on the carbon coating layer on at least partly surface of the metal state nickel, in the X ray diffracting spectrum of the nano particle, respectively 2 θ are 22 ° to 27 °, 2 θ are 43 ° to 45 °, 2 θ are 46 ° to 49 °, 2 θ are 50 ° to 54 ° and 2 θ are 75 ° to 80 ° there are diffraction maximums.The invention also discloses a kind of preparation method of carbon-coating nickel nano-particle, this method includes that pyridinedicarboxylic acid is coordinated the presoma to be formed with water soluble nickel salt to be pyrolyzed in inert atmosphere.Method of the invention, can be not only environmentally protective without organic solvent directly using water as dispersing agent when pyridinedicarboxylic acid and nickel salt being carried out coordination preparing presoma, but also significantly reduces production cost；The good dispersion of the carbon-coating nickel nano-particle of preparation simultaneously, size uniformity.
Description
Technical field
The present invention relates to a kind of carbon-coating nickel nano-particles and preparation method thereof.
Background technique
Nickel has special optics, electrical and magnetic performance as a kind of magnetic metal, and also has good catalysis
Performance.Nickel metal nano material has some special physicochemical characteristics for being different from stock size material, including surface effect
It answers, dielectric confinement, quantum size, small-size effect and macro quanta tunnel effect etc..But nickel metal nanoparticle activity
Height is easy to happen reunion or is oxidized or even burns in air, leverages the performance and its application of this kind of material.
In recent years, with the research boom of nano-carbon material and progress, nano-carbon coated metallic composite, which becomes, to be received
Rice one of carbon and the research hotspot of metallic composite.This kind of material is shell tight by single layer to several layers of bending graphite flake layer
Nanoparticle and extraneous progress physical isolation are substantially increased the stability of this kind of material by stratum nucleare metal nanoparticle.Together
When, since penetration of electrons effect realizes stratum nucleare metal nano material and extraneous chemical contact again.Therefore, this unique core
Shell structural nano material has broad application prospects in fields such as electro-catalysis, absorbing material, lube oil additives.
Summary of the invention
One of the objects of the present invention is to provide a kind of carbon-coating nickel nano-particle, which has face-centered cubic brilliant
The metallic nickel of two kinds of forms of lattice structure (fcc) and six a small amount of side's closely spaced lattice structures (hcp).
The second object of the present invention is to provide a kind of preparation method of carbon-coating nickel nano-particle, and this method uses pyridine
Dicarboxylic acids and nickel salt, which are coordinated, to be formed presoma and is pyrolyzed and prepares carbon-coating nickel nano-particle, can be only when preparing presoma
Using water as dispersing agent without using organic solvent.
According to the first aspect of the invention, the present invention provides a kind of carbon-coating nickel nano-particle, which contains
There is metal state nickel and be coated on the carbon coating layer on at least partly surface of the metal state nickel, the X-ray of the nano particle is spread out
It penetrates in map, respectively 2 θ are 22 ° to 27 °, 2 θ are 43 ° to 45 °, 2 θ are 46 ° to 49 °, 2 θ are 50 ° to 54 ° and 2 θ are 75 °
To 80 °, there are diffraction maximums.
According to the second aspect of the invention, the present invention provides a kind of preparation methods of carbon-coating nickel nano-particle, should
Method includes that pyridinedicarboxylic acid is coordinated the presoma to be formed with water soluble nickel salt to be pyrolyzed in inert atmosphere.
According to the third aspect of the present invention, the present invention provides the preparations of the method as described in the second aspect of the present invention
Carbon-coating nickel nano-particle.
The preparation method of carbon-coating nickel nano-particle according to the present invention, using pyridinedicarboxylic acid as ligand and nickel salt shape
At presoma, when pyridinedicarboxylic acid and nickel salt being carried out coordination preparing presoma, can be not necessarily to directly using water as dispersing agent
It is not only environmentally protective using organic solvent, but also significantly reduce production cost.
The preparation method of carbon-coating nickel nano-particle according to the present invention, the dispersibility of the carbon-coating nickel nano-particle of preparation
It is good, size uniformity.The preparation method of carbon-coating nickel nano-particle according to the present invention, can be to the carbon-coating nickel nanometer of preparation
The lattice form of metallic nickel is adjusted in grain, obtains the nano particle that metallic nickel is centroid cubic lattice structure (fcc), or
The metallic nickel of two kinds of forms with centroid cubic lattice structure (fcc) and six a small amount of side's closely spaced lattice structures (hcp) is received
Rice grain.
The preparation method of carbon-coating nickel nano-particle according to the present invention, using the pyridinedicarboxylic acid containing C, N and O as matching
Body is to Ni2+It is coordinated, pyridinedicarboxylic acid is carbonized under the high temperature conditions plays the role of carbonaceous reducing agent for Ni2+It carries out being reduced into Ni0 +, while oxygen doping and N doping in situ are carried out to the carbon-coating of preparation as oxygen source and nitrogen source.Therefore, it is no longer needed in preparation process
It is passed through the flammable reducing gas such as hydrogen or CH4、C2H4Equal imflammable gas, without being passed through NH3Equal irritative gas are made
For nitrogen source.
Detailed description of the invention
Fig. 1 is TG-DTA analysis (TG-DTA) curve graph of presoma prepared by embodiment 1.
Fig. 2A and Fig. 2 B is X-ray diffraction (XRD) spectrum of carbon-coating nickel Core-shell Structure Nanoparticles prepared by embodiment 1
Figure, wherein Fig. 2 B is the partial enlarged view that 2 θ are 44 ° to 54 ° sections in Fig. 2A.
Fig. 3 is x-ray photoelectron spectroscopy (XPS) spectrogram of carbon-coating nickel nano-particle prepared by embodiment 1.
Fig. 4 is transmission electron microscope (TEM) photo of carbon-coated nano particle prepared by embodiment 1.
Fig. 5 A and Fig. 5 B are the XRD spectras of carbon-coating nickel nano-particle prepared by embodiment 2, wherein Fig. 5 B is 2 in Fig. 5 A
θ is the partial enlarged view in 44 ° to 54 ° sections.
Fig. 6 A and Fig. 6 B are the XRD spectras of carbon-coating nickel nano-particle prepared by embodiment 3, wherein Fig. 6 B is 2 in Fig. 6 A
θ is the partial enlarged view in 44 ° to 54 ° sections.
Fig. 7 is transmission electron microscope (TEM) photo of carbon-coated nano particle prepared by embodiment 3.
Fig. 8 A and Fig. 8 B are the XRD spectras of carbon-coating nickel nano-particle prepared by embodiment 4, wherein Fig. 8 B is 2 in Fig. 8 A
θ is the partial enlarged view in 44 ° to 54 ° sections.
