CN103950989B - A kind of FeS nano material and preparation method - Google Patents
A kind of FeS nano material and preparation method Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 28
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007772 electrode material Substances 0.000 claims abstract description 23
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 14
- 239000013543 active substance Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000012456 homogeneous solution Substances 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 21
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- ICAIHGOJRDCMHE-UHFFFAOYSA-O ammonium cyanide Chemical compound [NH4+].N#[C-] ICAIHGOJRDCMHE-UHFFFAOYSA-O 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229960003067 cystine Drugs 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 239000003990 capacitor Substances 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 22
- 238000001291 vacuum drying Methods 0.000 description 15
- 238000013019 agitation Methods 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229960001149 dopamine hydrochloride Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Compounds Of Iron (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention discloses a kind of FeS nano material and preparation method, and FeS nano material, has sheet structure, and the thickness of sheet is 20～100 nanometers, and the length of sheet is 0.2～5 micron. Preparation method comprises: yellow prussiate of potash and sodium sulphite are dissolved in water by (1), then add tensio-active agent, mix; (2) react 3～50 hours under 140～220 DEG C of hydrothermal conditions, naturally cool to room temperature; (3) by the product obtained through centrifugal, wash, be drying to obtain sheet FeS capacitor electrode material. The present invention is simple, efficient, is applicable to scale operation, and prepared super capacitor material has bigger specific surface area and higher ratio capacitance, has potential using value.
Description
Technical field
The present invention relates to the preparation method of micro Nano material, in particular to the preparation method of a kind of FeS nano material, belong to technical field of new material preparation.
Background technology
Iron sulfuret is as a kind of important functional materials, and its structure and Graphene are similar, has good plasticity and lubricity, it is possible to be applied to manufacture solid lubricant; It has good activity, it is possible to for fields such as Industrial Waste Water Treatments; In addition, Iron sulfuret is also used as electrode materials, is applied in two molten salt lithium batteries. Therefore, the controlled synthesis of Iron sulfuret and scale operation cause and pay close attention to widely.
The preparation of Iron sulfuret mainly adopts high temperature direct synthesis technique and liquid phase synthesizing method. Such as: Wang Yunru (" Wuhan Institute of Chemical Technology's journal ", the 5th phase in 2005) etc., taking iron powder and sulphur as raw material, react 24 hours at 1000 DEG C in the airtight silica tube of high vacuum, obtain the Iron sulfuret powder body of fragility. But, the method can sinter in calcination process, the carrying out of impact reaction.
Chinese patent 200710099634.7 " preparation method of a kind of FeS ", on November 6 2008 publication date, reports one and adopts ferrous sulfate and carbon dust to be raw material, and the mode of segmented high-temperature calcining obtains Iron sulfuret nano material. But the method is loaded down with trivial details, and needing nitrogen protection to calcine, operation is loaded down with trivial details, cost is higher.
Chinese patent 200910094242.0, " synthetic method of a kind of active ferrous sulphide and application thereof ", report August 19 2009 publication date a kind of taking iron powder and SULPHUR POWDER as raw material, then add water moistening, in reaction vessel, heated and stirred prepares the method for Iron sulfuret, but product rate only has an appointment 75%.
Bao (Chem.Eur.J., 2009,15,4321-4326) etc. taking ferrous ammonium sulphate, dopamine hydrochloride, sodium sulphite as raw material, although the method adopting direct liquid-phase precipitation obtains the sheet structure of Iron sulfuret, but the product prepared by the method is mixed phase, and employ the higher dopamine hydrochloride of cost.
Chen Fan (" Fudan University's journal ", the 3rd phase in 2003) etc., taking ferrous ammonium sulphate, Trisodium Citrate, thioacetamide as raw material, obtain nano level Iron sulfuret nanometer crystalline substance under 70 DEG C of nitrogen protections. In addition, document also reports the method such as microemulsion method, electric glow discharge method of employing and prepares high-purity Iron sulfuret, but due to cost height, production capacity low, extensive promotion and application could not be obtained.
Summary of the invention
For the deficiencies in the prior art, the present invention provides the FeS nano material of a kind of sheet structure, and this invention has preparation and is simply easy to large-scale production.
Present invention also offers the preparation method of a kind of FeS nano material.
A kind of FeS nano material, has sheet structure, and the thickness of sheet is 20��100 nanometers, and the length of sheet is 0.2��5 micron.
The application of FeS nano material on electrode materials; Described electrode materials refers to electrode material for super capacitor.
