CN101891898A - Organic nano molybdenum-sodium metal compound polymer and preparation method and application thereof - Google Patents
Organic nano molybdenum-sodium metal compound polymer and preparation method and application thereof Download PDFInfo
- Publication number
- CN101891898A CN101891898A CN2009100847746A CN200910084774A CN101891898A CN 101891898 A CN101891898 A CN 101891898A CN 2009100847746 A CN2009100847746 A CN 2009100847746A CN 200910084774 A CN200910084774 A CN 200910084774A CN 101891898 A CN101891898 A CN 101891898A
- Authority
- CN
- China
- Prior art keywords
- sodium
- molybdenum
- organic
- solvent
- nanometer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses an organic nano molybdenum-sodium metal compound polymer and a preparation method and application thereof. The molecular formula of the polymer is {[NH3CH2CH(NH2)CH3](C6H4O2)[mu 2-OC6H4O](Mo-O-Na-O)[NH2CH2CH(NH2)CH3]}n, wherein n is 1 or any integer more than 1. The polymer is shaped like nano wires and nano sheets, wherein the diameter of the nano wires is 1-100nm and the length of the nano wires is 1-10<10>nm; and the length and the width of the nano sheets are 1-10<10>nm. The preparation method comprises the following steps: taking the mixture of sodium-molybdenum-bearing compounds or sodium salt and molybdenum-bearing compounds as the substrate, subjecting the substrate to react with an organic ligand in a solvent to obtain organic molybdenum-sodium metal hybrid crystals and then carrying out grinding and ultrasonic processing on the hybrid crystals, thus obtaining the polymer. The raw materials for preparation are low in price, the preparation process is simple and each step is easy to realize and the yield is high.
Description
Technical field
The present invention relates to the nano-high molecule polymkeric substance, relate in particular to organic cooperation polymkeric substance of molybdenum sodium metal that is nano wire and nanometer sheet pattern and its production and application, belong to the nano-high molecule polymer arts.
Background technology
The yardstick of material and form affect Substance Properties dramatically.Nano material is meant that yardstick is the material of 1～100nm, the branch that zero dimension, a peacekeeping two dimension are arranged, compare with three-dimensional block materials, because the Idiotype of its pattern, the small-size effect of nanoparticle and specific surface effect etc., make it demonstrate the character that many conventional particles do not have at aspects such as magnetic, light, electricity, heat, catalysis and medicines, show special physical and chemical performance, diving in fields such as Preparation of Catalyst, photoelectromagnetism material and medicine are synthetic has important use to be worth.
The molybdenum nanotechnology is a new and high technology that grows up for 20 end of the centurys, the development of molybdenum nanoscale goods is very rapid (opens civilian bell-shaped percussion instrument, used in ancient time by troops on march, molybdenum based nano-material research and development present situation, [J]. the China molybdenum industry, 2005,29 (1): 4-10), up to now, work out nano level molybdenumdisulphide both at home and abroad and (opened civilian bell-shaped percussion instrument, used in ancient time by troops on march, the research and development present situation of nano level molybdenumdisulphide, [J]. China molybdenum industry, 2000,24 (5): 23-26), nano-scale molybdenum powder, nano level molybdic oxide, nanometer level molybdate, nano level carbonization thing or the like, almost relate to the every field relevant with molybdenum.Yet, the research of molybdenum nano level science and technology, still there are many basic knowledge topics to need bright and limpid, mechanism as nano material molybdenum compound and complex molecule self-assembly, based on constructing of molybdenum oxide compound, molybdenum compound and molybdenum organic coordination compound nano-device, assembling of multi-level nanostructure or the like.And, based on the preparation of the nano wire of molybdenum sodium metal organic hybrid material and nanometer sheet with assemble rare report.
