CN110482480B - Cobalt-nickel bimetallic hydroxyl phosphite rod-like crystal array film and preparation method thereof - Google Patents
Cobalt-nickel bimetallic hydroxyl phosphite rod-like crystal array film and preparation method thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 49
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- WHZWVUKPJBNTAK-UHFFFAOYSA-N hydroxy dihydrogen phosphite Chemical compound OOP(O)O WHZWVUKPJBNTAK-UHFFFAOYSA-N 0.000 title claims abstract description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 10
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 10
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- BLDAZRRUONPTEL-UHFFFAOYSA-N OP(O)(O)O Chemical compound OP(O)(O)O BLDAZRRUONPTEL-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000006911 nucleation Effects 0.000 description 7
- 238000000635 electron micrograph Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- -1 Transition metal hydroxyphosphites Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 235000008409 marco Nutrition 0.000 description 1
- 244000078446 marco Species 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/58—Fabrics or filaments
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- B81B7/04—Networks or arrays of similar microstructural devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a cobalt-nickel bimetallic hydroxyl phosphite rodlike crystal array film and a preparation method thereof. Dissolving nickel nitrate hexahydrate, cobalt nitrate hexahydrate and sodium hypophosphite in deionized water, and adding N, N-dimethylacetamide; soaking the pre-cleaned activated carbon fiber in the prepared solution, and carrying out sealed reaction in a reaction kettle at the temperature of 140-160 ℃ for 10-20 h; after the reaction kettle is naturally cooled to normal temperature, taking out the activated carbon fiber, repeatedly cleaning the activated carbon fiber by absolute ethyl alcohol and deionized water, drying the activated carbon fiber at 60 ℃ for 8 hours to obtain compact and uniform M on the surface of the activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 (M = Ni + Co) rod-like crystal array film. The rod-like crystal array film obtained by the invention has the advantages of simple and safe preparation method, uniform and compact array crystal, stable and uniform surface performance, and can be applied to the fields of novel energy storage, catalysis and sensing.
Description
Technical Field
The invention relates to a crystal array film taking a porous fiber material as a substrate and a preparation method thereof, in particular to a cobalt-nickel bimetal hydroxyl phosphite rodlike crystal array film taking activated carbon fibers as a substrate and a preparation method thereof.
Background
Transition metal hydroxyphosphites M 11 (HPO 3 ) 8 (OH) 6 (M = Zn, Ni or Co) is a new inorganic material with a wide range of potential applications in adsorption, catalysis and energy storage due to its diversity of stoichiometric relationships and rich structural chemistry properties [ m.d. Marcos et al, j. Solid State chem., 107(1993), 250-; M.D. Marcos et al, chem. mater, 5(1993), 121-.]. It is well known that the properties of a material depend to a large extent on the size and morphology of the material. Researches find that the transition metal hydroxyphosphite with an ordered structure shows more excellent electrical and optical properties. It is noteworthy that transition metal hydroxyphosphites have been a new generation of high performance super-electrodes due to their high specific capacitance, cycling stability and fast charge-discharge capabilityThe effective positive electrode material of the container has begun to attract attention.
In the traditional super capacitor, an active material, a conductive agent (acetylene black), a binder and the like are uniformly coated on the surface of a current collector by a coating method to prepare an electrode. The electrode manufacturing method is suitable for application of powder active materials, but is limited by process stability and is not convenient to recycle. In contrast, the electrochemical active material is deposited on the surface of the current collector in the form of a thin film, so that the binderless electrode can be obtained, the possibility of efficient transmission of electrons between the active material and the current collector is provided, and the electrode performance is expected to be improved. At present, M is reported in the literature 11 (HPO 3 ) 8 (OH) 6 (M = Zn, Ni or Co) is a powder material, and most of the powder material is monometal hydroxyphosphite, and reports about a rod-shaped crystal array film material of the double-transition metal hydroxyphosphite are not found.