A preparation method for FeS nano material, comprises the following steps:
(1) ferrous salt and sulfocompound are dissolved in water, add tensio-active agent, stir evenly;
(2) homogeneous solution prepared by step (1) being put into autoclave, the compactedness of reactor is 50��80%, after hydro-thermal reaction, naturally cools to room temperature;
(3) by product centrifugation, washing, after dry, sheet FeS electrode materials is namely obtained.
In step (1), the concentration of iron ion is 0.01��1.0mol/L, and sulfonium ion concentration is 0.005��2.0mol/L, and the concentration of tensio-active agent is 0��4.0mol/L;
Ferrous salt described in step (1) be selected from ferrous sulfate, iron protochloride, ferrous ammonium sulphate, ferrous ammonium cyanide, yellow prussiate of potash one or more;
Sulfocompound described in step (1) be selected from thiocarbamide, thiosemicarbazide, Thiovanic acid, thioacetamide, CYSTINE, Cys, sodium sulphite one or more;
Tensio-active agent described in step (1) is one or more in polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), sodium laurylsulfonate (SDS), Sodium dodecylbenzene sulfonate (SDBS), cetyl trimethylammonium bromide (CTAB), palmityl trimethyl ammonium chloride (CTAC);
In step (2), hydro-thermal reaction Heating temperature is 140��220 DEG C, and the reaction times is 3��50 hours;
In step (2), the compactedness of reactor is 50��80%;
In step (3), washing is for washing with deionized water and alcohol solvent, and drying temperature is 30-80 DEG C, and the time is 5-10 hour.
The present invention is dissolved in water by the ferrous salt of solubility and Containing Sulfur thing, hydrothermal treatment consists at a certain temperature, final formation sheet FeS structure, and can be made into electrode material for super capacitor. At a certain temperature, the Fe that the ferrous salt of solubility discharges2+With the S that sulfide discharges2-In conjunction with, generate nanometer Fe S material. In this invention preparation method, control Fe2+And S2-Release rate be crucial, therefore, it is desired to ferrous salt discharges Fe2+Speed and sulfide discharge S2-Speed to be had certain matching relationship. On the one hand, when ferrous salt discharges Fe2+Speed very fast time, it is necessary to sulfide discharges S2-Speed also wants fast, otherwise the oxide byproducts just having iron in product exists; On the other hand, when ferrous salt discharges Fe2+Speed slower time, sulfide is discharged S2-Speed to be tried one's best soon, products therefrom is pure nanometer Fe S material.
Compared with prior art, reaction conditions is gentle, and made nanometer Fe S material has laminated structure, and product rate height, technique are simple in the present invention.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction pattern of embodiment 1 gained material;
Fig. 2 is scanning electronic microscope (SEM) photo of embodiment 1 gained material;
Fig. 3 is that embodiment 1 gained material sweeps speed figure when making electrode of super capacitor;
Fig. 4 is discharge and recharge figure under the different electric current of embodiment 1 gained material system.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 30��100 nanometers, diameter 0.2��5 micron.
A preparation method for FeS nano material, comprises the following steps:
(1) yellow prussiate of potash and sodium sulphite are dissolved in water and form homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 10 hours under 200 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 60 DEG C, vacuum-drying 6 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of yellow prussiate of potash is 0.05mol/L, and the concentration of sodium sulphite is 0.05mol/L; In step (2), the compactedness of reactor is 80%.
With Japan's Shimadzu XRD-6000 type x-ray powder diffraction instrument, nanometer Fe S material prepare by embodiment 1 being carried out Discriminating materials, as shown in fig. 1, it index can turn to the FeS structure of cubic phase, illustrates that the sample obtained is very pure, degree of crystallinity is very high; As shown in Figure 2, product characterizes through SEM, and result shows that the product obtained is the sheet structure of a dimension, and the size of sheet structure is at about 1.8 ��m.
Embodiment 1 is obtained nanometer Fe S material, carbon black, tackiness agent size mixing in the ratio of 8:1:1, be then coated in the surface of nickel foam, be placed in loft drier freeze-day with constant temperature, namely obtained pseudocapacitors electrode. Electro-chemical test carries out on CHI660D (Shanghai Chen Hua instrument company limited) electrochemical workstation, the work three-electrode system of electrode of the nickel foam that reference electrode made by mercurous chloride electrode, platinum wire electrode does supporting electrode, FeS modifies is adopted to test, if Fig. 3 is the cyclic voltammogram that its difference sweeps speed, along with the increase sweeping speed, electric current increases. Fig. 4 is the discharge and recharge figure under its different electric current, is 3A g in current density-1��4A��g-1��5A��g-1��6A��g-1��8A��g-1Time, calculate its electrical capacity according to formula C=(I �� �� t)/(m �� �� V) and it is respectively 243F g-1��190F��g-1��150F��g-1��112.5F��g-1��82F��g-1. As seen from Figure 4, it has good charge-discharge performance, will have certain potential using value in ultracapacitor field.