Summary of the invention
One of purpose of the present invention provides a kind of organic nano molybdenum-sodium metal compound polymer;
Two of purpose of the present invention provides a kind of method for preparing above-mentioned organic nano molybdenum-sodium metal compound polymer;
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of organic nano molybdenum-sodium metal compound polymer, its molecular chemistry formula is: { [NH
3CH
2CH (NH
2) CH
3] (C
6H
4O
2) [μ
2-OC
6H
4O] (Mo-O-Na-O) [NH
2CH
2CH (NH
2) CH
3]
n, n is any integer more than 1 or 1; Preferably, n is 1 to 1x10
10Any integer.Its structural formula is shown in Figure 1.
Organic nano molybdenum-sodium metal compound polymer of the present invention has nano wire and nanometer sheet yardstick and pattern, and described nanowire diameter is the 1-100 nanometer, and nanowire length is 1 nanometer to 10
10Nanometer; Described nanometer length of a film and wide 1 nanometer to 1010 nanometer that is.
Another object of the present invention provides a kind of method for preparing above-mentioned organic nano molybdenum-sodium metal compound polymer.
A kind of method for preparing above-mentioned organic nano molybdenum-sodium metal compound polymer, comprise: to contain the sodium molybdenum compound or to be that substrate and organic ligand react in solvent and obtain molybdenum sodium metal organic hybrid crystal with the mixture of sodium salt and molybdate compound, again through grinding and ultrasonic, promptly;
Wherein, the described sodium molybdenum compound that contains is preferably Sodium orthomolybdate.
Described sodium salt can be preferably sodium-chlor, SODIUMNITRATE, sodium sulfate, sodium oxalate etc. for all inorganic or organic sodium salts.
Described molybdate compound is preferably all molybdate compounds such as molybdic oxide, moly-sulfide, ammonium molybdate, ammonium thiomolybdate, positive tetrabutyl ammonium octamolybdate, the positive tetrabutyl six ammonium molybdates, positive tetrabutyl Ammonium Heptamolybdate, two ammonium molybdate, hexacarbonylmolybdenum or six molybdenum chlorides.
Described organic ligand is 1, the 2-propylene diamine, and the single of optional position replaces or polysubstituted substitutive derivative on pyrocatechol or its phenyl ring; Wherein, described replacement comprises that C1-C4 alkyl or halogen replace.
Described solvent is selected from the mixed organic solvents of one or more arbitrary proportions in the organic solvent (for example methyl alcohol, acetonitrile, acetone), perhaps inorganic solvent (for example water), the perhaps mixed solvent of organic and inorganic arbitrary proportion.Preferably, described solvent is the mixed solvent of methyl alcohol and acetonitrile arbitrary proportion, and is preferred, is methyl alcohol and the mixed solvent of acetonitrile equal-volume ratio.Preferably, the weight of substrate is 0.2-0.6g: 10-30ml with the ratio of the volume of solvent.
Concrete, the synthetic method of organic nano molybdenum-sodium metal compound polymer of the present invention can adopt the normal temperature solution synthetic method, comprising:
1. under the normal temperature, be substrate, place container, in solvent, be positioned on the magnetic stirrer and react with organic ligand with the mixture that contains sodium molybdenum compound or sodium salt and molybdate compound;
2. reacted solution is filtered, then clarifying mother liquor is placed container;
3. leave standstill (to-15 ℃ temperature, all can meet the demands), separate out crystal in the container in room temperature;
4. draw out crystal, promptly.。
Preferably, after clarified mother liquor is placed container, described leave standstill step before, above mother liquor, slowly add organic solvents such as the ether of arbitrary volume ratio or sherwood oil.The effect that adds ether is in order to promote product to separate out as early as possible, and when not adding diethyl ether, product is separated out slower, does not influence the result.