Fig. 9 A and Fig. 9 B are the XRD spectras of carbon-coating nickel nano-particle prepared by embodiment 5, wherein Fig. 9 B is 2 in Fig. 9 A
θ is the partial enlarged view in 44 ° to 54 ° sections.
Figure 10 A and Figure 10 B are the XRD spectras of carbon-coating nickel nano-particle prepared by embodiment 6, wherein Figure 10 B is figure
2 θ are the partial enlarged view in 44 ° to 54 ° sections in 10A.
Figure 11 A and Figure 11 B are the XRD spectras of carbon-coating nickel nano-particle prepared by embodiment 7, wherein Figure 11 B is figure
2 θ are the partial enlarged view in 44 ° to 54 ° sections in 11A.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of carbon-coating nickel nano-particle, which contains
There is metal state nickel and is coated on the carbon coating layer on at least partly surface of the metal state nickel.The metal state nickel is received as this
The kernel of rice material, at least partly surface of the kernel are coated by carbon coating layer, and preferably the surface of kernel is by carbon coating layer
Cladding.
In the present invention, term " metal state nickel " refers to that the valence state of nickel is zeroth order.
Carbon-coating nickel nano-particle according to the present invention in the X ray diffracting spectrum of the nano particle, is in 2 θ respectively
22 ° to 27 °, 2 θ be 43 ° to 45 °, 2 θ are 46 ° to 49 °, 2 θ are 50 ° to 54 ° and 2 θ are 75 ° to 80 ° there are diffraction maximums.This
In invention, position 2 θ as locating for the summit of diffraction maximum of diffraction maximum are determined.
Carbon-coating nickel nano-particle according to the present invention, in the X ray diffracting spectrum of the nano particle, 2 θ be 43 ° extremely
The diffraction maximum of 45 ° of appearance corresponds to the metallic nickel of face-centred cubic structure (fcc).In the X ray diffracting spectrum of the nano particle,
It is highest peak (that is, peak of maximum intensity) in the diffraction maximum that 2 θ are 43 ° to 45 ° appearance.
Carbon-coating nickel nano-particle according to the present invention, in the X ray diffracting spectrum of the nano particle, 2 θ be 50 ° extremely
54 ° appearance diffraction maximums and 2 θ be 75 ° to 80 ° appearance diffraction maximums be also face-centred cubic structure (fcc) metallic nickel spy
Levy diffraction maximum.To be diffraction maximum existing for 50 ° to 54 ° in 2 θ on the basis of the intensity for the diffraction maximum that 2 θ are 43 ° to 45 ° appearance
Relative intensity can be 20-40, preferably 22-35；It is 75 ° to 80 ° in 2 θ there are the relative intensity of diffraction maximum can be 11-
20, preferably 13-18.
Carbon-coating nickel nano-particle according to the present invention, in the X ray diffracting spectrum of the nano particle, 2 θ be 46 ° extremely
49 ° there is also diffraction maximum, which is the metallic nickel corresponding to six side's closely spaced lattice structures (hcp).It is according to the present invention to receive
Rice grain, to be 46 ° to the 49 ° diffraction maximums occurred in 2 θ on the basis of the intensity for the diffraction maximum that 2 θ are 43 ° to 45 ° appearance
Relative intensity can be 0.2-25, preferably 1-23, more preferably 2-21.
Carbon-coating nickel nano-particle according to the present invention is 22 ° to 27 ° there is also diffraction maximum in 2 θ, which is pair
It should be in the diffraction maximum of graphitic carbon.To be 22 ° to 27 ° in 2 θ and deposit on the basis of the intensity for the diffraction maximum that 2 θ are 43 ° to 45 ° appearance
The relative intensity of diffraction maximum can be 0.2-50, preferably 1-48, more preferably 4-46.
Carbon-coating nickel nano-particle according to the present invention, on the basis of the total amount of the nano particle, the content of nickel element can
Think 5-75 weight %, preferably 10-70 weight %, more preferably 15-68 weight %, further preferably 20-65 weight %,
It is still more preferably 25-63 weight %.
Carbon-coating nickel nano-particle according to the present invention, the nano particle also contain oxygen element, nitrogen and protium.Root
According to carbon-coating nickel nano-particle of the invention, oxygen element, nitrogen and protium are distributed in carbon coating layer.With the nano particle
Total amount on the basis of, the content of carbon can be 24-94 weight %, preferably 26-85 weight %, more preferably 30-70 weight
Measure %；The content of oxygen element can be 0.5-12 weight %, preferably 1-11 weight %, more preferably 3-10 weight %；Nitrogen member
The content of element can be 0.5-10 weight %, preferably 1-9.5 weight %, more preferably 2-9 weight %；The content of protium can
Think 0.1-2.5 weight %, preferably 0.3-2.2 weight %, more preferably 0.5-2 weight %.In the present invention, nano particle
In, the content of oxygen element, nitrogen and protium is measured using elemental microanalysis method, and the content of nickel element is normalizing in nano particle
Change the content after deducting carbon, oxygen element, nitrogen, protium.
Carbon-coating nickel nano-particle according to the present invention, the average thickness of the carbon coating layer can be 1-5nm.According to this
The carbon-coating nickel nano-particle of invention, the average grain diameter of the metal state nickel can be 7-20nm.Carbon coating according to the present invention
The average grain diameter of nano nickel particles, the nano particle is generally 8-25nm.In the present invention, the average thickness of carbon coating layer, conduct
The average grain diameter of the metal state nickel of kernel and the average grain diameter of nano particle are measured using transmission electron microscope method.
According to the second aspect of the invention, the present invention provides a kind of preparation methods of carbon-coating nickel nano-particle, should
Method includes that pyridinedicarboxylic acid is coordinated the presoma to be formed with water soluble nickel salt to be pyrolyzed in inert atmosphere.
According to the method for the present invention, pyridinedicarboxylic acid is coordinated the method to form presoma with water soluble nickel salt can wrap
It includes: under hydrothermal reaction condition, pyridinedicarboxylic acid being contacted with alkali and water soluble nickel salt.Pyridinedicarboxylic acid and water soluble nickel salt
Molar ratio can be 1:0.1-1.5, preferably 1:0.3-1.5, more preferably 1:0.5-1.5, further preferably 1:0.6-
1.5, the water soluble nickel salt is in terms of nickel element.Specifically, the molar ratio of pyridinedicarboxylic acid and water soluble nickel salt can be 1:
0.1,1:0.2,1:0.3,1:0.4,1:0.5,1:0.6,1:0.7,1:0.8,1:0.9,1:1,1:1.1,1:1.2,1:1.3,1:
1.4 or 1:1.5.
