CN1289405C - Wet chemical process of preparing low-dimensional nano nickel sulfide crystal - Google Patents
Wet chemical process of preparing low-dimensional nano nickel sulfide crystal Download PDFInfo
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- CN1289405C CN1289405C CN 03151097 CN03151097A CN1289405C CN 1289405 C CN1289405 C CN 1289405C CN 03151097 CN03151097 CN 03151097 CN 03151097 A CN03151097 A CN 03151097A CN 1289405 C CN1289405 C CN 1289405C
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Abstract
The present invention provides a wet chemical preparation method for low dimensional nickel sulfide nanometer crystals. The present invention is mainly characterized in that water-in-oil type microemulsion is used as reaction media, inorganic nickel salt, carbon disulfide and urea are used as reactants and synthesized into one-dimensional nickel sulfide nanometer needles, one-dimensional nickel sulfide nanometer tubes or two-dimensional nanometer thin layer sheet crystals through direct hydrothermal treatment in a reaction kettle. The water-in-oil type microemulsion comprises two systems, namely 'cetyl trimethyl ammonium bromide(CTAB)/ n-pentanol/ hexane/ water' and 'TritonX-100/isopropanol / cyclohexane / water'. the hydrothermal treatment is carried out for 5 to 48 hours under the temperature of 120 DEG C to 200 DEG C. each of the obtained nanometer thin layer sheets has a thickness of 2 to 10 nm, the diameter of each of the nanometer needles or the nanometer tubes is from 5 nm to 200 nm, and the length of each of the nanometer needles or the nanometer tubes is from 50 nm to 2000 nm. That the patterns of the products are controllable, and the components of the products are adjustable can be realized by changing reaction time, reactant concentration, reactant compounding ratio and reaction medium types, or adding dodecyl mercaptan. The method has the characteristics that the patterns of products are controllable, the components of products are adjustable, and the technology and the equipment are simple.
Description
Technical field
The present invention relates to the wet chemical preparation method of nickelous sulfide 1-dimention nano pin, pipe or two-dimensional nano thin layer platelet, the metal nanometer material field.
Background technology
Nano material is meant the material that has at least one dimension to be in 1～100nm on yardstick, and the branch of zero dimension, a peacekeeping two dimension is arranged.Than block materials, nano material has performances such as excellent mechanics, electricity, optics, catalysis, and the huge applications prospect is arranged, and becomes material science active research direction the most in recent years, belongs to the forward position of Materials science.Many physical and chemical performances and scientific phenomena all have substantial connection with the yardstick and the dimension of material, and therefore, the controlledly synthesis of the size of material, dimension and pattern becomes one of main contents of nano materials research.In recent years, the quantum dot of the one-dimensional nano line of metal oxide, metallic sulfide and metal (rod, pin), two-dimensional nano thin slice and zero dimension all has the lot of documents report.
