CN102817081B - Preparation method of flaky iron sulfide single crystal nano-material - Google Patents
Preparation method of flaky iron sulfide single crystal nano-material Download PDFInfo
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- CN102817081B CN102817081B CN201210300280.9A CN201210300280A CN102817081B CN 102817081 B CN102817081 B CN 102817081B CN 201210300280 A CN201210300280 A CN 201210300280A CN 102817081 B CN102817081 B CN 102817081B
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Abstract
The invention relates to a preparation method of a flaky iron sulfide single crystal nano-material. The method comprises the following steps of: (1) mixing an iron source and trioctylphosphine oxide, dissolving in oleylamine, stirring, feeding nitrogen or argon to remove oxygen, and then obtaining an iron source precursor; (2) heating and stirring the iron source precursor in oil bath to obtain iron source solution; (3) dissolving a sulfur source in the oleylamine, stirring, feeding argon or nitrogen to remove oxygen, and then obtaining sulfur source solution; (4) heating the sulfur source solution, extracting through a needle tube, quickly injecting into the iron source solution, carrying out warming reaction on the oil bath for heating the iron source, and obtaining a colloid of the flaky iron sulfide single crystal nano-material; and (5) cooling the colloid of the flaky iron sulfide single crystal nano-material to room temperature, adding trichloromethane-ethanol mixed solution, and carrying out washing and centrifugalizing processing for many times until centrifugate on an upper layer is colorless so as to obtain the flaky single-phase iron sulfide single crystal nano-material. The obtained product has uniform grain size and shape, good process repeatability, and stable quality.
Description
Technical field
The present invention relates to a kind of preparation method of ferriferrous sulfide, particularly relate to a kind of preparation method of flaky iron sulfide single crystal nano-material.
Background technology
Ferriferrous sulfide, as a kind of magneticsubstance, is ferromagnetic material.Ferromagnetic substance has a wide range of applications in industrial circle, can be used as microwave absorbing material, magnetic recording material, magnetic liquid, also has a wide range of applications at biomedicine field.Ferriferrous sulfide can be used for cancer hyperthermy; and the medium that its magnetic property makes this kind of material be expected to as target administration; medical field (M. Posfai can be applied in the near future; P. R. Buseck; D. A. Bazylinski and R. B. Frankel, Iron sulfides from magnetotactic bacteria; Structure, composition, and phase transitions [J]. Journal of the Mineralogical Society of America. 1998,83 (11-12), 1469-1481.; Y. S. Chang, S. Savitha, S. Sadhasivam, C. K. Hsu and F. H. Lin, Fabrication, characterization, and application of greigite nanoparticles for cancer hyperthermia [J]. Journal of Colloid and Interface Science. 2011,363,314-319.).
Hot injection is effective ways (the Z. T. Zhang being easy to synthesize single dispersing, high fluorescence semiconductor nanocrystalline material, B. Zhao and L. M. Hu, PVP Protective Mechanism of Ultrafine Silver Powder Synthesized by Chemical Reduction Processes [J]. Journal of solid state chemistry. 1996,121,105-110.).Researcher has successfully synthesized CdTe, CdSe, CdS, ZnS Monodisperse nanocrystals (C. de. M. Doneg, P. Liljeroth and D. Vanmaekelbergh by hot injection; Physicochemical Evaluation of the Hot-Injection Method, a Synthesis Route for Monodisperse Nanocrystal [J]. Small. 2005,1 (12), 1152-1162.; C. B. Murray, D. J. Norris and M. G. Bawendi, Synthesis and characterization of nearly monodisperse CdE (E=sulfur, selenium, tellurium) semiconductor nanocrystallites [J]. J. Am. Chem. Soc. 1993,115,8706-8715.; J. V. Williams, N. A. Kotov and P. E. Savage, A Rapid Hot-Injection Method for the Improved Hydrothermal Synthesis of CdSe Nanoparticles [J]. Ind. Eng. Chem. Res. 2009,48 (9), 4316-4321.; I. Sondi, O. Siiman, S. Koester and E. Matijevic, Preparation of aminodextran-CdS nanoparticle complexes and biologically active antibody-aminodextran-CdS nanoparticle conjugates [J]. Langmuir. 2000,16,3107-3118.).Hot injection adopts high boiling solvent, is injected into rapidly by precursor reagent solution in another phase reaction thing solution in high reaction temperatures, have be easy to synthesize zero-fault, pattern is easy to the small size nanocrystalline material that controls.