Disclosure of Invention
The invention aims to provide a cobalt-nickel bimetallic hydroxyphosphite rodlike crystal array film and a preparation method thereof (also can be expressed as M) 11 (HPO 3 ) 8 (OH) 6 (M = Ni + Co) rod-like crystal array film and a method for producing the same). The preparation method makes full use of the abundant pore structure on the surface of the activated carbon fiber, and the structure is M 11 (HPO 3 ) 8 (OH) 6 The (M = Ni + Co) rod-shaped crystal array film provides a large number of nucleation centers for heterogeneous nucleation crystallization on the surface of the activated carbon fiber, and the M is combined with the adjustment of reactant concentration, reaction time and reactant concentration ratio 11 (HPO 3 ) 8 (OH) 6 The (M = Ni + Co) crystals preferentially crystallize on the surface of the activated carbon fiber, and then grow anisotropically to form a rod-like morphology.
The invention establishes a stable hydrothermal reaction system based on the hydrothermal reaction characteristics and the crystal growth principle as guidance and the comprehensive action of various reaction parameters, and M is positioned on the surface of the activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 The nucleation environment, growth orientation and crystallization rate of (M = Ni + Co) crystals are precisely controlled, and M with anisotropic growth characteristics is promoted 11 (HPO 3 ) 8 (OH) 6 The (M = Ni + Co) rod-shaped crystals form a dense and uniform thin film layer arranged in an array on the surface of the activated carbon fiber.
The technical scheme adopted by the invention comprises the following steps:
a cobalt-nickel bi-metal hydroxyl phosphite rod-like crystal array film, the M 11 (HPO 3 ) 8 (OH) 6 The diameter of the (M = Ni + Co) rod-shaped crystal is 500 nm-1 micron, and the rod-shaped crystal is densely arranged in an array form to form a thin film.
Secondly, a preparation method of a cobalt-nickel bimetallic hydroxyphosphite rodlike crystal array film, which comprises the following steps:
1) dissolving nickel nitrate hexahydrate, cobalt nitrate hexahydrate and sodium hypophosphite into deionized water according to the molar concentration ratio of 1:1:2, wherein the total molar concentration of nickel ions and cobalt ions is 0.10-0.20 mol/L, and stirring to obtain a uniform solution;
2) adding N, N-dimethylacetamide into the solution, wherein the volume ratio of N, N-dimethylacetamide to deionized water is 1:1, and continuously stirring to obtain a uniform solution;
3) immersing the pre-cleaned activated carbon fiber in the solution obtained in the step 2) for 5 hours;
4) reacting the solution obtained in the step 3) and the activated carbon fiber together at the temperature of 140-160 ℃ for 10-20 h.
5) Naturally cooling the reaction kettle after the reaction in the step 4) to normal temperature, taking out the activated carbon fiber, repeatedly cleaning the activated carbon fiber with absolute ethyl alcohol and deionized water for three times, and drying the activated carbon fiber at the temperature of 60 ℃ for 8 hours to obtain compact and uniform M on the surface of the activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 (M = Ni + Co) rod-like crystal array film.
The activated carbon fiber is obtained by heat treatment of natural cotton fiber at 1000 ℃ for 1h in nitrogen atmosphere.