Metallic sulfide is the important semiconductor material of a class, has excellent electric property, luminescent properties and catalytic performance.As important a member of metallic sulfide, nickelous sulfide has many important performances and industrial application.For example, there is α-βXiang Bian in nickelous sulfide and follows volume change about 4%, and the steady nickelous sulfide that is situated between can be used as effective transformation toughening agent of semiconductor material; Nickelous sulfide has excellent catalytic performance, can be used as the catalyzer of hydrogenating desulfurization and hydrodenitrification process, especially the removing of sulphur and sulfocompound in the oil and natural gas.In addition, nickelous sulfide also can be used as photronic coated material.The prior synthesizing method of nickelous sulfide is metal nickel powder and elemental sulfur reaction at high temperature in the sealing boiler tube, and there is significant disadvantages in this method: one, and the fusing point of sulphur is low, volatile, and the composition of product is difficult to control; Its two, pyroprocessing always obtains thing phase stable on the thermodynamics, and is difficult to obtain being situated between steady phase.In recent years, the low temperature liquid phase of nickelous sulfide is synthetic has caused great interest.People such as J.Grau (J.Am.Ceram.Soc.Vol.80 (1997) No.4pp.941-951) have reported that nickel chloride aqueous solution and thioacetamide, urea react generation NiS down at 70～90 ℃
1.03, but the particle diameter of product is in micron dimension.People such as Y.U.Jeong (Inorg.Chem.Vol.40 (2001) No.1 pp.73-77) have reported that nickelous chloride and V-Brite B react synthetic crystallization Ni in room temperature water solution
3S
2, Ni
3S
4And weak crystalline nonstoichiometry product Ni
yS
xPeople such as B.Xie (Chem.Lett.Vol.31 (2002) pp.254-255) have reported that with nickelous chloride and Sulfothiorine be raw material, at C
17H
33(140 ℃) have synthesized the NiS nano whisker under the auxiliary thermal and hydric environment of COOK.People such as X.Jiang (Adv.Mater.Vol.13 (2001) No.16pp.1278-1281) have reported with the nickelous chloride to be that the nickel source has made sulfuration nickel dam volume structure in strong aqua-dithiocarbonic anhydride system, but diameter very big (0.5～1.0 μ m).People such as S.-H.Yu (Adv.Funct.Mater.Vol.12 (2002) No.4pp.277-285) have reported that be raw material with nickel block (or nickelous nitrate) with elementary sulfur, have synthesized the not nickelous sulfide of jljl phase in quadrol, water, ethanol, acetone, pyridine equal solvent.People such as R.D.Tilley (J.Phys.Chem.BVol.106 (2002) No.42pp.10895-10901) have reported with H
2S/H
2Mixed gas vulcanization has prepared the not nanometer nickel sulfide particle of jljl phase attached to the nickel ion on the graphitized carbon black.People such as Y.Hu (Adv.Mater.Vol.15 (2003) No.9pp.726-729) have reported the synthetic of nickelous sulfide micron ball.But the pattern of above-mentioned preparation method's products therefrom is single, uncontrollable, and size is bigger, the tightness system that also needs strictness that has, technology, equipment complexity.The present invention utilizes cheap chemical reagent to be raw material, is reaction vessel with easy reactor, has prepared 1-dimention nano pin, pipe and the two-dimensional nano thin layer platelet of nickelous sulfide.Suitably conditioned reaction condition and reactant ratio can obtain the product of heterogeneity and different-shape.Preparation method provided by the invention has controllable product shape, composition is adjustable, technology and the simple advantage of equipment.
Summary of the invention
The object of the present invention is to provide a kind of wet chemical synthesis of low-dimensional nanometer nickel sulfide crystalline substance, be characterized in: controllable product shape, composition is adjustable, technology and equipment are simple.
The wet chemical preparation method of described low-dimensional nanometer nickel sulfide crystalline substance, it is characterized in that: be reaction medium with the water in oil microemulsion, with inorganic nickel, dithiocarbonic anhydride, urea is reactant, in reactor, carry out hydrothermal treatment consists, gained suspension makes nickelous sulfide 1-dimention nano pin, pipe or two-dimensional nano thin layer platelet through underpressure distillation, washing, drying treatment.The wet chemical preparation method concrete steps that this shows low-dimensional nanometer nickel sulfide crystalline substance provided by the invention can be divided into for two steps:
The first step: the preparation of water in oil microemulsion; Second step: hydrothermal treatment consists.Now details are as follows respectively:
1, the preparation of water in oil microemulsion
Earlier inorganic nickel is dissolved in distilled water and is made into Ni
2+Concentration is the aqueous solution of 0.01～0.5mol/L, makes the water of microemulsion, and mole such as dithiocarbonic anhydride and urea adds its add-on and Ni
2+Mol ratio be 1～6.In " cetyl trimethylammonium bromide (CTAB)/Pentyl alcohol/normal hexane/water " reaction medium: CTAB is a tensio-active agent, and its concentration is 0.1mol/L; Pentyl alcohol is a cosurfactant, and the mol ratio of cosurfactant and tensio-active agent is 8.7; Normal hexane is an oil phase; The inorganic nickel aqueous solution is water, and the mol ratio W of water and tensio-active agent is 10～60.Earlier CTAB and urea are joined in the mixed solution of the inorganic nickel aqueous solution, Pentyl alcohol, normal hexane, magnetic agitation 10～15 minutes, then supersound process promptly got translucent emulsion in 10～15 minutes, again will this translucent emulsion place heat treated in 80～100 ℃ the baking oven got final product in 3～5 minutes the microemulsion of optical transparency, add dithiocarbonic anhydride (or adding Dodecyl Mercaptan simultaneously) and the magnetic agitation reactor of can packing in 5 minutes.In " Triton X-100 (Triton X-100)/Virahol/hexanaphthene/water " reaction medium: Triton X-100, Virahol, hexanaphthene, the inorganic nickel aqueous solution are respectively tensio-active agent, cosurfactant, oil phase and water, and its volume ratio is 6: 7.5: 30: 30.Triton X-100, urea are joined in the mixing solutions of the inorganic nickel aqueous solution, Virahol, hexanaphthene, magnetic agitation 10～15 minutes, got final product in ultrasonic then 10～15 minutes the microemulsion of clear, add dithiocarbonic anhydride and magnetic agitation again and can adorn still in 5 minutes.Described inorganic nickel be in nickelous nitrate, nickelous chloride and the nickel acetate a kind of, two kinds or three kinds.
2, hydrothermal treatment consists
The microemulsion of preparation is packed into and had in the teflon-lined reactor, and the compactedness of microemulsion is 70～80%, seal tightly then to naturally cool to room temperature after being incubated 5～48 hours under 120～200 ℃ the temperature.The grey black suspension of collecting temperature be lower than 60 ℃, vacuum tightness less than the condition of 0.1MPa under underpressure distillation to remove volatile organic solvent, then successively through acetone, water, absolute ethanol washing throw out, remove wherein sulphur or impurity such as other organism, tensio-active agent, then washed product is placed the moisture eliminator drying at room temperature.
By control soaking time, microemulsion system and parameter, Ni
2+Concentration or add Dodecyl Mercaptan can make the nanometer nickel sulfide crystalline substance of different-shape: the nanoneedle of different diameter or pipe, the nano thin-layer platelet of different thickness, monodispersed plate let, nano stick crystal.By control reactant Ni
2+Can obtain the product of heterogeneity: Ni with the ratio of dithiocarbonic anhydride
7S
6, millerite NiS, six side's phase NiS
1.03, Ni
3S
4, NiS
2
Reaction process is as follows:
The thickness of gained nanometer thin synusia is 2～10nm, and the diameter of nanoneedle or pipe is 5～200nm, and length is 50～2000nm.
Description of drawings
Fig. 1 is a reaction medium with " CTAB/ Pentyl alcohol/normal hexane/water ", [Ni
2+]=0.1mol/L, W=30, the X-ray diffracting spectrum of 130 ℃ of hydro-thermal products therefroms: (a) Ni
2+: CS
2: CO (NH
2)
2=1: 1: 1,15 hours; (b) Ni
2+: CS
2: CO (NH
2)
2=1: 3: 3,5 hours; (c) Ni
2+: CS
2: CO (NH
2)
2=1: 3: 3,15 hours; (d) Ni
2+: CS
2: CO (NH
2)
2=6: 6: 6,15 hours.●-NiS
1.03Zero-millerite NiS; ▼-Ni
7S
6■-S;-Ni
3S
4▲-NiS
2
Fig. 2 is a reaction medium with " CTAB/ Pentyl alcohol/normal hexane/water ", [Ni
2+]=0.1mol/L, W=30, Ni
2+: CS
2: CO (NH
2)
2=1: 3: 3, the hydro-thermal (a) 5 hours and (b) transmission electron microscope photo of 15 hours gained samples.