Ferriferrous sulfide is a kind of multiduty functional materials, due to the mutability of Fe:S ratio in the process of synthesis iron sulfide, causes the ferriferrous sulfide (gregite) synthesizing pure phase more difficult, usually can along with the generation of ferrous disulfide.Although also there is the research of synthesis ferriferrous sulfide in current bibliographical information, general phase purity is poor, many containing other sulphur iron cpd.Simultaneously pattern also more difficult control in the building-up process reported of ferriferrous sulfide, obtains size uniform, pattern rule and controlled ferriferrous sulfide is nanocrystalline certain difficulty.Still there is no the report of the preparation method of the iron sulfide single crystal nano-material of single dispersing, single-phase, size uniform and morphology controllable at present.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of with low cost, the simple flaky iron sulfide single crystal nano-material of technique.
For solving the problem, the preparation method of a kind of flaky iron sulfide single crystal nano-material of the present invention, comprises the following steps:
(1) by source of iron and trioctylphosphine oxide (TOPO) mixed in molar ratio by 1:1.5 ~ 1:3, and be dissolved in oleyl amine, through stir and logical purity be more than 98.5% nitrogen or argon gas removing oxygen after, obtain source of iron presoma; The mass volume ratio of described source of iron and described oleyl amine is 1:50 ~ 1:150;
(2) described source of iron presoma be heated to 120 ~ 170 DEG C in oil bath and stir 0.5 ~ 1.5 hour, obtaining source of iron solution;
(3) sulphur source is dissolved in oleyl amine, through stir and logical purity be more than 98.5% argon gas or nitrogen removing oxygen after, obtain sulphur source solution; The mass volume ratio of described sulphur source and described oleyl amine is 1:50 ~ 1:100;
(4) described sulphur source solution is heated to 60 ~ 90 DEG C, then extract with needle tubing, fast injection is entered in source of iron solution, then the oil bath of described heating source of iron is warming up to 190 ~ 250 DEG C of reactions 1 ~ 3 hour, obtains the colloid of flaky iron sulfide single crystal nano-material; The volume ratio of described sulphur source solution and described source of iron solution is 1:2 ~ 1:4;
(5) when the colloid of described flaky iron sulfide single crystal nano-material being cooled to room temperature, add that trichloromethane-alcohol mixeding liquid repeatedly washs, centrifugal treating until upper strata centrifugate is colourless, obtain sheet single-phase iron sulfide single crystal nano-material; Trichloromethane in described trichloromethane-alcohol mixeding liquid and the volume ratio of ethanol are 1:0.5 ~ 1:1; The colloid of described flaky iron sulfide single crystal nano-material and the volume ratio of described trichloromethane-alcohol mixeding liquid are 1:2 ~ 1:5.
Described step (1) in source of iron refer to that concentration is any one in the iron protochloride of 0.05 ~ 0.5 mol/L, iron nitrate, ferric acetyl acetonade.
Described step (3) in sulphur source refer to sulphur powder or thiocarbamide.
Described step (5) in trichloromethane-alcohol mixeding liquid the mass concentration of ethanol be 50%.
The present invention compared with prior art has the following advantages:
1, the present invention is without the need to the step of complexity, do not adopt the high toxicity solvent such as benzene, and adopt high boiling solvent---oleyl amine, and by selecting different sulphur sources, source of iron, just the phase purity of product can be controlled, make iron sulphur ratio in crystalline structure be ideal stoichiometric ratio (3:4), and be the single-phase ferriferrous sulfide without pyrite, the equal dephasign of smythite.
2, cheaper starting materials that the present invention adopts, therefore, greatly reduces production cost.
3, preparation method of the present invention is compared with existing wet chemistry method, has preparation process easy, and synthetic product is single dispersing flake nano monocrystal material, phase purity is high, pattern is regular, size uniform and the advantage such as the particle size of synthesized product and morphology controllable.
4, the product adopting the inventive method to obtain shows through X-ray diffraction analysis, it is single-phase ferriferrous sulfide (greigite) (see Fig. 1, Fig. 4, Fig. 8), fits like a glove with the peak position of ferriferrous sulfide (gregite) standard P DF card 42-1340.