Method according to the invention it is possible to pyridinedicarboxylic acid is reacted in water with alkali and water soluble nickel salt, thus
Presoma is obtained, using water as solvent, production cost can not only be reduced, and environmentally protective.
Specifically, pyridinedicarboxylic acid can be mixed with alkali and water, obtains pyridinedicarboxylic acid aqueous solution；By the pyridine two
Carboxylic acid aqueous solution is mixed with water soluble nickel salt, obtains the aqueous solution containing nickel ion；The aqueous solution containing nickel ion is existed
It is reacted under hydrothermal reaction condition.Pyridinedicarboxylic acid: the molar ratio of alkali can be 1:1-3, preferably 1:1.1-2.6, it is more excellent
It is selected as 1:1.2-2.3.Pyridinedicarboxylic acid: the molar ratio of water can be 1:1-1000, preferably 1:50-800, more preferably 1:
200-500.Generally, the mixing of pyridinedicarboxylic acid and alkali and water and the mixing of pyridinedicarboxylic acid aqueous solution and water soluble nickel salt
Respectively can 15-40 DEG C at a temperature of carry out.
The water soluble nickel salt can be conventional selection, preferably NiCl2、Ni(NO3)2And NiSO4One or both of
More than.The alkali is preferably alkali metal hydroxide, more preferably KOH and/or NaOH.
The hydro-thermal reaction can 100-200 DEG C at a temperature of carry out.Preferably, the hydro-thermal reaction is in 120-180
It is carried out at a temperature of DEG C.It is highly preferred that the hydro-thermal reaction 125-160 DEG C at a temperature of carry out.The hydro-thermal reaction is held
The continuous time can be 1 hour to 720 hours, preferably 1.2-360 hours, more preferably 1.5-180 hours, further preferably
1.8-90 hours, be still more preferably 2-45 hours.According to the method for the present invention, even if the hydro-thermal for carrying out the short period is anti-
It answers, can also obtain the presoma, such as: the duration of the hydro-thermal reaction can be 1.5-10 hours, preferably 2-8
Hour.The hydro-thermal reaction can carry out at autogenous pressures, can also carry out under conditions of additionally increasing pressure, preferably exist
It is carried out under self-generated pressure.The hydro-thermal reaction carries out in closed reactor, for example, can in common autoclave into
Row.
Solid matter can be isolated from the mixture that hydro-thermal reaction obtains using conventional method, and consolidated what is isolated
Body substance is washed and is dried, to obtain presoma.Specifically, conventional solid-liquid separation method can be used from hydro-thermal reaction
Solid matter is isolated in obtained mixture, the solid-liquid separating method can include but is not limited to: filtering, centrifugation, sedimentation
One or more of combination.The washing can be washed using deionized water.The drying is to be sufficient to make
Subject to non-volatile devolatilization in solid matter or basic removing, can 30-120 DEG C at a temperature of carry out.The drying
It can carry out under normal pressure, can also carry out, be not particularly limited at reduced pressure.The drying can be in air atmosphere
Middle progress can also carry out in inert atmosphere.The inert atmosphere can be to form gas by nitrogen and/or zero group gas
Atmosphere, the zero group gas for example can be argon gas.
According to the method for the present invention, the pyridinedicarboxylic acid be selected from 2,3- pyridinedicarboxylic acid, 2,4- pyridinedicarboxylic acid, 2,
One or more of 5- pyridinedicarboxylic acid, 2,6- pyridinedicarboxylic acid, 3,4- pyridinedicarboxylic acid and 3,5- pyridinedicarboxylic acid.
According to the method for the present invention, the pyrolysis can 400-850 DEG C at a temperature of carry out.Side according to the present invention
Method, it is described pyrolysis preferably 430-850 DEG C at a temperature of carry out, be pyrolyzed within this temperature range, what is obtained is carbon-coated
In nano nickel particles, metallic nickel is deposited in the form of two kinds of centroid cubic lattice structure (fcc) He Liufang closely spaced lattice structure (hcp)
In；However, lower than 430 DEG C at a temperature of be pyrolyzed, in obtained carbon-coated nano nickel particles, metallic nickel is vertical with the center of area
The form of square lattice structure (fcc) exists.It is described pyrolysis more preferably 500-850 DEG C at a temperature of carry out, such as: the pyrolysis
It can be in 500 DEG C, 510 DEG C, 520 DEG C, 530 DEG C, 540 DEG C, 550 DEG C, 560 DEG C, 570 DEG C, 580 DEG C, 590 DEG C, 600 DEG C, 610
℃、620℃、630℃、640℃、650℃、660℃、670℃、680℃、690℃、700℃、710℃、720℃、730℃、
740 DEG C, 750 DEG C, 760 DEG C, 770 DEG C, 780 DEG C, 790 DEG C, 800 DEG C, 810 DEG C, 820 DEG C, 830 DEG C, 840 DEG C or 850 DEG C
At a temperature of carry out.It is described pyrolysis further preferably 500-800 DEG C at a temperature of carry out.By pyrolysis, the presoma is turned
Chemical conversion is carbon-coated nano nickel particles.The duration of the pyrolysis can be selected according to the temperature of pyrolysis, generally may be used
Think 20-480 minutes, preferably 1-5 hours, more preferably 2-3 hours.
With the method for the invention it is preferred to by presoma from environment temperature (generally 25 DEG C) with 1-10 DEG C/min of speed
Rate is warming up to pyrolysis temperature.More preferably presoma is warming up to from environment temperature (generally 25 DEG C) with 2-5 DEG C/min of rate
Pyrolysis temperature.
According to the method for the present invention, the pyrolysis carries out in inert atmosphere, and the inert atmosphere can be for by nitrogen
The atmosphere that gas and/or zero group gas are formed, the zero group gas for example can be argon gas.
According to the method for the present invention, the product being pyrolyzed can be directly as carbon-coating nickel nano-particle, can also be into
One step is washed.Preferably, the product that pyrolysis obtains is washed, to further increase the pure of carbon-coating nickel nano-particle
Degree, washing the washing medium used can be the combination of one or more of water, acid solution.Side according to the present invention
Method, nickel is in the form of two kinds of centroid cubic lattice structure (fcc) He Liufang closely spaced lattice structure (hcp) in the product that pyrolysis obtains
In the presence of, compared with not using acid solution to carry out washing, thermal decomposition product, which is carried out washing using acid solution, can also be improved most
The content of six side's closely spaced lattice structures (hcp) in the carbon-coating nickel nano-particle obtained eventually.The acid solution is preferably hydrochloric acid
Or sulfuric acid.In the acid solution sour concentration can be 0.1-3mol/L, preferably 0.5-2.5mol/L, more preferably
0.8-2mol/L, further preferably 1-1.5mol/L.