Fig. 3 is a reaction medium with " CTAB/ Pentyl alcohol/normal hexane/water ", [Ni
2+]=0.1mol/L, Ni
2+: CS
2: CO (NH
2)
2=1: 3: 3, the transmission electron microscope photo of 15 hours gained samples of 130 ℃ of following hydro-thermals: (a) W=15, (b) W=45.
Fig. 4 is a reaction medium with " CTAB/ Pentyl alcohol/normal hexane/water ", [Ni
2+]=0.1mol/L, W=30, Ni
2+: CS
2: CO (NH
2)
2=1: 3: 3, add the 1.0mL Dodecyl Mercaptan, the transmission electron microscope photo of 15 hours gained samples of 130 ℃ of following hydro-thermals.
Fig. 5 is a reaction medium with " Triton X-100/ Virahol/hexanaphthene/water ", [Ni
2+]=0.1mol/L, Ni
2+: CS
2: CO (NH
2)
2=1: 3: 3, the transmission electron microscope photo of 15 hours gained samples of 130 ℃ of following hydro-thermals.
Fig. 6 is a reaction medium with " CTAB/ Pentyl alcohol/normal hexane/water ", [Ni
2+]=0.01mol/L, W=30, Ni
2+: CS
2: CO (NH
2)
2=1: 3: 3, the transmission electron microscope photo of 5 hours gained samples of 130 ℃ of following hydro-thermals.
Embodiment
Embodiment 1:
2.73g CTAB and 0.07g urea are dissolved in 7.0mL Pentyl alcohol and 4.0mL nickel salt aqueous solution (W=30, [Ni
2+In the mixed solution of]=0.1mol/L), add normal hexane then and be about 75mL until cumulative volume; This mixed solution respectively through magnetic agitation, supersound process after 15 minutes about 100 ℃ heating promptly got as clear as crystal microemulsion in 5 minutes; The dithiocarbonic anhydride that adds 0.07mL again, i.e. Ni
2+: CS
2: CO (NH
2)
2=1: 3: 3, magnetic agitation was packed into after 5 minutes in the reactor, naturally cools to room temperature after being incubated 5 and 15 hours respectively under 130 ℃.The grey black suspension of gained with after removing volatile organic solvent, successively through acetone, water, absolute ethanol washing, and then places the moisture eliminator drying at room temperature to get product 60 ℃ of following underpressure distillation.Fig. 1 (b) and Fig. 1 (c) are respectively the x-ray diffraction patterns of hydro-thermal 5 hours and 15 hours gained.As seen from the figure, 5 hours principal crystalline phase of hydro-thermal is six side's phase NiS
1.03, the principal crystalline phase of 15 hours products therefroms of hydro-thermal is six side's phase NiS
1.03With water chestnut side's mixture of millerite NiS mutually.Fig. 2 (a) and Fig. 2 (b) are respectively and 15 hours gained transmission electron microscope photos.5 hours product of hydro-thermal is two-dimentional thin-layer tablet structure, and its thickness is less than 10nm; 15 hours product of hydro-thermal is an acicular structure, and its diameter is 50～200nm, and length surpasses 1.0 μ m.
Embodiment 2:
2.73g CTAB and 0.03g (or 0.15g) urea are dissolved in 7.0mL Pentyl alcohol and 4.0mL nickel salt aqueous solution (W=30, [Ni
2+In the mixed solution of]=0.1mol/L), add normal hexane then and be about 75mL until cumulative volume; This mixed solution respectively through magnetic agitation, supersound process after 15 minutes about 100 ℃ heating promptly got as clear as crystal microemulsion in 5 minutes; The dithiocarbonic anhydride that adds 0.03mL (or 0.15mL) again, i.e. Ni
2+: CS
2: CO (NH
2)
2=1: 1: 1 (or Ni
2+: CS
2: CO (NH
2)
2=1: 6: 6), magnetic agitation is packed into after 5 minutes in the reactor, naturally cools to room temperature 130 ℃ of insulations after 15 hours.
