CN106882844A - Core shell structure NiO/Ni3The preparation method of N materials - Google Patents

Core shell structure NiO/Ni3The preparation method of N materials Download PDF

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CN106882844A
CN106882844A CN201510933741.XA CN201510933741A CN106882844A CN 106882844 A CN106882844 A CN 106882844A CN 201510933741 A CN201510933741 A CN 201510933741A CN 106882844 A CN106882844 A CN 106882844A
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shell structure
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CN106882844B (en
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杨明辉
冯璐
邹明明
焦雨桐
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • 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 present invention relates to a kind of nano material NiO/Ni with mesoporous core shell structure3The preparation method of N, the preparation method uses solvent thermal process, and water or ethanol are solvent, and the two is added in varing proportions；With urea and nickel sulfate as raw material, the two is respectively with 2:1~5:1 different mol ratio example is added；After being heated 4~24 hours at 100 DEG C~200 DEG C, presoma is carried out the calcining of 2~6 hours at 400 DEG C~600 DEG C.The NiO of generation is nitrogenized again, then NiO materials are nitrogenized 2~6 hours at 350 DEG C~450 DEG C.The NiO/Ni with mesoporous core shell structure can be obtained3N materials.The inventive method has the low advantage of simple synthetic method, reaction temperature.

Description

Core shell structure NiO/Ni3The preparation method of N materials
Technical field
The present invention relates to a kind of NiO/Ni3The preparation method of N compounds.
Background technology
Transition metal nitride with excellent characteristics such as high-melting-point, high rigidity, highly thermally conductive property, excellent electric conductivity, good chemical stability, corrosion-resistant and eka-platinium catalytic performances because turning into focus of concern.More in terms of being widely used in the numerous areas such as cutting element, wear parts, coating material on nitrogenizing the research of nickel composite metal, such as nickel oxide tungsten hydrogenation makees catalyst；Or the magnetic and microwave property for Fe-Ni-N compounds are studied, a series of Fe-Ni-N compounds of different Fe/Ni atomic ratios are respectively provided with saturation magnetization and less coercivity higher, show typical soft ferromagnetic feature.At the same time, Fe-Ni-N compound samples show good absorbing property；Relative to nickel oxide, nickel oxide is then relatively applied in terms of capacitor.Such as NiO with meso-hole structure can largely be used for making electrochemical capacitor electrode, and keep specific capacitance and good capacitive property higher.The preparation method of NiO has a lot, and such as Guo Wei, Xie Zhongwei et al. prepare NiO with sol-gal process, (with nickel sulfate (NiSO4·H2O obtained alkoxide in distilled water and ethanol) is dissolved in, and basic hydrolysis is carried out to solution with NaOH, NiO electrochomeric films are deposited with dip-coating-czochralski method again after being sufficiently stirred for.) and for example K.C.Min, Y.H.You et al. once prepares NiO using mocvd method, and for example L.Cattin, B.A.Reguig, A.KheLi et al. once prepares NiO using spray pyrolysis, using different precursor solutions, using glass as substrate, in deposition, underlayer temperature is 350 DEG C, respectively from NiCl2·6H2O、Ni(NO3)2·6H2O、NiSO4·4H2O forms NiO in being dissolved in acid salt solution as presoma, spraying.For another example radio-frequency magnetron sputter method prepares NiO films, and with silicon chip and quartzy two kinds of materials respectively as end liner, target is the NiO solid targets after sintering, is passed through argon gas and oxygen in coating process in reative cell.
The content of the invention
The purpose of the present invention is that a kind of raw material of offer is easy to get, and technical process simply prepares the NiO/Ni of mesoporous core shell structure3The preparation method of N.
The purpose of the present invention is reached by following proposal.