According to the method for the present invention, it when the product obtained using acid solution to pyrolysis is washed, can will be pyrolyzed
Obtained product is impregnated with acid solution, the solid matter water used wash for being then separated by solid-liquid separation, and being obtained.The immersion
Can 10-100 DEG C at a temperature of carry out, preferably 40-98 DEG C at a temperature of carry out, more preferably 50-95 DEG C at a temperature of
Carry out, further preferably 80-90 DEG C at a temperature of carry out.The duration of the immersion can carry out according to the temperature of immersion
Selection generally can be 0.5-10 hours, preferably 2-8 hours, more preferably 3-6 hours.
According to the third aspect of the present invention, the present invention provides the preparations of the method as described in the second aspect of the present invention
Carbon-coating nickel nano-particle.
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, TG-DTA analysis (TG-DTA) carries out on TA5000 thermal analyzer, test
Condition is nitrogen atmosphere, and heating rate is 5 DEG C/min, and temperature range is room temperature (25 DEG C) to 1000 DEG C.Sample exists before testing
150 DEG C of temperature and the pressure of 1 normal atmosphere are 3 hours dry in helium atmosphere.
In following embodiment and comparative example, height of the transmission electron microscope analysis (TEM) in the model G2F20 of FEI Co., the U.S.
It is carried out in resolved transmittance Electronic Speculum.
In following embodiment and comparative example, X-ray diffraction analysis (XRD) is in the model for being purchased from Holland PA Nalytical
It is carried out on the X-ray diffractometer of X ' Pert Pro, test condition includes: tube voltage 40kV, tube current 40mA, Cu target KαRadiation, 2
5 ° to 80 ° of θ scanning range.
In following embodiment and comparative example, X-ray photoelectron spectroscopic analysis (XPS) is in Thermo Scientific company
The ESCALab250 type x-ray photoelectron spectroscopy equipped with Thermo Avantage V5.926 software on tested,
Excitaton source is monochromatization AlKαX-ray, energy 1486.6eV, power 150W, penetrating used in narrow scan can be 30eV, analysis
Base vacuum when test is 6.5 × 10-10Mbar, the peak C1s (284.6eV) correction of electron binding energy simple substance carbon, In
Data processing is carried out on Thermo Avantage software, quantitative analysis is carried out using sensitivity factor method in analysis module.Sample
It is 3 hours dry in helium atmosphere in 150 DEG C of temperature and the pressure of 1 normal atmosphere before product test.
In following embodiment and comparative example, elemental analysis is in the model Vario MICRO cube for being purchased from Elementar
Elemental analyser on carry out；
Wherein, the content assaying method of carbon and protium are as follows: sample high-temp combustion in the presence of oxygen, in sample
Carbon, hydrogen are separately converted to CO2、H2O, after removing disturbing factor, reaction gas is carried along into chromatographic column by carrier gas and is separated.Finally
It is detected by conductance cell；
The content assaying method of oxygen element are as follows: sample cracks in the Pintsch process pipe equipped with carbon dust, wherein oxygen-containing chemical combination
Object is quantitatively converted into CO, and carrier gas carries pyrolysis product and enters in concatenated washer, to remove acid gas and water vapour.Finally
It is detected into infrared detector；
The content assaying method of nitrogen are as follows: use solid sampling mode, sample is sent into Pintsch process pipe, through aoxidizing
It cracks, the nitrogen in catalyst is converted into NO, NO and O3After contact, it is converted into the NO of excitation state2, the NO of excitation state2Hair when relaxation
It penetrates light to be detected by photomultiplier tube, the content of nitrogen in sample is calculated by resulting signal value.
Embodiment 1-7 is for illustrating the present invention.
Embodiment 1
(1) at 25 DEG C, 10mmol 2,5-Pyridinedicarboxylic acid and 20mmol NaOH is dissolved in 40mL deionized water, obtained
To pyridinedicarboxylic acid aqueous solution.
(2) at 25 DEG C, 20mL Ni containing 10mmol (NO is added into the pyridinedicarboxylic acid aqueous solution of step (1) preparation3)2's
Aqueous solution stirs 10min, obtains the aqueous solution containing nickel ion.
(3) aqueous solution containing nickel ion that step (2) obtains is transferred to the reaction under high pressure with polytetrafluoroethyllining lining
In kettle, the temperature in reaction kettle is increased to 130 DEG C by closed reactor, and carries out hydro-thermal reaction 5h at such a temperature.
(4) after the temperature inside reaction kettle naturally cools to 25 DEG C, reaction kettle is opened, reaction mixture was carried out
Filter, and with deionized water to the solid matter being obtained by filtration wash three times, by washed solid matter in air atmosphere in
75 DEG C of dry 5h, obtain presoma.
(5) presoma that step (4) obtains is placed in tube furnace, in a nitrogen atmosphere, by the temperature in tube furnace by
25 DEG C of heating rates with 5 DEG C/min are increased to 500 DEG C, and keep 2h in the temperature, are pyrolyzed.
(6) after naturally cooling to 25 DEG C to the temperature in tube furnace, thermal decomposition product is taken out from tube furnace, and will pyrolysis
Product is added in 1mol/L HCl solution, the temperature of solution is increased to 90 DEG C, and after the temperature keeps 4h, by solution temperature
25 DEG C are naturally cooled to, solution is filtered, and the solid matter being obtained by filtration is adopted and is washed with deionized to washing water
For neutrality.By washed solid matter in 100 DEG C of dry 6h in air atmosphere, obtains carbon-coating nickel according to the present invention and receive
Rice grain.
Fig. 1 is the presoma of step (4) preparation in N2TG-DTA analysis (TG-DTA) curve in atmosphere.It can from Fig. 1
To find out presoma, there are three apparent endothermic peaks in temperature-rise period, wherein corresponds to presoma in 123 DEG C of endothermic peaks
The removing peak of middle volatile materials corresponds to the disengaging process of the crystallization water in 185 DEG C of endothermic peaks, in 429 DEG C of endothermic peak pair
It should be in the carbonization of presoma high temperature pyrolysis and Ni2+It is reduced into the process of Ni simple substance；And the quality of presoma is opposite after 430 DEG C
Stablize.