The grey black suspension of gained with after removing volatile organic solvent, successively through acetone, water, absolute ethanol washing, and then places the moisture eliminator drying at room temperature to get product 60 ℃ of following underpressure distillation.Fig. 1 (a) and Fig. 1 (d) are respectively Ni
2+: CS
2: CO (NH
2)
2=1: 1: 1 and Ni
2+: CS
2: CO (NH
2)
2=1: the x-ray diffraction pattern of 6: 6 o'clock products therefroms.As seen from the figure, work as Ni
2+: CS
2: CO (NH
2)
2=1: 1: 1 o'clock products therefrom is Ni
7S
6With NiS
1.03Mixture, and work as Ni
2+: CS
2: CO (NH
2)
2=6: 6: 6 o'clock products therefroms are Ni
3S
4With NiS
2Mixture.
Embodiment 3:
2.73g CTAB and 0.035g (or 0.105g) urea are dissolved in 7.0mL Pentyl alcohol and 2.0mL (or 6.0mL) nickel salt aqueous solution (W=15 (or W=45), [Ni
2+In the mixed solution of]=0.1mol/L), add normal hexane then and be about 75mL until cumulative volume; This mixed solution respectively through magnetic agitation, supersound process after 15 minutes about 100 ℃ heating promptly got as clear as crystal microemulsion in 5 minutes; The dithiocarbonic anhydride that adds 0.035mL (or 0.105mL) again, i.e. Ni
2+: CS
2: CO (NH
2)
2=1: 3: 3, magnetic agitation was packed into after 5 minutes in the reactor, 130 ℃ down insulation naturally cool to room temperature after 15 hours.The grey black suspension of gained with after removing volatile organic solvent, is placed on that drying at room temperature gets product in the moisture eliminator 60 ℃ of following underpressure distillation successively through acetone, water, absolute ethanol washing.Products therefrom transmission electron microscope photo when Fig. 3 (a) and Fig. 3 (b) are W=15 and W=45 respectively.As shown in the figure, products therefrom is the needle-like pattern of diameter less than 10nm, the about 100nm of length during W=15; Products therefrom is that platelet and the diameter irregular, that thickness is bigger surpasses the excellent brilliant of 100nm during W=45.
Embodiment 4:
2.73g CTAB and 0.07g urea are dissolved in 7.0mL Pentyl alcohol and 4.0mL nickel salt aqueous solution (W=30, [Ni
2+In the mixed solution of]=0.1mol/L), add normal hexane then and be about 75mL until cumulative volume.This mixed solution respectively through magnetic agitation, supersound process after 15 minutes about 100 ℃ heating promptly got as clear as crystal microemulsion in 5 minutes, the dithiocarbonic anhydride and the 1.0mL Dodecyl Mercaptan that add 0.07mL again, magnetic agitation is packed into after 5 minutes in the reactor, 130 ℃ down insulation naturally cool to room temperature after 15 hours.The grey black suspension of gained with after removing volatile organic solvent, is placed on that drying at room temperature gets product in the moisture eliminator 60 ℃ of following underpressure distillation successively through acetone, water, absolute ethanol washing.Fig. 4 is the transmission electron microscope photo of product, as seen from the figure, and the erose single sheet structure of disperseing of product.
Embodiment 5:
With 7.5mL Triton X-100 and 6.0mL nickel salt aqueous solution ([Ni
2+]=0.1mol/L) joins the 30mL Virahol, adds 30mL hexanaphthene and 0.15g urea again, can get the microemulsion of clear respectively in 15 minutes through magnetic agitation, supersound process, adds dithiocarbonic anhydride 0.15mL (Ni again
2+: CS
2: CO (NH
2)
2=1: 3: 3), the magnetic agitation reactor of promptly packing in 5 minutes.130 ℃ down insulation naturally cool to room temperature after 15 hours and promptly get grey black suspension, after volatile organic solvent is removed in 60 ℃ of following underpressure distillation, be placed on through acetone, water, absolute ethanol washing successively again that drying at room temperature gets product in the moisture eliminator.Fig. 5 is the transmission electron microscope photo of product, and as seen from the figure, product is smooth thicker synusia structure of unfolding, and the acicular structure of non-crimping.