Embodiment 2
One FeS kind nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 20��60 nanometers, diameter 0.2��4.0 micron.
A preparation method for FeS nano material, comprises the following steps:
(1) being dissolved in water by ferrous ammonium cyanide and sodium sulphite, add a certain amount of polyvinylpyrrolidone, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 3 hours under 220 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 40 DEG C, vacuum-drying 8 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of yellow prussiate of potash is 0.1mol/L, and the concentration of sodium sulphite is 0.1mol/L, and the concentration of polyvinylpyrrolidone is 2.0mol/L; In step (2), the compactedness of reactor is 80%.
Embodiment 3
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 20��80 nanometers, diameter 0.3��4.5 micron.
A preparation method for FeS nano material, step comprises:
(1) being dissolved in water by ferrous sulfate and sodium sulphite, add a certain amount of polyvinyl alcohol, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 10 hours under 140 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 30 DEG C, vacuum-drying 10 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of ferrous sulfate is 1.0mol/L, and the concentration of sodium sulphite is 1.0mol/L, and the concentration of polyvinyl alcohol is 4.0mol/; In step (2), the compactedness of reactor is 80%.
Embodiment 4
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 20��40 nanometers, diameter 0.3��1.4 micron.
A preparation method for FeS nano material, step comprises:
(1) being dissolved in water by ferrous ammonium sulphate and sodium sulphite, add a certain amount of sodium laurylsulfonate, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 24 hours under 180 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 80 DEG C, vacuum-drying 5 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of ferrous ammonium sulphate is 0.5mol/L, and the concentration of sodium sulphite is 0.5mol/L, and the concentration of sodium laurylsulfonate is 0.5mol/L; In step (2), the compactedness of reactor is 60%.
Embodiment 5
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 20��50 nanometers, diameter 0.3��1.0 micron.
A preparation method for FeS nano material, step comprises:
(1) being dissolved in water by iron protochloride and sodium sulphite, add a certain amount of Sodium dodecylbenzene sulfonate, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 10 hours under 160 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 70 DEG C, vacuum-drying 4 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of iron protochloride is 0.01mol/L, and the concentration of sodium sulphite is 0.005mol/L, and the concentration of Sodium dodecylbenzene sulfonate is 0.05mol/L; In step (2), the compactedness of reactor is 80%.
Embodiment 6
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 40��90 nanometers, diameter 0.4��4.6 micron.
A preparation method for FeS nano material, step comprises:
(1) being dissolved in water by yellow prussiate of potash and thiocarbamide, add a certain amount of polyvinylpyrrolidone, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 20 hours under 200 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 60 DEG C, vacuum-drying 6 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of yellow prussiate of potash is 0.05mol/L, and the concentration of thiocarbamide is 2.0mol/L, and the concentration of polyvinylpyrrolidone is 1.0mol/L; In step (2), the compactedness of reactor is 80%.
Embodiment 7
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 30-100 nanometer, diameter 0.2-5 micron.
A preparation method for FeS nano material, step comprises:
(1) being dissolved in water by yellow prussiate of potash and thiosemicarbazide, add a certain amount of Sodium dodecylbenzene sulfonate, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 20 hours under 200 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 50 DEG C, vacuum-drying 8 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of yellow prussiate of potash is 0.2mol/L, and the concentration of thiosemicarbazide is 0.4mol/L, and the concentration of Sodium dodecylbenzene sulfonate is 0.2mol/L; In step (2), the compactedness of reactor is 80%.
Embodiment 8
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 30��80 nanometers, diameter 0.2��3.8 micron.
A preparation method for FeS nano material, step comprises:
(1) being dissolved in water by yellow prussiate of potash and CYSTINE, add a certain amount of cetyl trimethylammonium bromide, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 15 hours under 200 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 60 DEG C, vacuum-drying 6 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of yellow prussiate of potash is 0.8mol/L, and the concentration of CYSTINE is 1.6mol/L, and the concentration of cetyl trimethylammonium bromide is 2.4mol/L; In step (2), the compactedness of reactor is 80%.