5, the product adopting the inventive method to obtain shows (see Fig. 7 and Figure 12) through magnetic hysteresis loop (VSM) test, products obtained therefrom is good ferromagnetic substance, the nanocrystalline saturation magnetization (Ms) of trilateral sheet single-phase ferriferrous sulfide is 17.07 emu/g, residual magnetization (Mr) is 7.303 emu/g, and coercive force (Hc) is 296.02 Oe; Trilateral mixes the nanocrystalline saturation magnetization of sheet single-phase ferriferrous sulfide with long strip shape be 19.05emu/g, residual magnetization 5.909 emu/g, and coercive force is 150.332 Oe; The saturation magnetization (Ms) of the single-phase ferriferrous sulfide of sheet intercalation is 29.02 emu/g, and residual magnetization (Mr) is 16.51 emu/g, and coercive force (Hc) is 566.79 Oe.
6, the product adopting the inventive method to obtain is tested through X-ray diffraction, can find that prepared product is the ferriferrous sulfide (see Fig. 1, Fig. 4, Fig. 8) of single-phase.
7, the product adopting the inventive method to obtain, through transmission electron microscope and sem test, can find that prepared product is single dispersing, pattern rule, the more uniform flaky iron sulfide single crystal nano-material of size (see Fig. 2, Fig. 3, Fig. 5, Fig. 6, Fig. 9, Figure 10, Figure 11).
8, products obtained therefrom of the present invention has homogeneous particle diameter and pattern, good process repeatability, steady quality, is expected the field of medicaments such as the medium being applied to cancer hyperthermy and target administration.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the nanocrystalline X-ray diffraction spectrum of triangular single sheets shape single-phase ferriferrous sulfide of the present invention.
Fig. 2 is the nanocrystalline transmission electron microscope photo (in figure, scale is 100nm) of triangular single sheets shape single-phase ferriferrous sulfide of the present invention.
Fig. 3 is the nanocrystalline transmission electron microscope photo (in figure, scale is 20nm) of triangular single sheets shape single-phase ferriferrous sulfide of the present invention.
Fig. 4 is that trilateral of the present invention mixes the nanocrystalline X-ray diffraction spectrum of sheet single-phase ferriferrous sulfide with long strip shape.
Fig. 5 is that trilateral of the present invention mixes the nanocrystalline transmission electron microscope photo of sheet single-phase ferriferrous sulfide (in figure, scale is 100nm) with long strip shape.
Fig. 6 is that trilateral of the present invention mixes the nanocrystalline transmission electron microscope photo of sheet single-phase ferriferrous sulfide (in figure, scale is 20nm) with long strip shape.
Fig. 7 is that triangular single sheets shape of the present invention and trilateral mix the nanocrystalline VSM of sheet single-phase ferriferrous sulfide and scheme (a-triangular single sheets shape b-mixes sheet) with long strip shape.
Fig. 8 is the nanocrystalline X-ray diffraction spectrum of sheet intercalation single-phase ferriferrous sulfide of the present invention.
Fig. 9 is the nanocrystalline stereoscan photograph (in figure, scale is 200nm) of sheet intercalation single-phase ferriferrous sulfide of the present invention.
Figure 10 is the nanocrystalline transmission electron microscope photo (in figure, scale is 0.5 μm) of sheet intercalation single-phase ferriferrous sulfide of the present invention.
Figure 11 is the nanocrystalline transmission electron microscope photo (in figure, scale is 100nm) of sheet intercalation single-phase ferriferrous sulfide of the present invention.
Figure 12 be sheet intercalation single-phase ferriferrous sulfide of the present invention nanocrystalline VSM figure.
Embodiment
embodiment 1a preparation method for flaky iron sulfide single crystal nano-material, comprises the following steps:
(1) by source of iron---concentration is the iron protochloride of 0.05mol/L and trioctylphosphine oxide (TOPO) mixed in molar ratio by 1:1.5, and is dissolved in oleyl amine, through stir and logical purity be more than 98.5% nitrogen or argon gas removing oxygen after, obtain source of iron presoma.
Wherein: the mass volume ratio (g/ml) of source of iron and oleyl amine is 1:50.
(2) source of iron presoma be heated to 120 DEG C in oil bath and stir 1.5 hours, obtaining source of iron solution.
(3) by sulphur source---sulphur powder is dissolved in oleyl amine, through stir and logical purity be more than 98.5% argon gas or nitrogen removing oxygen after, obtain sulphur source solution.
Wherein: the mass volume ratio (g/ml) of sulphur source and oleyl amine is 1:50.