Fig. 2A and Fig. 2 B is the X-ray diffraction spectrogram for the carbon-coating nickel nano-particle that step (6) obtains, wherein Fig. 2 B is
2 θ are the partial enlarged view in 44 ° to 54 ° sections in Fig. 2A.It can be seen that the diffraction maximum, right respectively of graphitic carbon from Fig. 2A and Fig. 2 B
The Ni of two kinds of crystal phases of the side's Ying Yuliu closely spaced lattice structure nickel (hcp Ni) and face-centred cubic structure lattice structure nickel (fcc Ni)
Diffraction maximum.The relative intensity of each diffraction maximum is listed in table 1.
Table 1
| 2θ(°) | Relative intensity [100 × I/I0], using the intensity of the diffraction maximum within the scope of 43 ° -45 ° as I0 |
| 22-27 | 29.6 |
| 43-45 | 100 |
| 46-49 | 20.6 |
| 50-54 | 27.4 |
| 75-80 | 18.0 |
Fig. 3 is the XPS spectrum figure for the carbon-coating nickel nano-particle that step (6) obtains, and can be clearly seen that correspondence from Fig. 3
In the electron binding energy peak of C element, O element, N element and Ni element.Elemental analyser measures in carbon-coating nickel nano-particle, C
Content is 48.92 weight %, and H content is 1.83 weight %, and O content is 9.84 weight %, and N content is 8.15 weight %, normalizing
Determine that Ni content is 31.26 weight % after change.
Fig. 4 is the TEM photo for the carbon-coating nickel nano-particle that step (6) obtains.As can be seen from Figure 4 carbon-coating nickel is received
Rice grain is evenly dispersed and size uniformity.It is determined by tem analysis, in the carbon-coating nickel nano-particle, metallic nickel kernel is averaged
Partial size is 7nm, and the average thickness of carbon coating layer is 1nm, and the average grain diameter of the carbon-coating nickel nano-particle is 8nm.
Embodiment 2
(1) at 25 DEG C, by 15mmol 2,4- pyridinedicarboxylic acid and 20mmol NaOH are dissolved in 40mL deionized water, are obtained
To pyridinedicarboxylic acid aqueous solution.
(2) at 25 DEG C, 20mL NiCl containing 10mmol is added into the pyridinedicarboxylic acid aqueous solution of step (1) preparation2Water
Solution stirs 15min, obtains the aqueous solution containing nickel ion.
(3) aqueous solution containing nickel ion that step (2) obtains is transferred to the reaction under high pressure with polytetrafluoroethyllining lining
In kettle, the temperature in reaction kettle is increased to 125 DEG C by closed reactor, and carries out hydro-thermal reaction 5h at such a temperature.
(4) after the temperature inside reaction kettle naturally cools to 25 DEG C, reaction kettle is opened, reaction mixture was carried out
Filter, and with deionized water to the solid matter being obtained by filtration wash three times, by washed solid matter in air atmosphere in
85 DEG C of dry 4h, obtain presoma.
(5) presoma that step (4) obtains is placed in tube furnace, under an argon atmosphere, by the temperature in tube furnace by
25 DEG C of heating rates with 3 DEG C/min are increased to 600 DEG C, and keep 2h in the temperature, are pyrolyzed.To the temperature in tube furnace
It naturally cools to after 25 DEG C, thermal decomposition product is taken out from tube furnace, obtain carbon-coating nickel nano-particle according to the present invention.
Fig. 5 A and Fig. 5 B are the X-ray diffraction spectrograms for the carbon-coating nickel nano-particle that step (5) obtains, wherein Fig. 5 B is
2 θ are the partial enlarged view in 44 ° to 54 ° sections in Fig. 5 A.It can be seen that the diffraction maximum, right respectively of graphitic carbon from Fig. 5 A and Fig. 5 B
The Ni of two kinds of crystal phases of the side's Ying Yuliu closely spaced lattice structure nickel (hcp Ni) and face-centred cubic structure lattice structure nickel (fcc Ni)
Diffraction maximum.The relative intensity of each diffraction maximum is listed in table 2.
Table 2
| 2θ(°) | Relative intensity [100 × I/I0], using the intensity of the diffraction maximum within the scope of 43 ° -45 ° as I0 |
| 22-27 | 5.1 |
| 43-45 | 100 |
| 46-49 | 6.3 |
| 50-54 | 32.1 |
| 75-80 | 15.5 |
Elemental analyser measures in carbon-coating nickel nano-particle, and C content is 33.32 weight %, and H content is 0.86 weight
% is measured, O content is 4.01 weight %, and N content is 3.54 weight %, determines that Ni content is 58.27 weight % after normalization.
It is determined by tem analysis, evenly dispersed and size uniformity；Also, in the carbon-coating nickel nano-particle, metallic nickel kernel
Average grain diameter be 10nm, the average thickness of carbon coating layer is 2nm, and the average grain diameter of the carbon-coating nickel nano-particle is 12nm.
Embodiment 3
(1) at 30 DEG C, by 10mmol 3,5- pyridinedicarboxylic acid and 20mmol KOH are dissolved in 40mL deionized water, are obtained
To pyridinedicarboxylic acid aqueous solution.
(2) at 30 DEG C, 20mL Ni containing 10mmol (NO is added into the pyridinedicarboxylic acid aqueous solution of step (1) preparation3)2's
Aqueous solution stirs 20min, obtains the aqueous solution containing nickel ion.
(3) aqueous solution containing nickel ion that step (2) obtains is transferred to the reaction under high pressure with polytetrafluoroethyllining lining
In kettle, the temperature in reaction kettle is increased to 135 DEG C by closed reactor, and carries out hydro-thermal reaction 6h at such a temperature.
(4) after the temperature inside reaction kettle naturally cools to 25 DEG C, reaction kettle is opened, reaction mixture was carried out
Filter, and with deionized water to the solid matter being obtained by filtration wash three times, by washed solid matter in air atmosphere in
70 DEG C of dry 8h, obtain presoma.
(5) presoma that step (4) obtains is placed in tube furnace, under an argon atmosphere, by the temperature in tube furnace by
30 DEG C of heating rates with 2.5 DEG C/min are increased to 600 DEG C, and keep 2h in the temperature, are pyrolyzed.
(6) after naturally cooling to 25 DEG C to the temperature in tube furnace, thermal decomposition product is taken out from tube furnace, and will pyrolysis
1mol/L H is added in product2SO4In solution, the temperature of solution is increased to 90 DEG C, and after the temperature keeps 6h, by solution temperature
Degree naturally cools to 25 DEG C, solution is filtered, and the solid matter being obtained by filtration is adopted and is washed with deionized to washing
Water is neutrality.By washed solid matter in 90 DEG C of dry 8h in air atmosphere, carbon-coating nickel according to the present invention is obtained
Nano particle.