The invention has the beneficial effects that:
the invention adopts a mild, low-energy-consumption, nontoxic and safe hydrothermal method, takes the activated carbon fiber as a substrate and is based on crystal heterogeneous phaseNucleation and directional growth mechanism, combining the characteristics of hydrothermal reaction, starting from material selection, adding soluble nickel nitrate hexahydrate, cobalt nitrate hexahydrate and sodium hypophosphite, introducing a crystallization guiding agent N, N-dimethylacetamide, and comprehensively regulating and controlling various synthesis technical parameters to obtain compact and uniform M loaded on the surface of the activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 (M = Ni + Co) rod-like crystal array film. The invention takes the hydrothermal reaction principle as guidance, utilizes rich and developed pore structures on the surface of the activated carbon fiber, is beneficial to forming a crystal heterogeneous crystallization nucleation center, induces nickel ions, cobalt ions and hypophosphite ions to form a supersaturated micro-region in a pore environment for preferential nucleation, and takes the supersaturated micro-region as a substrate material for film growth; fully considering the thermodynamic influence factor of crystallization, setting proper reaction temperature and reaction time, and adopting hydrothermal reaction method to produce pure M on the surface of activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 (M = Ni + Co) rod-like crystal array film; the invention also takes the crystal growth mechanism as guidance to build the surface (Ni, Co) beneficial to the activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 A crystallization environment for heterogeneous crystallization and anisotropic growth of crystal comprises providing a large number of nucleation centers for crystallization by using the porous structure on the surface of activated carbon fiber, adjusting the crystal orientation and crystallization rate of hydroxyphosphite by using the complexation of N, N-dimethylacetamide, strengthening the anisotropic growth tendency of hydroxyphosphite, controlling the concentration of reactive ions and the reaction temperature, and accurately adjusting the crystal nucleation and growth rate to obtain M with rod-like shape and array arrangement which grows densely and uniformly on the surface of activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 (M = Ni + Co) film. The hydrothermal preparation method adopted by the invention has the advantages of short synthesis route, mildness, low energy consumption and rapidness, and the obtained thin film layer crystals have uniform size and uniform chemical components, thus being a synthesis method suitable for mass production. Such M 11 (HPO 3 ) 8 (OH) 6 The (M = Ni + Co) rod-shaped crystal array film and the substrate activated carbon fiber have good bonding strength, so that M 11 (HPO 3 ) 8 (OH) 6 Application of (M = Ni + Co) crystalThe properties are extended by the structural form of the composite material. In addition, the compact and uniform film form and the ordered rod-shaped array arrangement morphology are beneficial to M 11 (HPO 3 ) 8 (OH) 6 The (M = Ni + Co) crystal shows more stable and uniform performance and convenient application characteristics. M obtained by the invention 11 (HPO 3 ) 8 (OH) 6 The (M = Ni + Co) rod-shaped crystal array film can be applied to the fields of novel electrode materials, photocatalysis and the like, and is expected to be applied to the field of organic pollution decomposition.
Drawings
Figure 1 is the XRD pattern of the product obtained in example 1.
FIG. 2 is an electron micrograph of the product obtained in example 1.
FIG. 3 is an electron micrograph of the product obtained in example 2.
FIG. 4 is an electron micrograph of the product obtained in example 3.
Detailed Description
Invention M 11 (HPO 3 ) 8 (OH) 6 (M = Ni + Co) rod-like crystal array film, the M 11 (HPO 3 ) 8 (OH) 6 The (M = Ni + Co) rod-shaped crystals have a diameter of 100 nm to 1 μ M and are densely arranged in an array form to form a thin film.
Example 1:
0.2908 g of nickel nitrate hexahydrate, 0.2910 g of cobalt nitrate hexahydrate and 0.2120 g of sodium hypophosphite are dissolved in 10 ml of deionized water and stirred uniformly, wherein the molar concentration ratio of the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate and the sodium hypophosphite is 1:1:2, and the total molar concentration of nickel ions and cobalt ions is 0.20 mol/L. To the mixed solution was added 10 ml of N, N-dimethylacetamide, and the mixture was magnetically stirred to obtain a uniform solution. The natural cotton fiber is thermally treated for 1h at 1000 ℃ in nitrogen atmosphere to obtain the activated carbon fiber. The activated carbon fiber to be cleaned is immersed in the solution for 5 hours. The mixed solution and the activated carbon fiber react for 10 hours at the temperature of 160 ℃. After the reaction is finished, the reaction kettle is naturally cooled to normal temperature, the activated carbon fiber is taken out, the activated carbon fiber is repeatedly washed for three times by absolute ethyl alcohol and deionized water, and the bag is removedAdsorbing impurities such as ions and attachments on the surface, drying at 60 deg.C for 8 hr to obtain dense and uniform M on the surface of activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 (M = Ni + Co) rod-like crystal array film.