Embodiment 9
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 30��90 nanometers, diameter 0.2��4.0 micron.
A preparation method for FeS nano material, step comprises:
(1) being dissolved in water by yellow prussiate of potash and Cys, add a certain amount of palmityl trimethyl ammonium chloride, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 15 hours under 200 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 60 DEG C, vacuum-drying 5 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of yellow prussiate of potash ferrous salt is 0.05mol/L, and the concentration of Cys is 0.075mol/L, and the concentration of palmityl trimethyl ammonium chloride is 0.05mol/L; In step (2), the compactedness of reactor is 80%.
Embodiment 10
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 30��95 nanometers, diameter 0.2��4.8 micron.
A preparation method for FeS nano material, step comprises:
(1) being dissolved in water by yellow prussiate of potash and Thiovanic acid, add a certain amount of cetyl trimethylammonium bromide, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 10 hours under 200 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 60 DEG C, vacuum-drying 8 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of yellow prussiate of potash is 0.1mol/L, and the concentration of Thiovanic acid is 0.1mol/L, and the concentration of cetyl trimethylammonium bromide is 0.05mol/L; In step (2), the compactedness of reactor is 80%.
Embodiment 11
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 35��55 nanometers, diameter 0.2��3.5 micron.
A preparation method for FeS nano material, step comprises:
(1) being dissolved in water by yellow prussiate of potash and thioacetamide, add a certain amount of palmityl trimethyl ammonium chloride, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 12 hours under 200 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 60 DEG C, vacuum-drying 6 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of yellow prussiate of potash is 0.05mol/L, and the concentration of thioacetamide is 0.05mol/L, and the concentration of palmityl trimethyl ammonium chloride is 0.025mol/L; In step (2), the compactedness of reactor is 50%.
Embodiment 12
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 40��85 nanometers, diameter 0.2��4.5 micron.
A preparation method for FeS nano material, step comprises:
(1) being mixed in water by yellow prussiate of potash and sodium sulfide solution, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 30 hours under 210 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 60 DEG C, vacuum-drying 6 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of yellow prussiate of potash is 0.02mol/L, and the concentration of sodium sulfide solution is 0.02mol/L; In step (2), the compactedness of reactor is 80%.
Embodiment 13
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 40��90 nanometers, diameter 0.2��4 micron.
A preparation method for FeS nano material, step comprises:
(1) being mixed in water by iron protochloride, ferrous ammonium sulphate and sodium sulfide solution, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 20 hours under 200 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 60 DEG C, vacuum-drying 6 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of iron protochloride is 0.02mol/L, ferrous ammonium sulfate concentration 0.02mol/L, and the concentration of sodium sulfide solution is 0.02mol/L; In step (2), the compactedness of reactor is 80%.
Embodiment 14
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 30��75 nanometers, diameter 0.2��4.5 micron.
A preparation method for FeS nano material, step comprises:
(1) being dissolved in water by yellow prussiate of potash, ferrous ammonium cyanide and Cys, thiosemicarbazide, add a certain amount of palmityl trimethyl ammonium chloride, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 15 hours under 200 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 60 DEG C, vacuum-drying 5 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of yellow prussiate of potash is 0.05mol/L, ferrocyanide ammonium concentration is 0.05mol/L, the concentration of Cys is 0.075mol/L, and thiosemicarbazide concentration is 0.075mol/L, and the concentration of palmityl trimethyl ammonium chloride is 0.05mol/L; In step (2), the compactedness of reactor is 80%.
Embodiment 15
A kind of FeS nano material, has the sheet structure of a dimension, and the thickness of sheet structure FeS is 40��100 nanometers, diameter 0.4��4.6 micron.
A preparation method for FeS nano material, step comprises:
(1) being dissolved in water by yellow prussiate of potash, ferrous sulfate, ferrous ammonium sulphate and thiocarbamide, Cys, add a certain amount of polyvinylpyrrolidone, magnetic agitation forms homogeneous solution;
(2) above-mentioned homogeneous solution is put into polytetrafluoroethyllining lining autoclave, react 20 hours under 200 DEG C of hydrothermal conditions, then naturally cool to room temperature;
(3) by clean to product deionized water and ethanol centrifuge washing, at 60 DEG C, vacuum-drying 6 is little of constant weight, obtains sheet FeS electrode materials.