(4) sulphur source solution is heated to 60 DEG C, then extract with needle tubing, fast injection is entered in source of iron solution, then the oil bath of heating source of iron is warming up to 190 DEG C of reactions 3 hours, obtains the colloid of flaky iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of sulphur source solution and source of iron solution is 1:2.
(5) when the colloid of flaky iron sulfide single crystal nano-material being cooled to room temperature, add that trichloromethane-alcohol mixeding liquid repeatedly washs, centrifugal treating until upper strata centrifugate is colourless, obtain sheet single-phase iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of the trichloromethane in trichloromethane-alcohol mixeding liquid and ethanol is 1:0.5; The colloid of flaky iron sulfide single crystal nano-material and the volume ratio (ml/ml) of trichloromethane-alcohol mixeding liquid are 1:2; In trichloromethane-alcohol mixeding liquid, the mass concentration of ethanol is 50%.
embodiment 2a preparation method for flaky iron sulfide single crystal nano-material, comprises the following steps:
(1) by source of iron---concentration is the iron protochloride of 0.5 mol/L and trioctylphosphine oxide (TOPO) mixed in molar ratio by 1:3, and is dissolved in oleyl amine, through stir and logical purity be more than 98.5% nitrogen or argon gas removing oxygen after, obtain source of iron presoma.
Wherein: the mass volume ratio (g/ml) of source of iron and oleyl amine is 1:150.
(2) source of iron presoma be heated to 170 DEG C in oil bath and stir 0.5 hour, obtaining source of iron solution.
(3) by sulphur source---thiocarbamide is dissolved in oleyl amine, through stir and logical purity be more than 98.5% argon gas or nitrogen removing oxygen after, obtain sulphur source solution.
Wherein: the mass volume ratio (g/ml) of sulphur source and oleyl amine is 1:100.
(4) sulphur source solution is heated to 90 DEG C, then extract with needle tubing, fast injection is entered in source of iron solution, then the oil bath of heating source of iron is warming up to 250 DEG C of reactions 1 hour, obtains the colloid of flaky iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of sulphur source solution and source of iron solution is 1:4.
(5) when the colloid of flaky iron sulfide single crystal nano-material being cooled to room temperature, add that trichloromethane-alcohol mixeding liquid repeatedly washs, centrifugal treating until upper strata centrifugate is colourless, obtain sheet single-phase iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of the trichloromethane in trichloromethane-alcohol mixeding liquid and ethanol is 1:1; The colloid of flaky iron sulfide single crystal nano-material and the volume ratio (ml/ml) of trichloromethane-alcohol mixeding liquid are 1:5; In trichloromethane-alcohol mixeding liquid, the mass concentration of ethanol is 50%.
embodiment 3a preparation method for flaky iron sulfide single crystal nano-material, comprises the following steps:
(1) by source of iron---concentration is the iron protochloride of 0.25 mol/L and trioctylphosphine oxide (TOPO) mixed in molar ratio by 1:2.5, and is dissolved in oleyl amine, through stir and logical purity be more than 98.5% nitrogen or argon gas removing oxygen after, obtain source of iron presoma.
Wherein: the mass volume ratio (g/ml) of source of iron and oleyl amine is 1:100.
(2) source of iron presoma be heated to 150 DEG C in oil bath and stir 1 hour, obtaining source of iron solution.
(3) by sulphur source---sulphur powder is dissolved in oleyl amine, through stir and logical purity be more than 98.5% argon gas or nitrogen removing oxygen after, obtain sulphur source solution.
Wherein: the mass volume ratio (g/ml) of sulphur source and oleyl amine is 1:75.
(4) sulphur source solution is heated to 80 DEG C, then extract with needle tubing, fast injection is entered in source of iron solution, then the oil bath of heating source of iron is warming up to 220 DEG C of reactions 2 hours, obtains the colloid of flaky iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of sulphur source solution and source of iron solution is 1:3.
(5) when the colloid of flaky iron sulfide single crystal nano-material being cooled to room temperature, add that trichloromethane-alcohol mixeding liquid repeatedly washs, centrifugal treating until upper strata centrifugate is colourless, obtain sheet single-phase iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of the trichloromethane in trichloromethane-alcohol mixeding liquid and ethanol is 1:0.75; The colloid of flaky iron sulfide single crystal nano-material and the volume ratio (ml/ml) of trichloromethane-alcohol mixeding liquid are 1:3.5; In trichloromethane-alcohol mixeding liquid, the mass concentration of ethanol is 50%.
embodiment 4a preparation method for flaky iron sulfide single crystal nano-material, comprises the following steps:
(1) by source of iron---concentration is the iron nitrate of 0.05mol/L and trioctylphosphine oxide (TOPO) mixed in molar ratio by 1:1.5, and is dissolved in oleyl amine, through stir and logical purity be more than 98.5% nitrogen or argon gas removing oxygen after, obtain source of iron presoma.