The preparation method of organic nano molybdenum-sodium metal compound polymer of the present invention can also adopt hydro-thermal and solvent thermal synthesis method, comprising:
1. be substrate with the mixture that contains sodium molybdenum compound or sodium salt and molybdate compound, put into autoclave, autoclave is put into baking oven with organic ligand and solvent;
2. baking oven is provided with differing temps, range of temperature is 30-180 ℃, isothermal reaction; Cool to room temperature then;
3. solution is taken out, will precipitate respectively with mother liquor and handle, at first draw out the crystal of having separated out in the autoclave, this is a part of product, then mother liquor is filtered, and clarifying mother liquor is placed container;
4. leave standstill (room temperature to-15 ℃ the temperature all can), separate out crystal in the container, promptly;
Preferably, after clarified mother liquor is placed container, described leave standstill step before, above mother liquor, slowly add organic solvents such as the ether of arbitrary volume ratio or sherwood oil.The effect that adds ether is in order to promote product to separate out as early as possible, and when not adding diethyl ether, product is separated out slower, does not influence the result.
Two, grind
Above-mentioned crystal is ground grind into powder.Grinding can be adopted grinding plant commonly used such as ball mill or agate mortar.
Three, ultrasonic separation
Above-mentioned powder is put into container, and add organic solvents commonly used such as an amount of ether or sherwood oil, institute's solubilization dosage exceeds not have all powder, places ultrasonic instrument to carry out ultrasonic separation.Powder after the ultrasonic separation is product of the present invention: be the molybdenum sodium metal organic hybrid material of nano wire and nanometer sheet pattern, productive rate is more than 80%.
Beneficial effect of the present invention is: the molybdenum sodium metal organic hybrid material preparation cost of material that is nano wire and nanometer sheet pattern is cheap, prepare nano wire from the one-dimensional chain polymer molecule, draw nanometer sheet by being arranged in parallel of nano wire then, controllable product shape (that is: prepare nano wire from the one-dimensional chain polymer molecule, draw nanometer sheet by being arranged in parallel of nano wire then).Preparation technology is simple, and each step all is easy to realize and the productive rate height.
Description of drawings
Fig. 1 is the molecular structure of the basic structural unit of organic nano molybdenum-sodium metal compound polymer of the present invention.
Fig. 2 is the packing of molecules figure of organic nano molybdenum-sodium metal compound polymer of the present invention.
Fig. 3 is the transmission electron microscope picture of nano wire pattern for organic nano molybdenum-sodium metal compound polymer of the present invention.
Fig. 4 is the transmission electron microscope picture of nanometer sheet pattern for organic nano molybdenum-sodium metal compound polymer of the present invention.
Embodiment
The invention will be further described below in conjunction with embodiment, it should be understood that these embodiment only are used for the purpose of illustration, never limit protection scope of the present invention.
Embodiment 1
Take by weighing 0.3 gram Sodium orthomolybdate and 0.8 gram pyrocatechol respectively and put into the round-bottomed flask of 50ml, in flask, add 1 successively then, 2-propylene diamine 8ml (density 0.87g/ml), acetonitrile 10ml, anhydrous methanol 10ml stirred 1 hour on magnetic stirring apparatus.Reaction solution is filtered with glass funnel, filtrate is placed test tube, carry out the layering diffusion with the 10ml ether.Left standstill under the room temperature 1 hour, test tube wall and bottom have red crystals to generate.This crystalline X-single crystal diffraction structure elucidation data see Table 1, and used instrument is the ApexII single crystal diffractometer of Brooker company.
The X-single crystal diffraction structure elucidation data of table 1 polymer crystals of the present invention
Its molecular structural formula and packing of molecules figure see Fig. 1 and Fig. 2 respectively.Above-mentioned crystal is drawn out, air-dry, put into agate mortar and carry out grind into powder.Above-mentioned powder is put into the container that fills ether, place ultrasonic device, carry out ultrasonic separation.The powder that obtains is product, and productive rate is more than 80%.The transmission electron microscope picture of its nanotopography is seen Fig. 3 and Fig. 4 respectively.As seen this molybdenum sodium metal organic hybrid material that is nano wire and nanometer sheet pattern has nano wire and nanometer sheet pattern, and nanowire diameter is the 1-100 nanometer, and nanowire length is 1 nanometer to 10
10Nanometer, the nanometer sheet length and width is 1 nanometer to 10
10Nanometer; The n value is different and different with the length of nano wire.