1. respectively with 2:1~5:The urea and nickel sulfate of 1 mol ratio are material.
2. 4~24h of solvent thermal reaction at 100 DEG C~200 DEG C, after carry out suction filtration drying.
3. 2~6h is calcined at 400 DEG C~600 DEG C, black NiO materials are obtained.
4. the ammonia gas by the NiO materials with core shell structure at 350 DEG C~450 DEG C nitrogenize 2~6h.
Core shell structure NiO/Ni is prepared the invention provides one kind3The method of N, is characterized in：
1. preparation flow and equipment are simple.
2. nitrogen source used by is industrial ammonia, safer compared to hydrogen and nitrogen mixed gas.
3. course of reaction temperature of the invention is low, and the time is relatively short, is easily controlled.
4. this method is easy to operate.
Brief description of the drawings
Fig. 1 is Ni (HCO3)2XRD.
Fig. 2 is the XRD of NiO.
Fig. 3 is NiO/Ni3The XRD of N.
Fig. 4 is Ni3The XRD of N.
Fig. 5 is Ni (OH)2XRD.
Fig. 6 is Ni (OH)2SEM figure.
Fig. 7 is Ni (HCO3)2SEM figure.
Fig. 8 is NiO/Ni3The SEM figures of N.
Specific embodiment
In order to further illustrate the present invention, following embodiment is enumerated.
Embodiment 1
Nickel salt NiSO4·6H2O and urea are with 1:5 molar ratios mix, plus 50ml water and 30ml ethanol carry out solvent thermal reaction, are put into Muffle furnace and are warming up to 160 DEG C with 4 DEG C/min speed, lower the temperature after keeping 18h.It is cooled to room temperature taking-up, is characterized through XRD, Ni (HCO can be obtained3)2(Fig. 1), after being scanned through SEM, it can be seen that Ni (HCO3)2External morphology (Fig. 7).It is positioned in tube furnace by primary product, 500 DEG C is warming up to 4 DEG C/min, room temperature taking-up is down to after calcining 2h, NiO (Fig. 2) can be obtained, put it into again and vacuumize in nitriding furnace, lead to ammonia, be warming up to 400 DEG C, nitridation 2 hours, characterizes through XRD, can obtain NiO/Ni3N materials (Fig. 3), characterize, it can be seen that NiO/Ni through SEM3N materials have core shell structure (Fig. 8).
Embodiment 2
Nickel salt NiSO4·6H2O and urea are with 1:5 molar ratios mix, plus 50ml water and 30ml ethanol carry out solvent thermal reaction, are put into Muffle furnace and are warming up to 160 DEG C with 4 DEG C/min speed, lower the temperature after keeping 18h.It is cooled to room temperature taking-up, is characterized through XRD, Ni (HCO can be obtained3)2, it is positioned in tube furnace by primary product, it is warming up to 500 DEG C with 4 DEG C/min, room temperature taking-up is down to after calcining 2h, can obtain NiO, then put it into and vacuumize in nitriding furnace, lead to ammonia, 350 DEG C are warming up to, nitrogenize 4 hours, characterized through XRD, can obtain Ni3N materials (Fig. 4).
Embodiment 3
Nickel salt NiSO4·6H2O and urea are with 1:2 molar ratios mix, plus 50ml water and 30ml ethanol carry out solvent thermal reaction, are put into Muffle furnace and are warming up to 160 DEG C with 4 DEG C/min speed, lower the temperature after keeping 4h.It is cooled to room temperature taking-up, is characterized through XRD, Ni (OH) can be obtained2(Fig. 5), after being characterized through SEM, it can be seen that Ni (OH)2External morphology (such as Fig. 6).It is positioned in tube furnace by primary product, 600 DEG C is warming up to 4 DEG C/min, room temperature taking-up is down to after calcining 2h, can obtain NiO, then put it into and vacuumize in nitriding furnace, lead to ammonia, be warming up to 350 DEG C, nitrogenized 3 hours, characterized through XRD, can obtain NiO materials.
Embodiment 4
Nickel salt NiSO4·6H2O and urea are with 1:5 molar ratios mix, plus 50ml water and 30ml ethanol carry out solvent thermal reaction, are put into Muffle furnace and are warming up to 100 DEG C with 4 DEG C/min speed, lower the temperature after keeping 18h.It is cooled to room temperature taking-up, is characterized through XRD, Ni (OH) can be obtained2, it is positioned in tube furnace by primary product, it is warming up to 450 DEG C with 4 DEG C/min, room temperature taking-up is down to after calcining 2h, can obtain NiO, then put it into and vacuumize in nitriding furnace, lead to ammonia, 450 DEG C are warming up to, nitrogenize 2 hours, characterized through XRD, can obtain Ni3N materials.
