CN100509820C - Metal-aryl sulfide nanometer fiber material and preparation method thereof - Google Patents
Metal-aryl sulfide nanometer fiber material and preparation method thereof Download PDFInfo
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- CN100509820C CN100509820C CNB2006100969970A CN200610096997A CN100509820C CN 100509820 C CN100509820 C CN 100509820C CN B2006100969970 A CNB2006100969970 A CN B2006100969970A CN 200610096997 A CN200610096997 A CN 200610096997A CN 100509820 C CN100509820 C CN 100509820C
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Abstract
The invention discloses a metal-aromatic sulfide nanometer fiber material and making method, which is characterized by the following: allocating raw material from soluble organic acid salt, inorganic salt or complex salt or their metal salt with lead, cadmium, nickel, silver, cobalt, ruthenium or copper ion; blending with aromatic phenyl-sulfhydrate in the solution; filtering the sediment; washing; drying to obtain the product. The aromatic phenyl-sulfhydrate contains benzenethiol or mercapto pyridine with at least one electron-attacting substitute on the benzene ring if adopting benzenethiol, wherein the electron-attacting group contains halogen base, nitro group or nitrile radical. The diameter of nanometer fiber material is 10-500nm, which displays linear, bar and or pipe shape.
Description
Technical field
The invention belongs to inorganic-organic hybridization nano material preparation technical field, particularly organic sulfide nanocrystal and preparation method thereof.
Background technology
When adopting chemical solution reaction to prepare the metal inorganic sulfide nanometer fiber material, often need template, adopted inorganic mesoporous masterplate as Chinese patent CN1608998, patent CN1569637 has adopted porous anodic aluminium oxide, the semi-permeable membranes that patent CN1522953 has adopted collodion to make, the rod-shaped micelle masterplate of the trimethylammonium hexadecyl brometo de amonio that " applied chemistry " (2006 01 phase 7 pages) are introduced, the self-organization phantom version of polyoxyethylene glycol in water that " Yunnan University's journal natural science edition " [178 pages of 2005 27 (3A) volumes] introduced, and the duct of the chrysotile introduced of " Chenzhou pedagogical higher junior college journal " (2003 02 phase 51 pages) is as masterplate.And adopt the especially inorganic mould material of mould material, and increased the difficulty of purifying products on the one hand, also increased the cost of product on the other hand.
So far do not see the open report of the synthetic and performance study of aromatic metal base sulfide nano crystal as yet.
Summary of the invention
The objective of the invention is to propose a kind of metal-aryl sulfide nanometer fiber material and preparation method thereof.
The preparation method of metal-aryl sulfide nanometer fiber material of the present invention is characterized in that: metal-salt and aromatic base thiophenol are mixed in solution, the gained throw out after filtration, washing, drying, promptly get product; Described metal-salt is selected from leaded, the cadmium of solubility or the organic acid salt or the inorganic salt of nickel ion; Described aromatic base thiophenol is selected from the thiophenol that contains a halogenic substituent on the phenyl ring at least.
The mol ratio that described metal-salt and aromatic base thiophenol adopt usually is 1:0.1-10.
Described metal-salt if adopt inorganic salt then water make solvent, if adopt organic acid salt then to adopt alcoholic solvent.
Metal-aryl sulfide nanometer fiber material of the present invention, be characterised in that its be by aromatic base methylthio group and metal ion with chemical combination key or coordinate bond be combined into, diameter is the wire of 10-500 nanometer, bar-shaped and/or pipe; Described metal ion is selected from lead, cadmium or nickel ion.
Compared with prior art, advantage of the present invention is:
When (1) prior art adopts chemical solution reaction to prepare the metal inorganic sulfide nanometer fiber material, often need template, and the present invention just can obtain metal-aryl sulfide nanometer fiber material immediately owing to selected reactant mixes at normal temperatures and pressures, so do not need to add in addition the template material; Its reason is the growth that aromatic group has hindered some crystal face, makes crystal growth direction selectivity occur.Because the present invention does not need to use mould material, can avoid producing the cost that prepare the nano-form material early stage, can also avoid producing the later stage and remove the mould material step, simplified operation, reduced cost.
(2) disperse in organism with traditional inorganic sulphide or inorganic sulphide and the nano composite material that forms different be: product of the present invention is by aromatic base methylthio group and the metal ion aryl sulfide material with chemical combination key/coordinate bond be combined into, organic sulfide and organic polymer consistency are good, and introduce other functional group because aromatic group can further react, thereby can be used for further improving solvability or other is functional; Traditional inorganic sulphide material does not then possess such character, and dispersion and the miscibility of inorganic sulphide in organic polymer is poor in addition.
(3) compare with traditional inorganic sulphide, metal-aryl sulfide nanometer fiber material of the present invention is a kind of semiconductor material equally, but because the conjugation of phenyl ring, optical band gap is the 1.6-2.0 electron-volt, be lower than traditional nano inorganic sulphide thing semi-conductor, and traditional semi-conductive optical band gap of nano inorganic sulphide thing is higher than 2 electron-volts.