Embodiment 2
Take by weighing the positive tetrabutyl ammonium octamolybdate salt of 0.4 gram, 0.1 gram sodium-chlor and 0.8 gram pyrocatechol are put into the round-bottomed flask of 50ml, add 1 successively in flask then, 2-propylene diamine 8ml (density 0.87g/ml), acetonitrile 10ml, anhydrous methanol 10ml stirred 2 hours on magnetic stirring apparatus.Reaction solution is filtered with glass funnel, filtrate is placed test tube, carry out the layering diffusion with the 20ml ether.Leave standstill under the room temperature more than 2 hours, test tube wall and bottom have red crystals to generate.Its molecular structural formula and packing of molecules figure see Fig. 1 and Fig. 2 respectively.X-single crystal diffraction structure elucidation data see Table 1.
Fig. 1 is the basic structural unit { [NH that constructs organic nano molybdenum-sodium metal compound polymer of the present invention
3CH
2CH (NH
2) CH
3] (C
6H
4O
2) [μ
2-OC
6H
4O] (Mo-O-Na-O) [NH
2CH
2CH (NH
2) CH
3] molecular structural formula; Fig. 2 is the arrangement mode of organic nano molybdenum-sodium metal compound polymer of the present invention on the bc crystal face.
Above-mentioned crystal is drawn out, air-dry, carry out grind into powder with ball mill.Above-mentioned powder is put into the container that fills ether, place ultrasonic device, carry out ultrasonic separation.The powder that obtains is product, and productive rate is more than 80%.The transmission electron microscope picture of its nanotopography is seen Fig. 3 and Fig. 4.As seen this molybdenum sodium metal organic hybrid material that is nano wire and nanometer sheet pattern has nano wire and nanometer sheet pattern, and nanowire diameter is the 1-100 nanometer, nanowire length 1 nanometer to 10
10Nanometer, the nanometer sheet length and width is 1 nanometer to 10
10Nanometer; The n value is different and different with the length of nano wire.
The above only is preferred embodiment of the present invention, only is illustrative for the purpose of the present invention, and nonrestrictive.Those skilled in the art is understood, and can carry out many changes to it in the spirit and scope that claim of the present invention limited, revise, even equivalence, but all will fall within the scope of protection of the present invention.
Claims (10)
1. organic nano molybdenum-sodium metal compound polymer, its molecular formula is: { [NH
3CH
2CH (NH
2) CH
3] (C
6H
4O
2) [μ
2-OC
6H
4O] (Mo-O-Na-O) [NH
2CH
2CH (NH
2) CH
3]
n, wherein, n is any integer more than 1 or 1.
2. according to the described organic nano molybdenum-sodium metal compound polymer of claim 1, it is characterized in that: n is 1 to 1x10
10Any integer.
3. according to claim 1 or 2 described organic nano molybdenum-sodium metal compound polymers, it is characterized in that: it is nano wire and nanometer sheet pattern.
4. according to the described organic nano molybdenum-sodium metal compound polymer of claim 3, it is characterized in that: described nanowire diameter is the 1-100 nanometer, and nanowire length is 1 nanometer to 10
10Nanometer; Described nanometer length of a film and wide 1 nanometer to 10 that is
10Nanometer.
5. method for preparing claim 1 or 2 described organic nano molybdenum-sodium metal compound polymers, may further comprise the steps: with the mixture that contains sodium molybdenum compound or sodium salt and molybdate compound is substrate and organic ligand synthetic molybdenum sodium metal organic hybrid crystal that obtains in solvent, again through grinding and ultrasonic, promptly.