Fig. 6 A and Fig. 6 B are the X-ray diffraction spectrograms for the carbon-coating nickel nano-particle that step (6) obtains, wherein Fig. 6 B is
2 θ are the partial enlarged view in 44 ° to 54 ° sections in Fig. 6 A.It can be seen that the diffraction maximum, right respectively of graphitic carbon from Fig. 6 A and Fig. 6 B
The Ni of two kinds of crystal phases of the side's Ying Yuliu closely spaced lattice structure nickel (hcp Ni) and face-centred cubic structure lattice structure nickel (fcc Ni)
Diffraction maximum.The relative intensity of each diffraction maximum is listed in table 3.
Table 3
| 2θ(°) | Relative intensity [100 × I/I0], using the intensity of the diffraction maximum within the scope of 43 ° -45 ° as I0 |
| 22-27 | 15.2 |
| 43-45 | 100 |
| 46-49 | 14.5 |
| 50-54 | 30.3 |
| 75-80 | 14.8 |
Fig. 7 is the TEM figure for the carbon-coated nano particle that step (6) obtains.Apparent graphite shell as can see from Figure 7
With metal inner core, the core-shell structure of nano particle is directly demonstrated.It is determined by tem analysis, in the carbon-coating nickel nano-particle, gold
The average grain diameter for belonging to nickel kernel is 9nm, and the average thickness of carbon coating layer is 2nm, the average grain diameter of the carbon-coating nickel nano-particle
For 11nm.
Elemental analyser measures in carbon-coating nickel nano-particle, and C content is 43.42 weight %, and H content is 0.98 weight
% is measured, O content is 6.02 weight %, and N content is 4.34 weight %, determines that Ni content is 45.24 weight % after normalization.
Embodiment 4
(1) at 25 DEG C, by 10mmol 2,3- pyridinedicarboxylic acid and 22mmol NaOH are dissolved in 40mL deionized water, are obtained
To pyridinedicarboxylic acid aqueous solution.
(2) at 25 DEG C, 20mL NiSO containing 15mmol is added into the pyridinedicarboxylic acid aqueous solution of step (1) preparation4Water
Solution stirs 15min, obtains the aqueous solution containing nickel ion.
(3) aqueous solution containing nickel ion that step (2) obtains is transferred to the reaction under high pressure with polytetrafluoroethyllining lining
In kettle, the temperature in reaction kettle is increased to 160 DEG C by closed reactor, and carries out hydro-thermal reaction 8h at such a temperature.
(4) after the temperature inside reaction kettle naturally cools to 25 DEG C, reaction kettle is opened, reaction mixture was carried out
Filter, and with deionized water to the solid matter being obtained by filtration wash three times, by washed solid matter in air atmosphere in
100 DEG C of dry 2h, obtain presoma.
(5) presoma that step (4) obtains is placed in tube furnace, under an argon atmosphere, by the temperature in tube furnace by
25 DEG C of heating rates with 5 DEG C/min are increased to 700 DEG C, and keep 3h in the temperature, are pyrolyzed.To the temperature in tube furnace
It naturally cools to after 25 DEG C, thermal decomposition product is taken out from tube furnace, obtain carbon-coating nickel nano-particle according to the present invention.
Fig. 8 A and Fig. 8 B are the X-ray diffraction spectrograms for the carbon-coating nickel nano-particle that step (5) obtains, wherein Fig. 8 B is
2 θ are the partial enlarged view in 44 ° to 54 ° sections in Fig. 8 A.It can be seen that the diffraction maximum, right respectively of graphitic carbon from Fig. 8 A and Fig. 8 B
The Ni of two kinds of crystal phases of the side's Ying Yuliu closely spaced lattice structure nickel (hcp Ni) and face-centred cubic structure lattice structure nickel (fcc Ni)
Diffraction maximum.The relative intensity of each diffraction maximum is listed in table 4.
Table 4
| 2θ(°) | Relative intensity [100 × I/I0], using the intensity of the diffraction maximum within the scope of 43 ° -45 ° as I0 |
| 22-27 | 4.0 |
| 43-45 | 100 |
| 46-49 | 2.8 |
| 50-54 | 33.9 |
| 75-80 | 15.0 |
Elemental analyser measures in carbon-coating nickel nano-particle, and C content is 31.14 weight %, and H content is 0.66 weight
% is measured, O content is 3.27 weight %, and N content is 2.01 weight %, determines that Ni content is 62.92 weight % after normalization.
It is determined by tem analysis, in the carbon-coating nickel nano-particle, the average grain diameter of metallic nickel kernel is 13nm, carbon coating
The average thickness of layer is 2nm, and the average grain diameter of the carbon-coating nickel nano-particle is 15nm.
Embodiment 5
(1) at 25 DEG C, by 15mmol 2, dipicolimic acid 2 and 30mmol KOH are dissolved in 40mL deionized water, are obtained
To pyridinedicarboxylic acid aqueous solution.
(2) at 25 DEG C, 20mL NiSO containing 10mmol is added into the pyridinedicarboxylic acid aqueous solution of step (1) preparation4Water
Solution stirs 10min, obtains the aqueous solution containing nickel ion.
(3) aqueous solution containing nickel ion that step (2) obtains is transferred to the reaction under high pressure with polytetrafluoroethyllining lining
In kettle, the temperature in reaction kettle is increased to 150 DEG C by closed reactor, and carries out hydro-thermal reaction 10h at such a temperature.
(4) after the temperature inside reaction kettle naturally cools to 25 DEG C, reaction kettle is opened, reaction mixture was carried out
Filter, and with deionized water to the solid matter being obtained by filtration wash three times, by washed solid matter in air atmosphere in
90 DEG C of dry 3h, obtain presoma.
(5) presoma that step (4) obtains is placed in tube furnace, under an argon atmosphere, by the temperature in tube furnace by
25 DEG C of heating rates with 2.5 DEG C/min are increased to 700 DEG C, and keep 2h in the temperature, are pyrolyzed.
(6) after naturally cooling to 25 DEG C to the temperature in tube furnace, thermal decomposition product is taken out from tube furnace, and will pyrolysis
Product is added in 1.5mol/L HCl solution, the temperature of solution is increased to 85 DEG C, and after the temperature keeps 3h, by solution temperature
Degree naturally cools to 25 DEG C, solution is filtered, and the solid matter being obtained by filtration is adopted and is washed with deionized to washing
Water is neutrality.By washed solid matter in 100 DEG C of dry 4h in air atmosphere, carbon-coating nickel according to the present invention is obtained
Nano particle.