Description of drawings:
Fig. 1 is the surface scan electron micrograph of embodiment 1 product;
Fig. 2 is the uv-visible absorption spectroscopy of embodiment 1 product.
Fig. 3 is the transmission electron microscope photo of embodiment 2 products.
Fig. 4 is the surface scan electron micrograph of embodiment 3 products.
Fig. 5 is the transmission electron microscope photo of embodiment 4 products.
Fig. 6 is the transmission electron microscope photo of embodiment 5 products.
Embodiment:
The preparation of embodiment 1, aryl cadmium sulfide nano wires
In the present embodiment, metal-salt adopts cadmium acetate, and the aromatic base thiophenol is the 2,4 dichloro benzene thiophenol with two halogenic substituents, selects the solvent of methyl alcohol as cadmium acetate and 2,4 dichloro benzene thiophenol for use.The mol ratio of selecting cadmium acetate and aromatic base thiophenol for use is 1:1.
Be furnished with in the 250ml there-necked flask of mechanical stirring device, under nitrogen atmosphere, add 50 milliliters of methanol solutions that are dissolved with 1.1 milliliters of 2,4 dichloro benzene thiophenols (10 mmole), under agitation pour 50 milliliters of methanol solutions that are dissolved with 10 mmole cadmium acetates then into, the adularescent precipitation generates immediately; Continue to stir 5-20 minute.Throw out after filtration and water, washing with alcohol for several times, promptly obtain the white powder product after the drying.
X-ray diffraction spectrum analysis (XRD) shows that this product belongs to rhombic system, does not contain inorganic sulphide cadmium crystalline component fully;
X ray electronic spectrum (XPS) analysis revealed, Cd and S atomic ratio are near 1:2 in the line, and product is an aromatic base cadmium sulfide nano linear array;
The infrared spectra of product and nuclear magnetic resonance spectrum and 2,4 dichloro benzene thiophenol are compared as can be known, and product is a 2,4 dichloro benzene base Cadmium Sulfide, and chlorine substituent does not participate in chemical reaction.
This product shows that through differential thermal analysis (DSC) second-order transition temperature is 173 degree Celsius; Thermogravimetric analysis (TG) shows that the thermal degradation temperature of this product is 380 degree Celsius.
Accompanying drawing 1 has provided the surface scan electron micrograph that present embodiment prepares product.This photo shows that the present embodiment product is the nano wire of diameter 70-90nm, length 5-40 micron, and its purity is uniformly dispersed near 100%, is highly purified nanofiber.
Accompanying drawing 2 has provided the uv-visible absorption spectroscopy that present embodiment prepares product.Optical band gap with uv-visible absorption spectra test present embodiment product is 1.6 electron-volts.
The mole proportioning of cadmium acetate and aromatic base thiophenol only influences productive rate, does not influence product and forms and pattern.
Electron-withdrawing group on the phenyl ring can increase the acidity of thiophenol group, thereby increases the reactivity and the product stability of organic thiophenol and metal ion.
Metal ion and aromatic base thiophenol can not react, and perhaps the two resultant can be dissolved in the reaction system, then can not be used to prepare metal-aryl sulfide nanometer fiber material of the present invention.
The preparation of embodiment 2, aryl cadmium sulfide nano wires
Metal-salt adopts Cadmium chloride fine powder in the present embodiment, and water is as solvent.
Being furnished with in the 250ml there-necked flask of mechanical stirring device, under nitrogen atmosphere, add 1.1 milliliters of 2,4 dichloro benzene thiophenols and 50 ml methanol, stir, pour 50 milliliters of the aqueous solution that are dissolved with 0.05 mole of Cadmium chloride fine powder again into, there is precipitation to generate immediately; Stirred 20 minutes, and promptly obtained flocks.Decompress filter is carried out in this flocks, and water, washing with alcohol obtain softish felted thing for several times after the drying.
Accompanying drawing 3 has provided the transmission electron microscope photo of this felted thing that present embodiment obtains.This transmission electron microscope photo shows that this felted thing that present embodiment obtains is a 2,4 dichloro benzene base cadmium sulfide nano wires.
The preparation of embodiment 3, aryl lead sulfide nano wire
In the present embodiment, the aromatic base thiophenol adopts 3, and the 5-thiophenol dichlorobenzene selects for use methyl alcohol as solvent.
Being furnished with in the 250ml there-necked flask of mechanical stirring device, under nitrogen atmosphere, add 1.1 milliliter 3,5-thiophenol dichlorobenzene (10 mmole) and 50 ml methanol stir, and pour 50 milliliters of methanol solutions that are dissolved with 10 mmole lead acetate again into, stirred 20 minutes, and promptly obtained flocks.With this throw out after filtration, and water, washing with alcohol promptly obtain yellow powder shape product for several times after the drying.