In described step (1), the concentration of yellow prussiate of potash is 0.05mol/L, ferrous sulfate concentration is 0.05mol/L, and ferrous ammonium sulfate concentration is 0.05mol/L, and the concentration of thiocarbamide is 1.0mol/L, Cys 1.0mol/L, the concentration of polyvinylpyrrolidone is 1.0mol/L; In step (2), the compactedness of reactor is 80%.
Claims (4)
1. the preparation method of a FeS nano material, it is characterised in that, comprise the following steps:
(1) ferrous salt and sulfocompound are dissolved in water, then add tensio-active agent, stir evenly;
(2) homogeneous solution prepared by step (1) is put into autoclave, after hydro-thermal reaction, naturally cool to room temperature;
(3) by product centrifugation, washing, after dry, sheet FeS electrode materials is namely obtained;
Tensio-active agent described in step (1) is one or more in polyvinylpyrrolidone, polyvinyl alcohol, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride; The concentration of ferrous salt is 0.01 ~ 1.0mol/L, and the concentration of sulfocompound is 0.005 ~ 2.0mol/L, and the concentration of tensio-active agent is 0 ~ 4.0mol/L; Described ferrous salt be selected from ferrous sulfate, iron protochloride, ferrous ammonium sulphate, ferrous ammonium cyanide, yellow prussiate of potash one or more; Described sulfocompound be selected from thiocarbamide, thiosemicarbazide, Thiovanic acid, thioacetamide, CYSTINE, Cys, sodium sulphite one or more;
Described FeS nano material has sheet structure, and the thickness of sheet is 20 ~ 100 nanometers, and the length of sheet is 0.2 ~ 5 micron.
2. preparation method according to claim 1, it is characterised in that, in step (2), temperature of reaction is 140 ~ 220 DEG C.
3. preparation method according to claim 1, it is characterised in that, in step (2), the compactedness of reactor is 50 ~ 80%.
4. preparation method according to claim 1, it is characterised in that, in step (3), washing is for washing with deionized water and alcohol solvent, and drying temperature is 30 ~ 80 DEG C, and the time is 5 ~ 10 hours.
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| CN104538587B (en) * | 2014-12-12 | 2017-01-04 | 浙江大学 | FeS micron ball structural membrane and preparation method thereof |
| CN104466089B (en) * | 2014-12-12 | 2017-05-24 | 浙江大学 | FeS flaky array film and preparation method thereof |
| CN105314686A (en) * | 2015-09-25 | 2016-02-10 | 浙江大学宁波理工学院 | FeS nanosheet preparing method |
| CN105776888B (en) * | 2016-02-02 | 2019-01-29 | 中国科学院合肥物质科学研究院 | A method of preparing pyrite phase ferrous disulfide film |
| CN107634193B (en) * | 2017-08-25 | 2021-04-27 | 武汉理工大学 | Porous ferrous sulfide nanowire and nitrogen-doped carbon composite material as well as preparation method and application thereof |
| CN108144631B (en) * | 2017-12-25 | 2020-12-25 | 中国科学技术大学 | Transition metal sulfide catalyst, method for producing same, and method for producing aromatic amine compound |
| CN109004190A (en) * | 2018-07-11 | 2018-12-14 | 大同新成新材料股份有限公司 | A kind of ferrous sulfide anode material and preparation method |
| CN110124695B (en) * | 2019-06-12 | 2021-07-30 | 南昌航空大学 | Catalyst for degrading organic pollutants in printing and dyeing wastewater, preparation method and application |
| CN110526300B (en) * | 2019-06-28 | 2022-01-04 | 中冶华天工程技术有限公司 | Preparation method of magnetic nano Fe-S material for heavy metal treatment |
| CN110776920A (en) * | 2019-09-30 | 2020-02-11 | 南京师范大学 | Soil remediation agent, preparation method and application |
| CN112209448B (en) * | 2020-08-27 | 2023-04-07 | 南京邮电大学 | Ultra-small FeS nanodot and preparation method and application thereof |
| CN112830474B (en) * | 2020-12-31 | 2023-05-02 | 青岛科技大学 | Carbon-based two-dimensional composite electrode material and preparation method thereof |
| CN114429865B (en) * | 2022-01-10 | 2023-10-13 | 重庆文理学院 | Preparation method of nickel wire/ferric oxide/manganese dioxide composite fiber |
| CN115634698B (en) * | 2022-11-08 | 2024-03-01 | 江南大学 | Micro/nano hierarchical flower-like direct Z-shaped heterojunction visible light catalyst and preparation method thereof |
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