Embodiment 6:
2.73g CTAB and 0.01g urea are dissolved in 7.0mL Pentyl alcohol and 4.0mL nickel salt aqueous solution (W=30, [Ni
2+In the mixed solution of]=0.01mol/L), add normal hexane then and be about 75mL until cumulative volume.This mixed solution respectively through magnetic agitation, supersound process after 15 minutes about 100 ℃ heating promptly got as clear as crystal microemulsion in 5 minutes, the dithiocarbonic anhydride that adds 0.01mL again, magnetic agitation is packed into after 5 minutes in the reactor, 130 ℃ down insulation naturally cool to room temperature after 15 hours.The grey black suspension of gained with after removing volatile organic solvent, is placed on that drying at room temperature gets product in the moisture eliminator 60 ℃ of following underpressure distillation successively through acetone, water, absolute ethanol washing.Fig. 6 is the transmission electron microscope photo of product.As shown in the figure, product is the two-dimentional laminate structure of very thin thickness (less than 5nm).
Claims (5)
1. the wet chemical preparation method of low-dimensional nanometer nickel sulfide crystalline substance, it is characterized in that: be reaction medium with the water in oil microemulsion, with inorganic nickel, dithiocarbonic anhydride, urea is reactant, in reactor, carry out hydrothermal treatment consists, gained suspension makes nickelous sulfide 1-dimention nano pin, pipe or two-dimensional nano thin layer platelet through underpressure distillation, washing, drying treatment;
Described water in oil microemulsion is cetyl trimethylammonium bromide/Pentyl alcohol/normal hexane/water or Triton X-100/Virahol/hexanaphthene/water; Wherein the preparation of cetyl trimethylammonium bromide/Pentyl alcohol/normal hexane/water is to be tensio-active agent with the cetyl trimethylammonium bromide, its concentration is 0.1mol/L, with the Pentyl alcohol is cosurfactant, the mol ratio of cosurfactant and tensio-active agent is 8.7, with the normal hexane is oil phase, the inorganic nickel aqueous solution is water, and the mol ratio of water and tensio-active agent is 10～60; The preparation of Triton X-100/Virahol/hexanaphthene/water is to be tensio-active agent with the Triton X-100, with the Virahol is cosurfactant, with the hexanaphthene is oil phase, with the inorganic nickel aqueous solution is water, and the volume ratio of Triton X-100, Virahol, hexanaphthene, the inorganic nickel aqueous solution is 6: 7.5: 30: 30;
Described inorganic nickel Ni
2+Concentration is 0.01-0.5mol/L; Mole such as described dithiocarbonic anhydride and urea adds add-on and Ni
2+Mol ratio be 1-6; Described hydrothermal treatment consists is under 120-200 ℃, is incubated 5-48 hour.
2. by the preparation method of the wet-chemical of the described low-dimensional nanometer nickel sulfide of claim 1 crystalline substance, it is characterized in that: the inorganic nickel aqueous solution be by in nickelous nitrate, nickelous chloride and the nickel acetate a kind of, two or three be dissolved in distilled water and make.
3. by the wet chemical preparation method of the described low-dimensional nanometer nickel sulfide of claim 1 crystalline substance, it is characterized in that: reactor is stainless steel and polytetrafluoroethyllining lining is arranged, the compactedness 70～80% of microemulsion.
4. by the wet chemical preparation method of the described low-dimensional nanometer nickel sulfide of claim 1 crystalline substance, it is characterized in that: the service temperature of underpressure distillation is lower than 60 ℃, and vacuum tightness is less than 0.1MPa.
5. by the wet chemical preparation method of the described low-dimensional nanometer nickel sulfide of claim 1 crystalline substance, the thickness that it is characterized in that obtained nanometer thin synusia is 2-10nm, and the diameter of nanoneedle or pipe is 5-200nm, and length is 50～2000nm.
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