CN106115649A - A kind of nickel phosphate nano-tube material with crystallization tube wall and preparation method thereof - Google Patents
A kind of nickel phosphate nano-tube material with crystallization tube wall and preparation method thereof Download PDFInfo
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- CN106115649A CN106115649A CN201610500328.9A CN201610500328A CN106115649A CN 106115649 A CN106115649 A CN 106115649A CN 201610500328 A CN201610500328 A CN 201610500328A CN 106115649 A CN106115649 A CN 106115649A
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- nickel phosphate
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- 239000002071 nanotube Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 44
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 title claims abstract description 42
- 229910000159 nickel phosphate Inorganic materials 0.000 title claims abstract description 39
- 238000002425 crystallisation Methods 0.000 title claims abstract description 19
- 230000008025 crystallization Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 claims description 5
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 4
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims 1
- -1 octylame Chemical compound 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 229910001463 metal phosphate Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013086 LiNiPO Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000005498 Setaria italica Species 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- FIQNIRPYLPNUDK-UHFFFAOYSA-K calcium;nickel(2+);phosphate Chemical compound [Ca+2].[Ni+2].[O-]P([O-])([O-])=O FIQNIRPYLPNUDK-UHFFFAOYSA-K 0.000 description 1
- UUVBYOGFRMMMQL-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca].OP(O)(O)=O UUVBYOGFRMMMQL-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- AFYAQDWVUWAENU-UHFFFAOYSA-H nickel(2+);diphosphate Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O AFYAQDWVUWAENU-UHFFFAOYSA-H 0.000 description 1
- 235000002252 panizo Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
A kind of nickel phosphate nano-tube material, is characterized in that: a diameter of 4 ~ 20 nanometers, the hollow tubular structure of a length of 100 ~ 1000 nanometers, its tube wall is the nickel phosphate structure of crystallization.The synthesis of the nickel phosphate nano-tube material with crystallization tube wall synthesized by the present invention belongs to reported first.Utilizing phosphorus source, nickel source and organic amine cheap and easy to get is reactant, just can prepare nickel phosphate nano-tube material by liquid homogeneous precipitation method and hydrothermal synthesis method.The inventive method technique is simple, be applicable to industrial mass production and low cost, substantially do not have an environmental pollution.The invention discloses its preparation method.
Description
Technical field:
The present invention relates to a kind of nickel phosphate nano-tube material with crystallization tube wall and preparation method thereof.
Background technology:
Nano-tube material, from carbon nano-tube material in 1991 is in the news, the always focus of research.In catalytic applications
Aspect, nanotube, the particularly nanotube of tube wall crystallization, be 1-dimention nano level pipeline (duct) structural material of a kind of hollow,
Have the following characteristics that (1) nano level pipeline (duct) structure has the advantages that the aperture of mesopore molecular sieve is big, be beneficial to reaction point
The diffusion of son, the tube wall (duct) of (2) crystallization can keep the similar specific crystallographic structure of micro porous molecular sieve and constitutionally stable
Feature, (3) bending tube wall produces unique surface and interface effect that stress is caused, the titania nanotube such as protonated by
Confinement effect in the tube wall bent creates highly active Br nsted acid position and (4) nanotubes (duct), such as,
The confinement effect of CNT.Therefore, the focus of nanotube catalysis always nano-catalytic field focus of attention and research it
One.The nanotube of numerous kinds is successively synthesized and is applied to catalytic reaction, such as, CNT, vanadic anhydride,
Excellent the urging that the amorphous nano pipes such as titania nanotube, iron molybdate and nickel boron etc. and each of which embody in catalysis
Change performance.But, due to the restriction in nanotube synthesis, to cause the catalysis of nanotube to be limited only to some structure and compositions simple
Nano-tube material on, more complex compound such as metal phosphate nanotube then synthesize more difficulty, research
It is in progress the most relatively fewer.Metal phosphate is due to the property complicated and changeable (chemical composition and crystal structure are numerous) of its structure with molten
The easily characteristic such as crystallization in liquid, this makes the method utilizing soft chemical synthesis go to prepare the difficulty of metal phosphate nanotube
Very big, always one problem the most challenging.At present, a few metal phosphate nano-tube material is only had
It is seen in document report, such as titanium phosphate, Cerium monophosphate, and the aluminum phosphate synthesized by the seminar of inventor place, phosphoric acid
Calcium and cupric phosphate nanotube etc..