FIG. 1 is the XRD pattern of the product of example 1 showing the characteristic diffraction peaks and Ni of the crystalline material 11 (HPO 3 ) 8 (OH) 6 Standard XRD spectrum (JCPDS No 81-1065) and Co 11 (HPO 3 ) 8 (OH) 6 The standard XRD spectrum (JCPDS No 81-1064) is matched, and the crystal structure of the crystallized product is proved to be matched with that of Ni 11 (HPO 3 ) 8 (OH) 6 Or Co 11 (HPO 3 ) 8 (OH) 6 Where the cobalt and nickel atoms occupy lattice sites in substitutional form in the crystal structure. FIG. 2 is an electron micrograph of a product of example 1, in which M is formed on the surface of activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 The (M = Ni + Co) rod-shaped crystal array film has uniform rod size, the diameter of 500-800 nanometers, array arrangement perpendicular to the fiber surface and dense array arrangement.
Example 2:
0.2908 g of nickel nitrate hexahydrate, 0.2910 g of cobalt nitrate hexahydrate and 0.2120 g of sodium hypophosphite are dissolved in 20 ml of deionized water and stirred uniformly, wherein the molar concentration ratio of the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate and the sodium hypophosphite is 1:1:2, and the total molar concentration of nickel ions and cobalt ions is 0.10 mol/L. To the mixed solution was added 20 ml of N, N-dimethylacetamide, and the mixture was magnetically stirred to obtain a uniform solution. The natural cotton fiber is thermally treated for 1h at 1000 ℃ in nitrogen atmosphere to obtain the activated carbon fiber. The pre-cleaned activated carbon fiber was immersed in the above solution for 5 hours. The mixed solution and the activated carbon fiber react for 20 hours at the temperature of 140 ℃. After the reaction is finished, naturally cooling the reaction kettle to normal temperature, taking out the activated carbon fiber, repeatedly cleaning the activated carbon fiber for three times by absolute ethyl alcohol and deionized water to remove impurities including surface adsorbed ions, attachments and the like, drying the activated carbon fiber at 60 ℃ for 8 hours to obtain compact and uniform M on the surface of the activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 (M = Ni + Co) rod-like crystal array film.
FIG. 3 is an electron micrograph of a product of example 2, in which M is formed on the surface of activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 The (M = Ni + Co) rod-shaped crystal array film has uniform rod size, the diameter of 700 nanometers-1 micron, array arrangement vertical to the surface of the fiber and dense array arrangement.
Example 3:
0.5816 g of nickel nitrate hexahydrate, 0.5820 g of cobalt nitrate hexahydrate and 0.4140 g of sodium hypophosphite are dissolved in 30 ml of deionized water and stirred uniformly, wherein the molar concentration ratio of the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate and the sodium hypophosphite is 1:1:2, and the total molar concentration of nickel ions and cobalt ions is 0.13 mol/l. To the mixed solution was added 30 ml of N, N-dimethylacetamide, and stirred magnetically to obtain a uniform solution. And (3) carrying out heat treatment on the natural cotton fiber at 1000 ℃ for 1h in a nitrogen atmosphere to obtain the activated carbon fiber. The pre-cleaned activated carbon fiber was immersed in the above solution for 5 hours. The mixed solution and the activated carbon fiber react for 12 hours at the temperature of 150 ℃. After the reaction is finished, naturally cooling the reaction kettle to normal temperature, taking out the activated carbon fiber, repeatedly cleaning the activated carbon fiber for three times by absolute ethyl alcohol and deionized water to remove impurities including surface adsorbed ions, attachments and the like, drying the activated carbon fiber at 60 ℃ for 8 hours to obtain compact and uniform M on the surface of the activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 (M = Ni + Co) rod-like crystal array film.