Embodiment 5
Nickel salt NiSO4·6H2O and urea are with 1:5 molar ratios mix, plus 50ml water and 30ml ethanol carry out solvent thermal reaction, are put into Muffle furnace and are warming up to 200 DEG C with 4 DEG C/min speed, lower the temperature after keeping 4.It is cooled to room temperature taking-up, is characterized through XRD, Ni (OH) can be obtained2, it is positioned in tube furnace by primary product, it is warming up to 600 DEG C with 4 DEG C/min, room temperature taking-up is down to after calcining 2h, can obtain NiO, then put it into and vacuumize in nitriding furnace, lead to ammonia, 450 DEG C are warming up to, nitrogenize 2 hours, characterized through XRD, can obtain Ni3N materials.
Embodiment 6
Nickel salt NiSO4·6H2O and urea are with 1:2 molar ratios mix, plus 50ml water and 30ml ethanol carry out solvent thermal reaction, are put into Muffle furnace and are warming up to 100 DEG C with 4 DEG C/min speed, lower the temperature after keeping 18h.It is cooled to room temperature taking-up, is characterized through XRD, Ni (OH) can be obtained2, it is positioned in tube furnace by primary product, it is warming up to 400 DEG C with 4 DEG C/min, room temperature taking-up is down to after calcining 2h, can obtain NiO, then put it into and vacuumize in nitriding furnace, lead to ammonia, 450 DEG C are warming up to, nitrogenize 2 hours, characterized through XRD, can obtain Ni3N materials.
Embodiment 7
Nickel salt NiSO4·6H2O and urea are with 1:5 molar ratios mix, plus 80ml water carries out solvent thermal reaction, are put into Muffle furnace and are warming up to 160 DEG C with 4 DEG C/min speed, lower the temperature after keeping 20h.It is cooled to room temperature taking-up, is characterized through XRD, Ni (HCO can be obtained3)2, it is positioned in tube furnace by primary product, it is warming up to 500 DEG C with 4 DEG C/min, room temperature taking-up is down to after calcining 2h, can obtain NiO, then put it into and vacuumize in nitriding furnace, lead to ammonia, 375 DEG C are warming up to, nitrogenize 2 hours, characterized through XRD, can obtain NiO materials.
Embodiment 8
Nickel salt NiSO4·6H2O and urea are with 1:2 molar ratios mix, plus 80ml water carries out solvent thermal reaction, are put into Muffle furnace and are warming up to 170 DEG C with 4 DEG C/min speed, lower the temperature after keeping 24h.It is cooled to room temperature taking-up, is characterized through XRD, Ni (OH) can be obtained2, it is positioned in tube furnace by primary product, it is warming up to 600 DEG C with 4 DEG C/min, room temperature taking-up is down to after calcining 2h, can obtain NiO, then put it into and vacuumize in nitriding furnace, lead to ammonia, 400 DEG C are warming up to, nitrogenize 2 hours, characterized through XRD, can obtain NiO/Ni3N materials.
Embodiment 9
Nickel salt NiSO4·6H2O and urea are with 1:5 molar ratios mix, plus 80ml water carries out solvent thermal reaction, are put into Muffle furnace and are warming up to 160 DEG C with 4 DEG C/min speed, lower the temperature after keeping 24h.It is cooled to room temperature taking-up, is characterized through XRD, Ni (HCO can be obtained3)2, it is positioned in tube furnace by primary product, it is warming up to 600 DEG C with 4 DEG C/min, room temperature taking-up is down to after calcining 2h, can obtain NiO, then put it into and vacuumize in nitriding furnace, lead to ammonia, 400 DEG C are warming up to, nitrogenize 3 hours, characterized through XRD, can obtain NiO/Ni3N materials.
Embodiment 10
Nickel salt NiSO4·6H2O and urea are with 1:5 molar ratios mix, plus 80ml water carries out solvent thermal reaction, are put into Muffle furnace and are warming up to 160 DEG C with 4 DEG C/min speed, lower the temperature after keeping 24h.It is cooled to room temperature taking-up, is characterized through XRD, Ni (HCO can be obtained3)2, it is positioned in tube furnace by primary product, it is warming up to 600 DEG C with 4 DEG C/min, room temperature taking-up is down to after calcining 2h, can obtain NiO, then put it into and vacuumize in nitriding furnace, lead to ammonia, 400 DEG C are warming up to, nitrogenize 2 hours, characterized through XRD, can obtain NiO/Ni3N materials.