Nickel phosphate material, as a member of metal phosphate material family, it can apply to catalytic field, such as fourth two
The selective hydrogenation reaction of alkene and the epoxidation reaction etc. of cyclohexene, it is also possible to be applied to the electrode material of lithium ion battery, such as
LiNiPO material.Concrete research work is as follows: calendar year 2001, and the G. Ferey of Versailles, France university teaches seminar and exists
The article delivered in " Germany's applied chemistry ", it was recently reported that a kind of nickel phosphate (VSB-5) micro porous molecular sieve material is also answered
Selective hydrogenation reaction for butadiene.2010, the Wang An outstanding person seminar of big Polytechnics delivered on " catalysis journal "
One article, it was recently reported that the synthesis of a kind of unbodied nickel phosphate nanotube and catalysis epoxidation of cyclohexene reactivity worth thereof.
2015, the article that the Cao Dian seminar of Harbin Engineering University delivers on " colleges and universities' chemistry journal ", it was recently reported that
Plant the LiNiPO material of carbon modification for lithium ion battery material.2013, foxtail millet intelligence et al. applied for " lithium ion battery phosphorus
Acid nickel lithium/carbon composite material green synthesis method (application number: CN201310286222.X) " patent of invention.2015, Nie
Sending out of application that scholar is refined et al. " a kind of mushroom porous calcium phosphate nickel and preparation method thereof (application number: CN201510159080.X) "
Bright patent.
Summary of the invention:
Problem to be solved: sum up near for many years about the preparation of nickel phosphate material and the result by references of application, although previously
There is the report of nickel phosphate nano-tube material, but the most do not found that a kind of method prepares the nickel phosphate with crystallization tube wall
Nano-tube material, and the invention provides a kind of nickel phosphate nano-tube material with crystallization tube wall and preparation method thereof.
Technical scheme
The purpose of the present invention can be achieved through the following technical solutions:
The nickel phosphate nano-tube material of a kind of crystallization, it has a diameter of 4 ~ 20 nanometers, the hollow of a length of 100 ~ 1000 nanometers
Tubular structure, its tube wall is the nickel phosphate structure of crystallization.
The preparation method of a kind of above-mentioned nickel phosphate nano-tube material, comprises the following steps:
Step 1. is containing the dihydrogen phosphate ions that concentration is 0.050-0.600 mol/L and 0.040-0.500 mol/L
In nickel ion solution, add the organic amine of amount 1.4-5.2 times of dihydrogen phosphate ions material as template, stirring, mixing
Uniformly；
Suspension in step 1 has been transferred in teflon-lined water heating kettle by step 2., after sealing, and 150 ~ 200 °
Hydro-thermal 14-30 days under C.Afterwards, it is cooled to room temperature, opens water heating kettle, obtain jade-green suspension.
Step 3. is by the suspension sucking filtration in step 2, and repeatedly washs with ethanol, is dried under 60 ° of C, and obtain is emerald green
The powder of color is nickel phosphate nano-tube material.
Above-mentioned preparation method, the dihydrogen phosphate ions described in step 1 and the solution of nickel ion, preferably phosphoric acid, phosphoric acid
The aqueous solution of ammonium dihydrogen, sodium dihydrogen phosphate, potassium dihydrogen phosphate, Nickel dichloride., nickel nitrate, nickel sulfate and nickel acetate.
Above-mentioned preparation method, the organic amine described in step 1, preferably pentanediamine, Tetramethylammonium hydroxide, cyclohexylamine, oneself
Amine, octylame, decyl amine, lauryl amine, tetradecy lamine, cetylamine or 18-amine. or their mixture.
The beneficial effects of the present invention is:
The synthesis of the nickel phosphate nano-tube material 1, with crystallization tube wall belongs to reported first.
2, utilizing phosphorus source, nickel source and organic amine cheap and easy to get is reactant, by liquid homogeneous precipitation method and hydro-thermal
Synthetic method just can prepare nickel phosphate nano-tube material.
3, the inventive method technique is simple, be applicable to industrial mass production and low cost, substantially do not have an environmental pollution.
Accompanying drawing illustrates:
Fig. 1 is the X-ray powder diffraction figure of the nickel phosphate nano-tube material of the embodiment of the present invention 1 preparation.
Fig. 2 is the TEM transmission electron microscope photo of the nickel phosphate nano-tube material of the embodiment of the present invention 1 preparation.
Fig. 3 is the TEM transmission electron microscope photo of the nickel phosphate nano-tube material of the embodiment of the present invention 2 preparation.