Wherein: the mass volume ratio (g/ml) of source of iron and oleyl amine is 1:50.
(2) source of iron presoma be heated to 120 DEG C in oil bath and stir 1.5 hours, obtaining source of iron solution.
(3) by sulphur source---thiocarbamide is dissolved in oleyl amine, through stir and logical purity be more than 98.5% argon gas or nitrogen removing oxygen after, obtain sulphur source solution.
Wherein: the mass volume ratio (g/ml) of sulphur source and oleyl amine is 1:50.
(4) sulphur source solution is heated to 60 DEG C, then extract with needle tubing, fast injection is entered in source of iron solution, then the oil bath of heating source of iron is warming up to 190 DEG C of reactions 3 hours, obtains the colloid of flaky iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of sulphur source solution and source of iron solution is 1:2.
(5) when the colloid of flaky iron sulfide single crystal nano-material being cooled to room temperature, add that trichloromethane-alcohol mixeding liquid repeatedly washs, centrifugal treating until upper strata centrifugate is colourless, obtain sheet single-phase iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of the trichloromethane in trichloromethane-alcohol mixeding liquid and ethanol is 1:0.5; The colloid of flaky iron sulfide single crystal nano-material and the volume ratio (ml/ml) of trichloromethane-alcohol mixeding liquid are 1:2; In trichloromethane-alcohol mixeding liquid, the mass concentration of ethanol is 50%.
embodiment 5a preparation method for flaky iron sulfide single crystal nano-material, comprises the following steps:
(1) by source of iron---concentration is the iron nitrate of 0.5 mol/L and trioctylphosphine oxide (TOPO) mixed in molar ratio by 1:3, and is dissolved in oleyl amine, through stir and logical purity be more than 98.5% nitrogen or argon gas removing oxygen after, obtain source of iron presoma.
Wherein: the mass volume ratio (g/ml) of source of iron and oleyl amine is 1:150.
(2) source of iron presoma be heated to 170 DEG C in oil bath and stir 0.5 hour, obtaining source of iron solution.
(3) by sulphur source---sulphur powder is dissolved in oleyl amine, through stir and logical purity be more than 98.5% argon gas or nitrogen removing oxygen after, obtain sulphur source solution.
Wherein: the mass volume ratio (g/ml) of sulphur source and oleyl amine is 1:100.
(4) sulphur source solution is heated to 90 DEG C, then extract with needle tubing, fast injection is entered in source of iron solution, then the oil bath of heating source of iron is warming up to 250 DEG C of reactions 1 hour, obtains the colloid of flaky iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of sulphur source solution and source of iron solution is 1:4.
(5) when the colloid of flaky iron sulfide single crystal nano-material being cooled to room temperature, add that trichloromethane-alcohol mixeding liquid repeatedly washs, centrifugal treating until upper strata centrifugate is colourless, obtain sheet single-phase iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of the trichloromethane in trichloromethane-alcohol mixeding liquid and ethanol is 1:1; The colloid of flaky iron sulfide single crystal nano-material and the volume ratio (ml/ml) of trichloromethane-alcohol mixeding liquid are 1:5; In trichloromethane-alcohol mixeding liquid, the mass concentration of ethanol is 50%.
embodiment 6a preparation method for flaky iron sulfide single crystal nano-material, comprises the following steps:
(1) by source of iron---concentration is the iron nitrate of 0.2 mol/L and trioctylphosphine oxide (TOPO) mixed in molar ratio by 1:2, and is dissolved in oleyl amine, through stir and logical purity be more than 98.5% nitrogen or argon gas removing oxygen after, obtain source of iron presoma.
Wherein: the mass volume ratio (g/ml) of source of iron and oleyl amine is 1:100.
(2) source of iron presoma be heated to 150 DEG C in oil bath and stir 1 hour, obtaining source of iron solution.
(3) by sulphur source---thiocarbamide is dissolved in oleyl amine, through stir and logical purity be more than 98.5% argon gas or nitrogen removing oxygen after, obtain sulphur source solution.