Claims (10)

1. core shell structure NiO/Ni3The preparation method of N materials, it is characterized in that：Nickel source is mixed molten with urea In solvent, hydro-thermal reaction is carried out, the persursor material of generation is sintered, then the NiO that will be generated Material carries out nitrogen treatment, can prepare mesoporous core shell structure NiO/Ni3N materials.
2. according to the preparation method described in claim 1, it is characterized in that：Described nickel source is NiSO4·6H2O；It is 1 with the mol ratio of urea to control nickel source:2~1:5.
3. according to the preparation method described in claim 1, it is characterized in that：Described solvent is water or ethanol Or the two is mixed with arbitrary proportion.
4. according to the preparation method of the presoma described in claim 1, it is characterized in that：Described hydro-thermal temperature Spend is 100 DEG C~200 DEG C.
5. according to the preparation method of the presoma described in claim 1, it is characterized in that：The time of hydro-thermal is 4~24 hours, the presoma for being generated was Ni (HCO3)2Or Ni (OH)2。
6. according to the preparation method of the NiO described in claim 1, it is characterized in that：Described sintering temperature Control is at 400 DEG C~600 DEG C.
7. according to the preparation method of the NiO described in claim 1, it is characterized in that：During described sintering Between control at 2~6 hours, product is NiO.
8. according to the preparation method described in claim 1, it is characterized in that：Described nitrogen source is ammonia.
9. according to the preparation method described in claim 1 or 8, it is characterized in that：By NiO in ammonia Nitrogen treatment is carried out, described nitriding temperature is 350 DEG C~450 DEG C.
10. according to the preparation method described in claim 1 or 8, it is characterized in that：Described nitridation time It is 2~6 hours.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109055974A (en) * 2018-07-23 2018-12-21 电子科技大学 A kind of porous Ni-N-O nano-particle material and its preparation method and application
CN110171807A (en) * 2019-06-10 2019-08-27 陕西师范大学 A method of preparing three nickel by powder of nano silicon nitride
CN112058299A (en) * 2020-09-10 2020-12-11 中山大学 Multi-shell nickel-based nitride nano composite material and preparation method and application thereof
CN114214663A (en) * 2022-01-06 2022-03-22 武汉工程大学 Nitrogen vacancy modified nickel nitride electrocatalytic material and preparation method and application thereof
CN114573028A (en) * 2022-04-28 2022-06-03 华中科技大学 Transition metal compound with heterojunction structure, preparation method thereof and composite lithium supplement material
CN115744841A (en) * 2022-11-15 2023-03-07 西安近代化学研究所 Nickel-based nitride nano combustion catalyst and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN1251351A (en) * 1998-10-21 2000-04-26 中国科学院金属腐蚀与防护研究所 Method for producing spheroidal nickelous hydroxide series powder
CN1861528A (en) * 2005-05-13 2006-11-15 黄石理工学院 Process for preparing nano NiO by ammonia water single phase precipitation
CN103946146A (en) * 2011-10-24 2014-07-23 康奈尔大学 Mesoporous metal nitride materials and methods

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1251351A (en) * 1998-10-21 2000-04-26 中国科学院金属腐蚀与防护研究所 Method for producing spheroidal nickelous hydroxide series powder
CN1861528A (en) * 2005-05-13 2006-11-15 黄石理工学院 Process for preparing nano NiO by ammonia water single phase precipitation
CN103946146A (en) * 2011-10-24 2014-07-23 康奈尔大学 Mesoporous metal nitride materials and methods

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109055974A (en) * 2018-07-23 2018-12-21 电子科技大学 A kind of porous Ni-N-O nano-particle material and its preparation method and application
CN110171807A (en) * 2019-06-10 2019-08-27 陕西师范大学 A method of preparing three nickel by powder of nano silicon nitride
CN112058299A (en) * 2020-09-10 2020-12-11 中山大学 Multi-shell nickel-based nitride nano composite material and preparation method and application thereof
CN114214663A (en) * 2022-01-06 2022-03-22 武汉工程大学 Nitrogen vacancy modified nickel nitride electrocatalytic material and preparation method and application thereof
CN114214663B (en) * 2022-01-06 2024-06-14 武汉工程大学 Nickel nitride electrocatalytic material modified by nitrogen vacancy and preparation method and application thereof
CN114573028A (en) * 2022-04-28 2022-06-03 华中科技大学 Transition metal compound with heterojunction structure, preparation method thereof and composite lithium supplement material
CN114573028B (en) * 2022-04-28 2022-08-12 华中科技大学 Transition metal compound with heterojunction structure, preparation method thereof and composite lithium-supplementing material
CN115744841A (en) * 2022-11-15 2023-03-07 西安近代化学研究所 Nickel-based nitride nano combustion catalyst and preparation method thereof
CN115744841B (en) * 2022-11-15 2024-05-10 西安近代化学研究所 Nickel-based nitride nano combustion catalyst and preparation method thereof

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