Fig. 9 A and Fig. 9 B are the X-ray diffraction spectrograms for the carbon-coating nickel nano-particle that step (6) obtains, wherein Fig. 9 B is
2 θ are the partial enlarged view in 44 ° to 54 ° sections in Fig. 9 A.It can be seen that the diffraction maximum, right respectively of graphitic carbon from Fig. 9 A and Fig. 9 B
The Ni of two kinds of crystal phases of the side's Ying Yuliu closely spaced lattice structure nickel (hcp Ni) and face-centred cubic structure lattice structure nickel (fcc Ni)
Diffraction maximum.The relative intensity of each diffraction maximum is listed in table 5.
Table 5
| 2θ(°) | Relative intensity [100 × I/I0], using the intensity of the diffraction maximum within the scope of 43 ° -45 ° as I0 |
| 22-27 | 44.0 |
| 43-45 | 100 |
| 46-49 | 11.3 |
| 50-54 | 31.4 |
| 75-80 | 13.9 |
Elemental analyser measures in carbon-coating nickel nano-particle, and C content is 58.69 weight %, and H content is 0.84 weight
% is measured, O content is 4.55 weight %, and N content is to determine that Ni content is 32.64 weight % after 3.28 weight % are normalized.
It is determined by tem analysis, in the carbon-coating nickel nano-particle, the average grain diameter of metallic nickel kernel is 13nm, carbon coating
The average thickness of layer is 2nm, and the average grain diameter of the carbon-coating nickel nano-particle is 15nm.
Embodiment 6
(1) at 25 DEG C, by 10mmol 3,4- pyridinedicarboxylic acid and 20mmol KOH are dissolved in 40mL deionized water, are obtained
To pyridinedicarboxylic acid aqueous solution.
(2) at 25 DEG C, 20mL Ni containing 10mmol (NO is added into the pyridinedicarboxylic acid aqueous solution of step (1) preparation3)2's
Aqueous solution stirs 15min, obtains the aqueous solution containing nickel ion.
(3) aqueous solution containing nickel ion that step (2) obtains is transferred to the reaction under high pressure with polytetrafluoroethyllining lining
In kettle, the temperature in reaction kettle is increased to 150 DEG C by closed reactor, and carries out hydro-thermal reaction 2h at such a temperature.
(4) after the temperature inside reaction kettle naturally cools to 25 DEG C, reaction kettle is opened, reaction mixture was carried out
Filter, and with deionized water to the solid matter being obtained by filtration wash three times, by washed solid matter in air atmosphere in
75 DEG C of dry 8h, obtain presoma.
(5) presoma that step (4) obtains is placed in tube furnace, under an argon atmosphere, by the temperature in tube furnace by
25 DEG C of heating rates with 2 DEG C/min are increased to 800 DEG C, and keep 1h in the temperature, are pyrolyzed.
(6) after naturally cooling to 25 DEG C to the temperature in tube furnace, thermal decomposition product is taken out from tube furnace, and will pyrolysis
Product is added in 1.2mol/L HCl solution, the temperature of solution is increased to 90 DEG C, and after the temperature keeps 4h, by solution temperature
Degree naturally cools to 25 DEG C, solution is filtered, and the solid matter being obtained by filtration is adopted and is washed with deionized to washing
Water is neutrality.By washed solid matter in 100 DEG C of dry 4h in air atmosphere, carbon-coating nickel according to the present invention is obtained
Nano particle.
Figure 10 A and Figure 10 B are the X-ray diffraction spectrograms for the carbon-coating nickel nano-particle that step (6) obtains, wherein Figure 10 B
It is the partial enlarged view that 2 θ are 44 ° to 54 ° sections in Figure 10 A.It can be seen that the diffraction maximum of graphitic carbon from Figure 10 A and Figure 10 B, divide
Not Dui Yingyu six side's closely spaced lattice structure nickel (hcp Ni) and face-centred cubic structure lattice structure nickel (fcc Ni) two kinds of crystal phases
Ni diffraction maximum.The relative intensity of each diffraction maximum is listed in table 6.
Table 6
| 2θ(°) | Relative intensity [100 × I/I0], using the intensity of the diffraction maximum within the scope of 43 ° -45 ° as I0 |
| 22-27 | 45.8 |
| 43-45 | 100 |
| 46-49 | 9.6 |
| 50-54 | 31.6 |
| 75-80 | 16.6 |
Elemental analyser measures in carbon-coating nickel nano-particle, and C content is 68.66 weight %, and H content is 0.74 weight
% is measured, O content is 3.14 weight %, and N content is 2.25 weight %, determines that Ni content is 25.21 weight % after normalization.
It is determined by tem analysis, in the carbon-coating nickel nano-particle, the average grain diameter of metallic nickel kernel is 20nm, carbon coating
The average thickness of layer is 5nm, and the average grain diameter of the carbon-coating nickel nano-particle is 25nm.
Embodiment 7
Carbon-coating nickel nano-particle is prepared using method same as Example 1, wherein in step (5), by step (4)
Obtained presoma is placed in tube furnace, under an argon atmosphere, by the temperature in tube furnace by 25 DEG C of heating speed with 5 DEG C/min
Rate is increased to 415 DEG C, and keeps 2h in the temperature, is pyrolyzed, to obtain carbon-coating nickel nano-particle.
Figure 11 A and Figure 11 B are the X-ray diffraction spectrograms of obtained carbon-coating nickel nano-particle, wherein Figure 11 B is figure
2 θ are the partial enlarged view in 44 ° to 54 ° sections in 11A.By in the X-ray diffraction spectrogram it can be seen that diffraction maximum of graphitic carbon and face
The diffraction maximum of the corresponding Ni of heart cubic structure lattice structure nickel (fcc Ni), without corresponding to six side's closely spaced lattice structure nickel (hcp
Ni diffraction maximum).The relative intensity of each diffraction maximum is listed in table 7.
Table 7
| 2θ(°) | Relative intensity [100 × I/I0], using the intensity of the diffraction maximum within the scope of 43 ° -45 ° as I0 |
| 22-27 | 11.8 |
| 43-45 | 100 |
| 46-49 | 0 |
| 50-54 | 23.0 |
| 75-80 | 13.6 |
Elemental analyser measures in carbon-coating nickel nano-particle, and C content is 35.51 weight %, and H content is 1.12 weights
% is measured, O content is 4.76 weight %, and N content is 4.45 weight %, determines that Ni content is 54.16 weight % after normalization.
It is determined by tem analysis, in the carbon-coating nickel nano-particle, the average grain diameter of metallic nickel kernel is 7nm, carbon coating layer
Average thickness be 1nm, the average grain diameter of the carbon-coating nickel nano-particle is 8nm.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (18)
1. a kind of carbon-coating nickel nano-particle, which contains metal state nickel and is coated on the metal state nickel at least
The carbon coating layer of part of the surface, in the X ray diffracting spectrum of the nano particle, respectively 2 θ be 22 ° to 27 °, 2 θ be 43 ° extremely
45 °, 2 θ be 46 ° to 49 °, 2 θ are 50 ° to 54 ° and 2 θ are 75 ° to 80 ° there are diffraction maximums.