FIG. 4 is an electron micrograph of a product of example 3, in which M is formed on the surface of activated carbon fiber 11 (HPO 3 ) 8 (OH) 6 The (M = Ni + Co) rod-shaped crystal array film has uniform rod size, the diameter of 100-500 nanometers, array arrangement vertical to the fiber surface and dense array arrangement.
Claims (3)
1. A method for preparing a cobalt-nickel bimetal hydroxyl phosphite rodlike crystal array film is characterized in that the film is 100 nanometers to 1 micrometer (Ni, Co) in diameter 11 (HPO 3 ) 8 (OH) 6 Rod-shaped crystalThe film is formed by densely arranging the bodies in an array form; the preparation method of the film comprises the following steps:
1) dissolving nickel nitrate hexahydrate, cobalt nitrate hexahydrate and sodium hypophosphite into deionized water according to the molar concentration ratio of 1:1:2, wherein the total molar concentration of nickel ions and cobalt ions is 0.10-0.20 mol/L, and stirring to obtain a uniform solution;
2) adding N, N-dimethylacetamide into the solution, wherein the volume ratio of N, N-dimethylacetamide to deionized water is 1:1, and continuously stirring to obtain a uniform solution;
3) immersing the pre-cleaned activated carbon fiber in the solution obtained in the step 2) for 5 hours;
4) reacting the solution obtained in the step 3) and the activated carbon fiber for 10-20 hours at the temperature of 140-160 ℃;
5) naturally cooling the reaction kettle after the reaction in the step 4) to normal temperature, taking out the activated carbon fiber, repeatedly cleaning the activated carbon fiber for three times by absolute ethyl alcohol and deionized water, and drying the activated carbon fiber at the temperature of 60 ℃ for 8 hours to obtain a compact and uniform cobalt-nickel bimetallic hydroxyl phosphite rodlike crystal array film on the surface of the activated carbon fiber.
2. The method for preparing a cobalt-nickel bi-metal hydroxy phosphite rod-like crystal array film according to claim 1, wherein the method comprises the following steps: the activated carbon fiber is obtained by heat treatment of natural cotton fiber at 1000 ℃ for 1h in nitrogen atmosphere.
3. The film prepared by the method for preparing a cobalt-nickel bimetallic hydroxyphosphite rodlike crystal array film according to claim 1 or 2, wherein the method comprises the following steps: (Ni, Co) 11 (HPO 3 ) 8 (OH) 6 The diameter of the rod-shaped crystal is 100 nanometers to 1 micron, and the rod-shaped crystal is densely arranged in an array form to form a film.
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| CN104088016A (en) * | 2014-07-03 | 2014-10-08 | 浙江理工大学 | One-dimensional NiCo2S4 crystal array on surface of activated carbon fiber and preparation method of one-dimensional NiCo2S4 crystal array |
| CN108538611A (en) * | 2018-02-23 | 2018-09-14 | 中国石油大学(北京) | A kind of nano-chip arrays cobalt acid nickel-carbon composite and its preparation method and application |
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| CN104088016A (en) * | 2014-07-03 | 2014-10-08 | 浙江理工大学 | One-dimensional NiCo2S4 crystal array on surface of activated carbon fiber and preparation method of one-dimensional NiCo2S4 crystal array |
| CN108538611A (en) * | 2018-02-23 | 2018-09-14 | 中国石油大学(北京) | A kind of nano-chip arrays cobalt acid nickel-carbon composite and its preparation method and application |
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| 廖开明等."梭状(CoxNi1-x)11(HPO3)8(OH)6(x≈0.25)微晶的水热制备与表征".《中国化学会第26届学术年会纳米化学分会场论文集》.2008, * |
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