6. it is characterized in that in accordance with the method for claim 5: the described sodium molybdenum compound that contains is a Sodium orthomolybdate;
Described sodium salt is inorganic or organic sodium salt;
Described molybdate compound is selected from molybdic oxide, moly-sulfide, ammonium molybdate, ammonium thiomolybdate, positive tetrabutyl ammonium octamolybdate, the positive tetrabutyl six ammonium molybdates, positive tetrabutyl Ammonium Heptamolybdate, two ammonium molybdate, hexacarbonylmolybdenum or six molybdenum chlorides;
Described organic ligand is by 1, and 2-propylene diamine and pyrocatechol are formed; Or by 1, single replacement in optional position or polysubstituted substitutive derivative are formed on the phenyl ring of 2-propylene diamine and pyrocatechol, and described replacement comprises with C1-C4 alkyl or halogen and replacing;
Described solvent is selected from the mixed organic solvents of one or more arbitrary proportions in the organic solvent, or inorganic solvent, or by organic mixed solvent of forming by arbitrary proportion with inorganic solvent.
7. want 6 described methods according to right, it is characterized in that: described sodium salt is selected from sodium-chlor, SODIUMNITRATE, sodium sulfate or sodium oxalate; Described solvent is taken over the mixing solutions that the meaning ratio is formed by acetonitrile and methyl alcohol.
8. method for preparing claim 1 or 2 described organic nano molybdenum-sodium metal compound polymers may further comprise the steps:
A. under the normal temperature, be substrate, place container, in solvent, be positioned on the magnetic stirring apparatus and react with organic ligand with the mixture that contains sodium molybdenum compound or sodium salt and molybdate compound;
B. resulting solution is filtered, the filtrate room temperature is left standstill to-15 ℃ temperature, separate out crystal, promptly.
9. a method for preparing claim 1 or 2 described organic nano molybdenum-sodium metal compound polymers comprises the steps:
A. be substrate with the mixture that contains sodium molybdenum compound or sodium salt and molybdate compound, put into autoclave, autoclave is put into baking oven with organic ligand and solvent;
B. baking oven is provided with differing temps, range of temperature is the 30-180 degree, isothermal reaction; Cool to room temperature then;
C. solution is taken out, will precipitate respectively with mother liquor and handle; Draw out the crystal of having separated out in the autoclave, this is a part of product; Then mother liquor is filtered, the filtrate room temperature is left standstill to-15 ℃ temperature, separate out crystal, promptly.
10. according to claim 8 or 9 described methods, it is characterized in that: after clarified mother liquor is placed container, described leave standstill step before, above mother liquor, slowly add the organic solvent of arbitrary volume ratio; Wherein, described organic solvent is preferably ether or sherwood oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910084774A CN101891898B (en) | 2009-05-19 | 2009-05-19 | Organic nano molybdenum-sodium metal compound polymer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910084774A CN101891898B (en) | 2009-05-19 | 2009-05-19 | Organic nano molybdenum-sodium metal compound polymer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101891898A true CN101891898A (en) | 2010-11-24 |
| CN101891898B CN101891898B (en) | 2012-09-26 |
Family
ID=43101265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910084774A Expired - Fee Related CN101891898B (en) | 2009-05-19 | 2009-05-19 | Organic nano molybdenum-sodium metal compound polymer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101891898B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634944A (en) * | 2004-12-02 | 2005-07-06 | 首都师范大学 | Molybdenum, wolfram, molybdenum and wolfram complex, method for making and use in preparing anticancer, antitumor medicament |
| CN1786008A (en) * | 2005-11-30 | 2006-06-14 | 首都师范大学 | Preparation method of low dimension molybdenum match crystal |
| CN101172659A (en) * | 2007-10-10 | 2008-05-07 | 新疆大学 | Method for producing barium molybdate nano-stick with solid phase chemical reaction |