2. nano particle according to claim 1, wherein using the intensity in the diffraction maximum that 2 θ are 43 ° to 45 ° appearance as base
Standard is 0.2-25 in the relative intensity for the diffraction maximum that 2 θ are 46 ° to 49 ° appearance, preferably 1-23, more preferably 2-21；
Preferably, to be 50 ° to the 54 ° diffraction occurred in 2 θ on the basis of the intensity for the diffraction maximum that 2 θ are 43 ° to 45 ° appearance
The relative intensity at peak is 20-40, preferably 22-35, is 11-20 in the relative intensity for the diffraction maximum that 2 θ are 75 ° to 80 ° appearance,
Preferably 13-18；
Preferably, to be 22 ° to the 27 ° diffraction occurred in 2 θ on the basis of the intensity for the diffraction maximum that 2 θ are 43 ° to 45 ° appearance
The relative intensity at peak is 0.2-50, preferably 1-48, more preferably 4-46.
3. nano particle according to claim 1 or 2, wherein on the basis of the total amount of the nano particle, nickel element contains
Amount be 5-75 weight %, preferably 10-70 weight %, more preferably 15-68 weight %, further preferably 20-65 weight %,
It is still more preferably 25-63 weight %.
4. nano particle according to claim 1, wherein the nano particle also contains oxygen element, nitrogen and protium,
On the basis of the total amount of the nano particle, the content of carbon is 24-94 weight %, preferably 26-85 weight %, more preferably
30-70 weight %；The content of oxygen element is 0.5-12 weight %, preferably 1-11 weight %, more preferably 3-10 weight %；Nitrogen
The content of element is 0.5-10 weight %, preferably 1-9.5 weight %, more preferably 2-9 weight %；The content of protium is
0.1-2.5 weight %, preferably 0.3-2.2 weight %, more preferably 0.5-2 weight %.
5. nano particle according to claim 4, wherein the oxygen element, nitrogen and protium are distributed in the carbon
In clad.
6. nano particle described in any one of -5 according to claim 1, wherein the average thickness of the carbon coating layer is 1-
5nm；
Preferably, the average grain diameter of the metal state nickel is 7-20nm；
Preferably, the average grain diameter of the carbon-coating nickel nano-particle is 8-25nm.
7. a kind of preparation method of carbon-coating nickel nano-particle, this method includes by pyridinedicarboxylic acid and water soluble nickel salt coordination type
At presoma be pyrolyzed in inert atmosphere.
8. preparation method according to claim 7, wherein be coordinated pyridinedicarboxylic acid and water soluble nickel salt to form presoma
Method include: to contact pyridinedicarboxylic acid with alkali and water soluble nickel salt under hydrothermal reaction condition；
Preferably, pyridinedicarboxylic acid is mixed with alkali and water, obtains pyridinedicarboxylic acid aqueous solution；The pyridinedicarboxylic acid is water-soluble
Liquid is mixed with water soluble nickel salt, obtains the aqueous solution containing nickel ion；By the aqueous solution containing nickel ion in hydro-thermal reaction
Under the conditions of reacted.
9. preparation method according to claim 8, wherein the molar ratio of pyridinedicarboxylic acid and water soluble nickel salt is 1:0.1-
1.5, preferably 1:0.3-1.5, more preferably 1:0.5-1.5, further preferably 1:0.6-1.5, the water soluble nickel salt with
Nickel element meter；
Preferably, pyridinedicarboxylic acid: alkali: the molar ratio of water be 1:1-3:1-1000, preferably 1:1.1-2.6:50-800, it is more excellent
It is selected as 1:1.2-2.3:200-500.
10. the preparation method according to any one of claim 7-9, wherein the pyridinedicarboxylic acid is selected from 2,3-
Pyridinedicarboxylic acid, 2,4 pyridine dicarboxylic acid, 2,5- pyridinedicarboxylic acid, 2,6- pyridinedicarboxylic acid, 3,4- pyridinedicarboxylic acid and 3,5-
One or more of pyridinedicarboxylic acid.
11. preparation method according to any one of claims of claim 7-10, wherein the water soluble nickel salt be selected from
NiCl2、Ni(NO3)2And NiSO4One or more of.
12. the preparation method according to any one of claim 7-11, wherein the alkali is KOH and/or NaOH.
13. the preparation method according to any one of claim 7-12, wherein the hydrothermal reaction condition includes: temperature
Degree is 100-200 DEG C, preferably 120-180 DEG C, more preferably 125-160 DEG C；Duration is 1 hour to 720 hours, preferably
It is 1.5-10 hours, more preferably 2-8 hours.
14. preparation method according to claim 7, wherein it is described pyrolysis 400-850 DEG C at a temperature of carry out, preferably
430-850 DEG C at a temperature of carry out, more preferably 500-850 DEG C at a temperature of carry out；
Preferably, the duration of the pyrolysis is 20-480 minutes, preferably 1-5 hours, more preferably 2-3 hours.
15. the preparation method according to claim 7 or 14, wherein by the presoma with 1-10 DEG C/min of rate liter
Temperature is to pyrolysis temperature；
Preferably, the presoma is warming up to pyrolysis temperature with 2-5 DEG C/min of rate.
16. the preparation method according to any one of claim 7,14 and 15, wherein the inert atmosphere is by nitrogen
The atmosphere that gas and/or argon gas are formed.
17. the preparation method according to any one of claim 7-16, wherein the preparation method further include: use water
Or the product that acid solution obtains pyrolysis washs；
Preferably, the acid solution is hydrochloric acid or sulfuric acid；
It is highly preferred that concentration sour in the acid solution be 0.1-3mol/L, preferably 0.5-2.5mol/L, more preferably
0.8-2mol/L, further preferably 1-1.5mol/L.
18. a kind of carbon-coating nickel nano-particle of the preparation of the preparation method as described in any one of claim 7-17.
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| CN112404447A (en) * | 2020-11-18 | 2021-02-26 | 云南电网有限责任公司电力科学研究院 | Preparation method and application of metallic nickel |
| CN114535569A (en) * | 2022-01-24 | 2022-05-27 | 同济大学 | Magnetic metal composite material and preparation method thereof |
| CN114535569B (en) * | 2022-01-24 | 2024-05-03 | 同济大学 | Magnetic metal composite material and preparation method thereof |
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