Wherein: the mass volume ratio (g/ml) of sulphur source and oleyl amine is 1:80.
(4) sulphur source solution is heated to 70 DEG C, then extract with needle tubing, fast injection is entered in source of iron solution, then the oil bath of heating source of iron is warming up to 200 DEG C of reactions 2 hours, obtains the colloid of flaky iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of sulphur source solution and source of iron solution is 1:3.
(5) when the colloid of flaky iron sulfide single crystal nano-material being cooled to room temperature, add that trichloromethane-alcohol mixeding liquid repeatedly washs, centrifugal treating until upper strata centrifugate is colourless, obtain sheet single-phase iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of the trichloromethane in trichloromethane-alcohol mixeding liquid and ethanol is 1:0.65; The colloid of flaky iron sulfide single crystal nano-material and the volume ratio (ml/ml) of trichloromethane-alcohol mixeding liquid are 1:3; In trichloromethane-alcohol mixeding liquid, the mass concentration of ethanol is 50%.
embodiment 7a preparation method for flaky iron sulfide single crystal nano-material, comprises the following steps:
(1) by source of iron---concentration is the ferric acetyl acetonade of 0.05mol/L and trioctylphosphine oxide (TOPO) mixed in molar ratio by 1:1.5, and is dissolved in oleyl amine, through stir and logical purity be more than 98.5% nitrogen or argon gas removing oxygen after, obtain source of iron presoma.
Wherein: the mass volume ratio (g/ml) of source of iron and oleyl amine is 1:50.
(2) source of iron presoma be heated to 120 DEG C in oil bath and stir 1.5 hours, obtaining source of iron solution.
(3) by sulphur source---thiocarbamide is dissolved in oleyl amine, through stir and logical purity be more than 98.5% argon gas or nitrogen removing oxygen after, obtain sulphur source solution.
Wherein: the mass volume ratio (g/ml) of sulphur source and oleyl amine is 1:50.
(4) sulphur source solution is heated to 60 DEG C, then extract with needle tubing, fast injection is entered in source of iron solution, then the oil bath of heating source of iron is warming up to 190 DEG C of reactions 3 hours, obtains the colloid of flaky iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of sulphur source solution and source of iron solution is 1:2.
(5) when the colloid of flaky iron sulfide single crystal nano-material being cooled to room temperature, add that trichloromethane-alcohol mixeding liquid repeatedly washs, centrifugal treating until upper strata centrifugate is colourless, obtain sheet single-phase iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of the trichloromethane in trichloromethane-alcohol mixeding liquid and ethanol is 1:0.5; The colloid of flaky iron sulfide single crystal nano-material and the volume ratio (ml/ml) of trichloromethane-alcohol mixeding liquid are 1:2; In trichloromethane-alcohol mixeding liquid, the mass concentration of ethanol is 50%.
embodiment 8a preparation method for flaky iron sulfide single crystal nano-material, comprises the following steps:
(1) by source of iron---concentration is the ferric acetyl acetonade of 0.5 mol/L and trioctylphosphine oxide (TOPO) mixed in molar ratio by 1:3, and is dissolved in oleyl amine, through stir and logical purity be more than 98.5% nitrogen or argon gas removing oxygen after, obtain source of iron presoma.
Wherein: the mass volume ratio (g/ml) of source of iron and oleyl amine is 1:150.
(2) source of iron presoma be heated to 170 DEG C in oil bath and stir 0.5 hour, obtaining source of iron solution.
(3) by sulphur source---sulphur powder is dissolved in oleyl amine, through stir and logical purity be more than 98.5% argon gas or nitrogen removing oxygen after, obtain sulphur source solution.
Wherein: the mass volume ratio (g/ml) of sulphur source and oleyl amine is 1:100.
(4) sulphur source solution is heated to 90 DEG C, then extract with needle tubing, fast injection is entered in source of iron solution, then the oil bath of heating source of iron is warming up to 250 DEG C of reactions 1 hour, obtains the colloid of flaky iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of sulphur source solution and source of iron solution is 1:4.