| CN101376745A (en) * | 2008-10-13 | 2009-03-04 | 复旦大学 | Method for synthesizing molybdena-polyaniline polyaniline composite single crystal nanowire |
-
2009
- 2009-05-19 CN CN200910084774A patent/CN101891898B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634944A (en) * | 2004-12-02 | 2005-07-06 | 首都师范大学 | Molybdenum, wolfram, molybdenum and wolfram complex, method for making and use in preparing anticancer, antitumor medicament |
| CN1786008A (en) * | 2005-11-30 | 2006-06-14 | 首都师范大学 | Preparation method of low dimension molybdenum match crystal |
| CN101172659A (en) * | 2007-10-10 | 2008-05-07 | 新疆大学 | Method for producing barium molybdate nano-stick with solid phase chemical reaction |
| CN101376745A (en) * | 2008-10-13 | 2009-03-04 | 复旦大学 | Method for synthesizing molybdena-polyaniline polyaniline composite single crystal nanowire |
Non-Patent Citations (1)
| Title |
|---|
| 周菊红,王涛,陈友存,等: "水热法合成一维纳米材料的研究进展", 《化学通报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101891898B (en) | 2012-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107486231B (en) | A kind of preparation method of graphite phase carbon nitride colloid photochemical catalyst | |
| Jincheng et al. | Synthesis of hyper-branched quaternary ammonium salt and its application into montmorillonite | |
| CN104479675A (en) | Large-scaled industrial preparation method for fluorescent graphene quantum dot material | |
| CN102963898A (en) | Preparation method of dual-functional group organically modified montmorillonite | |
| CN101311382A (en) | Te/Bi or Te/Bi2Te3 nucleocapsid heterojunction structure nanometer wire and method for preparing same | |
| CN100535022C (en) | Method for preparing polymetallic oxo cluster hybrid polymer microspheres | |
| CN101524762A (en) | Method for preparing ferroplatinum nano-particle | |
| Sanatkar et al. | Dinuclear Zn (II) and tetranuclear Co (II) complexes of a tetradentate N2O2 Schiff base ligand: Synthesis, crystal structure, characterization, DFT studies, cytotoxicity evaluation, and catalytic activity toward benzyl alcohol oxidation | |
| CN108525679A (en) | A method of preparing ZnS quantum dots and redox graphene compound by presoma of metal organic frame | |
| CN109456486A (en) | A kind of multi-functional high temperature resistant POSS nano molecular material and preparation method thereof | |
| CN106966382A (en) | A kind of method of overcritical continuous hydrothermal synthesizing graphite alkene quantum dot | |
| CN111233038A (en) | Spherical molybdenum disulfide, preparation method and application thereof | |
| WO2019037438A1 (en) | Pentamethylenediamine adipate and crystal thereof | |
| CN102502839A (en) | Method for preparing flaky bismuth molybdate nano material with uniform thickness | |
| Boyle et al. | Synthesis and characterization of germanium coordination compounds for production of germanium nanomaterials | |
| CN102941045B (en) | Method for preparing multiple nano-composite balls with uniform size and CdS-C core-shell structures shaped like trivalvular flowers | |
| CN101891898B (en) | Organic nano molybdenum-sodium metal compound polymer and preparation method and application thereof | |
| CN102603787B (en) | Synthesis method of monodisperse bridged polysilsesquioxanes microspheres | |
| CN1786008B (en) | Preparation method of low dimension molybdenum match crystal | |
| Xue et al. | Controlled fabrication of polypyrrole capsules and nanotubes in the presence of Rhodamine B | |
| CN114988498B (en) | Nickel hydroxychloride micron flower and preparation method thereof | |
| Akhbari et al. | Thallium (I) supramolecular polymer with Tl⋯ π secondary interactions; preparation of nano-structures by sonochemical method as a new precursor for preparation of Tl2O3 with nano-structural surface | |
| CN102602983A (en) | Method for solvothermal-method synthesis of zinc oxide nano particle assembly assisted by nitrogen-contained organic micromolecule ligand | |
| CN101973537A (en) | Method for preparing transition metal phosphide | |
| CN104668577B (en) | A kind of nickel micro-and nano-particles and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120926 Termination date: 20150519 |
|
| EXPY | Termination of patent right or utility model |