Accompanying drawing 4 has provided the surface scan electron micrograph of the yellow powder shape product that present embodiment obtains.This photo shows that product is finely dispersed diameter 30-200 nanometer, reaches several microns pure nano line.
X ray electronic spectrum (XPS) analysis revealed, Pb and S atomic ratio are near 1:2 in the line.Hence one can see that, and the white powder product that present embodiment obtains is 3,5-dichlorophenyl lead sulfide nano wire.
Uv-visible absorption spectrum shows that the optical band gap of present embodiment product is 1.67 electron-volts.
The preparation of embodiment 4, aryl nickel sulfide nano-wire
Metal-salt adopts nickelous acetate in the present embodiment.
Being furnished with in the 250ml there-necked flask of mechanical stirring device, under nitrogen atmosphere, add 1.1 milliliters of 2,4 dichloro benzene thiophenols and 50 ml methanol, stir, pour 50 milliliters of methanol solutions that are dissolved with 0.01 mole of acetic acid nickel again into, there is precipitation to generate immediately; Stirred 20 minutes, and promptly obtained flocks.With this flocks decompress filter, and water, washing with alcohol promptly obtain red powder for several times after the drying.
This red powder product is contrasted with X-ray diffraction analysis and with inorganic sulphide nickel, can get rid of inorganic sulphide nickel composition.
XPS analysis shows that Ni and S atomic ratio are near 1:2 in the line.
Accompanying drawing 5 has provided the transmission electron microscope photo of present embodiment product.This photo shows that product is that diameter 20-500 nanometer, length reach several microns very straight nanometer rod, wherein contains a small amount of nanotube-shaped thing.Hence one can see that, and it is 2,4 dichloro benzene base nickel sulfide nano-wire that present embodiment obtains product.
Uv-visible absorption spectrum shows that the optical band gap of present embodiment product is about 1.7 electron-volts.
The preparation of embodiment 5, phenyl cadmium sulfide nano powder
Being furnished with in the 250ml there-necked flask of mechanical stirring device, under nitrogen atmosphere, add 1.1 milliliters of thiophenols and 50 ml methanol, stir, pour 50 milliliters of methanol solutions that are dissolved with 0.01 mole of acetic acid cadmium again into, stirred 20 minutes, promptly obtain flocks.Decompress filter is carried out in this flocks, and water, washing with alcohol promptly obtain the white powder product for several times after the drying.
Accompanying drawing 6 has provided the transmission electron microscope photo of the product that present embodiment obtains.Electron microscopic analysis shows that product is the random crystal of phenyl Cadmium Sulfide.
The aromatic base thiophenol has adopted and has not contained substituent thiophenol in the present embodiment, selects for use methyl alcohol as solvent.Product is random nano-multicrystal.Since do not contain in the substituent thiophenol thiophenol acidity a little less than, combine with metal ion not strong, thereby growth that can not fine some crystal face of shielding, crystalline direction of growth selectivity is relatively poor.
Claims (3)
1. the preparation method of a metal-aryl sulfide nanometer fiber material is characterized in that: metal-salt and aromatic base thiophenol are mixed in solution, the gained throw out after filtration, washing, drying, promptly get product; Described metal-salt is selected from leaded, the cadmium of solubility or the organic acid salt or the inorganic salt of nickel ion; Described aromatic base thiophenol is selected from the thiophenol that contains a halogenic substituent on the phenyl ring at least; Described metal-salt if adopt inorganic salt then water make solvent, if adopt organic acid salt then to adopt alcoholic solvent.
2. the preparation method of metal-aryl sulfide nanometer fiber material according to claim 1, the mol ratio that is characterised in that described metal-salt and aromatic base thiophenol is 1:0.1-10.
3. the metal-aryl sulfide nanometer fiber material of the described method of claim 1 preparation is characterised in that it is is the wire of 10-500 nanometer, bar-shaped and/or pipe by aromatic base methylthio group and metal ion with the diameter of chemical combination key or coordinate bond be combined into; Described metal ion is selected from lead, cadmium or nickel ion.
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| CN104232075B (en) * | 2014-09-30 | 2016-04-13 | 郑州大学 | A kind of thermochromism fluorescence thermometer material and preparation method thereof |
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| JP2005325016A (en) * | 2004-04-20 | 2005-11-24 | Samsung Electronics Co Ltd | Manufacturing method of metal nanocrystalline sulfide using thiol compound as sulfur precursor |
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| JP2005325016A (en) * | 2004-04-20 | 2005-11-24 | Samsung Electronics Co Ltd | Manufacturing method of metal nanocrystalline sulfide using thiol compound as sulfur precursor |
Non-Patent Citations (1)
| Title |
|---|
| 半导体Cds簇合物的制备及性能. 张敬波等.半导体学报，第21卷第3期. 2000 * |
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