Fig. 4 is the TEM transmission electron microscope photo of the nickel phosphate nano-tube material of the embodiment of the present invention 3 preparation.
Fig. 5 is nitrogen adsorption desorption curve (a) and the pore size distribution figure of the nickel phosphate nano-tube material of the embodiment of the present invention 4 preparation
(b)。
Fig. 6 is the TEM transmission electron microscope photo of the nickel phosphate nano-tube material of the embodiment of the present invention 6 preparation.
Fig. 7 is the TEM transmission electron microscope photo of the nickel phosphate nano-tube material of the embodiment of the present invention 7 preparation.
Detailed description of the invention:
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1:
The ammonium dihydrogen phosphate of 0.005 mol and the Nickel dichloride. of 0.040 mol are dissolved in 80 ml water, are subsequently adding 20 ml and contain
There are the lauryl amine of 0.006 mol and the ethanol solution of the cetylamine of 0.001 mol, stir 24 hours.Above-mentioned suspension is shifted
To having in teflon-lined water heating kettle, after sealing, hydro-thermal 30 days under 180 ° of C.Afterwards, it is cooled to room temperature, opens hydro-thermal
Still, obtains jade-green suspension.By this jade-green suspension sucking filtration, and repeatedly wash with ethanol, be dried under 60 ° of C,
To emerald green powder be nickel phosphate nano-tube material.Product is accredited as the nickel phosphate of crystallization (see figure through X-ray powder diffraction
1), TEM Electronic Speculum detection product pattern (see figure 2), its caliber is about 8 nanometers.
Embodiment 2:
The sodium dihydrogen phosphate of 0.010 mol and the Nickel dichloride. of 0.009 mol are dissolved in 80 ml water, are subsequently adding 20 ml and contain
There are the lauryl amine of 0.010 mol and the ethanol solution of the pentanediamine of 0.004 mol, stir 16 hours.Above-mentioned suspension is shifted
To having in teflon-lined water heating kettle, after sealing, hydro-thermal 20 days under 200 ° of C.Afterwards, it is cooled to room temperature, opens hydro-thermal
Still, obtains jade-green suspension.By this jade-green suspension sucking filtration, and repeatedly wash with ethanol, be dried under 60 ° of C,
To emerald green powder be nickel phosphate nano-tube material.Product is accredited as the nickel phosphate of crystallization, TEM through X-ray powder diffraction
Electronic Speculum detection product pattern (see figure 3), its caliber is about 4 nanometers.In wherein in Fig. 3 b, illustration shows the phosphorus that its tube wall is crystallization
Acid nickel crystal structure, its interplanar distance is 0.214 nanometer.
Embodiment 3:
The potassium dihydrogen phosphate of 0.025 mol and the nickel sulfate of 0.020 mol are dissolved in 70 ml water, are subsequently adding 30 ml and contain
There is the ethanol solution of the Tetramethylammonium hydroxide of 0.075 mol, stir 8 hours.Above-mentioned suspension has been transferred to polytetrafluoroethyl-ne
In the water heating kettle of alkene liner, after sealing, hydro-thermal 24 days under 150 ° of C.Afterwards, it is cooled to room temperature, opens water heating kettle, obtain yellowish green
The suspension of color.By this yellowish green suspension sucking filtration, and repeatedly wash with ethanol, be dried under 60 ° of C, the yellowish green toner obtained
End is nickel phosphate nano-tube material.Product is accredited as nickel phosphate through X-ray powder diffraction, TEM Electronic Speculum detection product pattern (see
Fig. 4), its caliber is about 15 nanometers.
Embodiment 4:
The ammonium dihydrogen phosphate of 0.036 mol and the nickel nitrate of 0.030 mol are dissolved in 70 ml water, are subsequently adding 30 ml and contain
There are pentanediamine and the ethanol solution of 0.009 cyclohexylamine of 0.060 mol, stir 12 hours.Above-mentioned suspension has been transferred to poly-
In the water heating kettle of tetrafluoroethene liner, after sealing, hydro-thermal 14 days under 200 ° of C.Afterwards, it is cooled to room temperature, opens water heating kettle,
To yellowish green suspension.By this yellowish green suspension sucking filtration, and repeatedly wash with ethanol, be dried under 60 ° of C, the Huang obtained
Green powder is nickel phosphate nano-tube material.Product is accredited as nickel phosphate, TEM Electronic Speculum detection product through X-ray powder diffraction
Pattern, nitrogen adsorption desorption curve (a) and pore size distribution figure (b), its caliber is about 6 nanometers.