(5) when the colloid of flaky iron sulfide single crystal nano-material being cooled to room temperature, add that trichloromethane-alcohol mixeding liquid repeatedly washs, centrifugal treating until upper strata centrifugate is colourless, obtain sheet single-phase iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of the trichloromethane in trichloromethane-alcohol mixeding liquid and ethanol is 1:1; The colloid of flaky iron sulfide single crystal nano-material and the volume ratio (ml/ml) of trichloromethane-alcohol mixeding liquid are 1:5; In trichloromethane-alcohol mixeding liquid, the mass concentration of ethanol is 50%.
embodiment 9a preparation method for flaky iron sulfide single crystal nano-material, comprises the following steps:
(1) by source of iron---concentration is the ferric acetyl acetonade of 0.3 mol/L and trioctylphosphine oxide (TOPO) mixed in molar ratio by 1:2.5, and is dissolved in oleyl amine, through stir and logical purity be more than 98.5% nitrogen or argon gas removing oxygen after, obtain source of iron presoma.
Wherein: the mass volume ratio (g/ml) of source of iron and oleyl amine is 1:125.
(2) source of iron presoma be heated to 155 DEG C in oil bath and stir 1 hour, obtaining source of iron solution.
(3) by sulphur source---thiocarbamide is dissolved in oleyl amine, through stir and logical purity be more than 98.5% argon gas or nitrogen removing oxygen after, obtain sulphur source solution.
Wherein: the mass volume ratio (g/ml) of sulphur source and oleyl amine is 1:85.
(4) sulphur source solution is heated to 70 DEG C, then extract with needle tubing, fast injection is entered in source of iron solution, then the oil bath of heating source of iron is warming up to 200 DEG C of reactions 1.5 hours, obtains the colloid of flaky iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of sulphur source solution and source of iron solution is 1:3.5.
(5) when the colloid of flaky iron sulfide single crystal nano-material being cooled to room temperature, add that trichloromethane-alcohol mixeding liquid repeatedly washs, centrifugal treating until upper strata centrifugate is colourless, obtain sheet single-phase iron sulfide single crystal nano-material.
Wherein: the volume ratio (ml/ml) of the trichloromethane in trichloromethane-alcohol mixeding liquid and ethanol is 1:0.9; The colloid of flaky iron sulfide single crystal nano-material and the volume ratio (ml/ml) of trichloromethane-alcohol mixeding liquid are 1:4; In trichloromethane-alcohol mixeding liquid, the mass concentration of ethanol is 50%.
Claims (1)
1. a preparation method for flaky iron sulfide single crystal nano-material, comprises the following steps:
(1) source of iron and trioctylphosphine oxide are pressed the mixed in molar ratio of 1:1.5 ~ 1:3, and are dissolved in oleyl amine, through stir and logical purity be more than 98.5% nitrogen or argon gas removing oxygen after, obtain source of iron presoma; The mass volume ratio of described source of iron and described oleyl amine is 1:50 ~ 1:150; Described source of iron refers to that concentration is any one in the iron protochloride of 0.05 ~ 0.5 mol/L, iron nitrate, ferric acetyl acetonade;
(2) described source of iron presoma be heated to 120 ~ 170 DEG C in oil bath and stir 0.5 ~ 1.5 hour, obtaining source of iron solution;
(3) sulphur source is dissolved in oleyl amine, through stir and logical purity be more than 98.5% argon gas or nitrogen removing oxygen after, obtain sulphur source solution; The mass volume ratio of described sulphur source and described oleyl amine is 1:50 ~ 1:100; Described sulphur source refers to sulphur powder or thiocarbamide;
(4) described sulphur source solution is heated to 60 ~ 90 DEG C, then extract with needle tubing, fast injection is entered in source of iron solution, then the oil bath of described heating source of iron is warming up to 190 ~ 250 DEG C of reactions 1 ~ 3 hour, obtains the colloid of flaky iron sulfide single crystal nano-material; The volume ratio of described sulphur source solution and described source of iron solution is 1:2 ~ 1:4;
(5) when the colloid of described flaky iron sulfide single crystal nano-material being cooled to room temperature, add that trichloromethane-alcohol mixeding liquid repeatedly washs, centrifugal treating until upper strata centrifugate is colourless, obtain sheet single-phase iron sulfide single crystal nano-material; Trichloromethane in described trichloromethane-alcohol mixeding liquid and the volume ratio of ethanol are 1:0.5 ~ 1:1; The colloid of described flaky iron sulfide single crystal nano-material and the volume ratio of described trichloromethane-alcohol mixeding liquid are 1:2 ~ 1:5; In described trichloromethane-alcohol mixeding liquid, the mass concentration of ethanol is 50%.
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