Embodiment 5:
The phosphoric acid of 0.06 mol and the nickel acetate of 0.050 mol are dissolved in 50 ml water, are subsequently adding 50 ml and contain 0.300
The octylame of mol and the ethanol solution of the tetradecy lamine of 0.012 mol, stir 8 hours.Above-mentioned suspension has been transferred to polytetrafluoroethyl-ne
In the water heating kettle of alkene liner, after sealing, hydro-thermal 18 days under 160 ° of C.Afterwards, it is cooled to room temperature, opens water heating kettle, obtain yellowish green
The suspension of color.By this yellowish green suspension sucking filtration, and repeatedly wash with ethanol, be dried under 60 ° of C, the yellowish green toner obtained
End is nickel phosphate nano-tube material.Product is accredited as nickel phosphate through X-ray powder diffraction, TEM Electronic Speculum detection product pattern (see
Fig. 6).
Embodiment 6:
The ammonium dihydrogen phosphate of 0.015 mol and the nickel sulfate of 0.012 mol are dissolved in 80 ml water, are subsequently adding 40 ml and contain
There is the ethanol solution of the cetylamine of 0.033 mol, stir 18 hours.Above-mentioned suspension has been transferred to teflon-lined
In water heating kettle, after sealing, hydro-thermal 30 days under 170 ° of C.Afterwards, it is cooled to room temperature, opens water heating kettle, obtain jade-green suspended
Liquid.By this jade-green suspension sucking filtration, and repeatedly washing with ethanol, be dried under 60 ° of C, the emerald green powder obtained is phosphorus
Acid Nickel nanotubes material.Product is accredited as nickel phosphate, TEM Electronic Speculum detection product pattern (see figure 7) through X-ray powder diffraction.
Claims (4)
1. a nickel phosphate nano-tube material for crystallization, is characterized in that: a diameter of 4 ~ 20 nanometers, a length of 100 ~ 1000 nanometers
Hollow tubular structure, its tube wall is the nickel phosphate structure of crystallization.
2. the method preparing the nickel phosphate nano-tube material of crystallization described in claim 1, is characterized in that including following step
Rapid:
Step 1: containing the dihydrogen phosphate ions that concentration is 0.050-0.600 mol/L and 0.040-0.500 mol/L
In nickel ion solution, add the organic amine of amount 1.4-5.2 times of dihydrogen phosphate ions material as template, stirring, mixing
Uniformly；
Step 2: the suspension in step 1 has been transferred in teflon-lined water heating kettle, after sealing, 150 ~ 200 °
Under C after hydro-thermal 14-30 days, it is cooled to room temperature, opens water heating kettle, obtain jade-green suspension；
Step 3: by the suspension sucking filtration in step 2, and repeatedly wash with ethanol, is dried under 60 ° of C, obtain emerald green or
Yellowish green powder is nickel phosphate nano-tube material.
3. according to the preparation method that claim 2 is above-mentioned, it is characterized in that: dihydrogen phosphate ions described in step 1 and nickel ion
Solution is, the water of phosphoric acid, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, Nickel dichloride., nickel nitrate, nickel sulfate and nickel acetate
Solution.
Preparation method the most according to claim 2, is characterized in that: the organic amine described in step 1 is, pentanediamine, tetramethyl hydrogen-oxygen
Change ammonium, cyclohexylamine, hexylamine, octylame, decyl amine, lauryl amine, tetradecy lamine, cetylamine or 18-amine. or their mixture.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108083250A (en) * | 2018-02-07 | 2018-05-29 | 济南大学 | A kind of porous amorphous phosphoric acid nickel nano particle of soft pompon shape and preparation method thereof |
| CN113264515A (en) * | 2021-05-19 | 2021-08-17 | 西北工业大学 | Nickel phosphate nanotube multi-stage assembly structure material and preparation method and application thereof |
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| CN108083250A (en) * | 2018-02-07 | 2018-05-29 | 济南大学 | A kind of porous amorphous phosphoric acid nickel nano particle of soft pompon shape and preparation method thereof |
| CN113264515A (en) * | 2021-05-19 | 2021-08-17 | 西北工业大学 | Nickel phosphate nanotube multi-stage assembly structure material and preparation method and application thereof |
| CN113264515B (en) * | 2021-05-19 | 2023-11-17 | 西北工业大学 | Nickel phosphate nanotube multistage assembly structure material and preparation method and application thereof |
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