CN1203155C - Water heat systhesis method for preparing phosphide nanometre wire - Google Patents
Water heat systhesis method for preparing phosphide nanometre wire Download PDFInfo
- Publication number
- CN1203155C CN1203155C CN 03131771 CN03131771A CN1203155C CN 1203155 C CN1203155 C CN 1203155C CN 03131771 CN03131771 CN 03131771 CN 03131771 A CN03131771 A CN 03131771A CN 1203155 C CN1203155 C CN 1203155C
- Authority
- CN
- China
- Prior art keywords
- metal oxide
- phosphide
- water
- added
- product
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The present invention discloses a water-heating synthesis method for preparing a nanometer phosphide wire, which relates to a method for preparing a luminescent material of metal phosphide. The method comprises: metal oxide and sodium hydroxide are added to an autoclave according to the molar ratio of 1: 8, wherein the metal oxide is gallium phosphide or indium phosphide; water is added to make the concentration of the sodium hydroxide reach 0.4 mol/L, and after solid is completely dissolved, hexadecanetrimethyl ammonium bromide (C16H33 (CH3)3Nbr)is added, and the molar ratio of the hexadecyltrimethylammonium bromide is 2 times to 4 times of that of the metal oxide; hexyl ethanol and heptane are added, and the volume ratio of the hexyl alcohol to the heptane to the water is 30: 3: 10; after the mixture is uniformly stirred, and white phosphorus with 5 times of the molar ratio of the metal oxide and simple substance iodine (I2) with 2 times of the molar ratio of the metal oxide are added; the mixture reacts in a closed condition at temperature of 160 to 200 DEG C for 24 to 48 hours, and a coarse product is obtained after the mixture is filtered; the coarse product is normally washed and dried by benzene, ethanol, 1 to 5 mol/L of diluted hydrochloric acid and water in turn. Finally, the nanometer phosphide wire is obtained, wherein the errors of the proportion and multiple are 10%.
Description
One, technical field:
The invention belongs to the hydro-thermal synthetic preparation method technical field, particularly relate to the preparation method of metal phosphide luminescent material.
Two, background technology:
Nanometer gallium phosphide, indium phosphide are having a wide range of applications aspect photodiode, light-filter, super ionic material and the semiconductor material.Their nano wire has the potential application prospect as the minimum unit of electric transmission." chemical physics wall bulletin " (Chemistry Physical Letters, 2003 the 367th volume 717-722 pages or leaves) reported the synthetic gallium phosphide nano wire of vapour deposition process, and products therefrom is impure.U.S.'s " physical chemistry magazine " (Journal of Physical Chemistry B, calendar year 2001 the 105th volume 4062-4064 page or leaf) reported laser catalytic growth indium phosphide nano line, but this method needs complicated synthesis device, and cost is very high, is difficult to realize scale operation.Britain's " chemical communication " (Chemical Commnunications, 2564-2565 page or leaf in 2002), Germany " advanced material " (Advanced Msterials, 2000 the 12nd volume 1346-1348 pages or leaves), Britain's " nature material " (Nature Materials, 2003 the 2nd volume 155-158 pages or leaves) reported respectively by distillation GaP powder, carbon nanotube template and with the TOPO reduction method and prepared gallium phosphide, indium phosphide nano line or nanometer rod, but used temperature of reaction height, raw material is not easy to obtain, the cost costliness is difficult to realize producing in batches." JACS " (Journal of the American Chemical Society, 2002 the 124th volume 13656-13657 pages or leaves) reported with the synthetic gallium phosphide nanometer rod of metal organic precursor thing method, but the used metal organic precursor thing synthesis condition of this method is very harsh, severe toxicity, and extremely responsive to air; Simultaneously, the metallic compound of organic phosphine or phosphorus is severe toxicity and to air and its sensitivity of water electrode mostly, be difficult to enlarge produces.U.S.'s " science " (Science, nineteen ninety-five the 270th is rolled up the 1791-1793 page or leaf) though the method cost and the clean aspect of the solution-liquid phase-solid phase synthesis indium phosphide nano fiber of report are more satisfactory, but products therefrom size heterogeneity is unfavorable for the application of its semiconductor light emitting performance.
Three, summary of the invention:
1, technical problem
The objective of the invention is to propose a kind of in hydrothermal system the hydro-thermal synthetic preparation method of the phosphide nano wire under lesser temps and the lower pressure, to overcome in the existing method or to use organometallics presoma or starting material and the equipment cost costliness or the uneven first-class defective of product particle size of severe toxicity.
2, technical scheme
The hydro-thermal synthetic preparation method of phosphide nano wire of the present invention is: the mol ratio according to 1: 8 in autoclave adds metal oxide and sodium hydroxide, wherein metal oxide is gallium oxide or Indium sesquioxide, adds entry again and makes concentration sodium hydroxide reach 0.4mol/L; After dissolving fully to solid, add 2 times of cetyl trimethylammonium bromide (C of metal oxide to 4 times of mol ratios
16H
33(CH
3)
3NBr), adding with water volume ratio is 30: 3: 10 n-hexyl alcohol and heptane again; After stirring, add the white phosphorus of 5 times of mol ratios of metal oxide, the iodine (I of 2 times of mol ratios
2), make in confined conditions to be reflected at and carried out under 160-200 ℃ 24-48 hour, filter and promptly obtain crude product; Crude product is carried out routine washing, drying successively with benzene, ethanol, 1-5mol/L dilute hydrochloric acid, water, promptly obtain product, wherein the error of each ratio and multiple equal 10%.Mechanism of the present invention is: metal oxide (M
2O
3) under the effect of NaOH, generate M (OH)
4 -, can with tensio-active agent cetyl trimethylammonium bromide (C
16H
33(CN
3)
3NBr) form inorganic-surfactant intercalated compound, can curl in subsequent reactions becomes the tubulose microreactor, the target product material grow nanowire that the control reaction generates.
The principal reaction that relates among the preparation method of the present invention has:
The present invention adopts cetyl trimethylammonium bromide (C
16H
33(CH
3)
3NBr) as the M (OH) that produces in tensio-active agent and the reaction
4 -Forming inorganic-surfactant intercalated compound is the key in the building-up process.
The diameter of nano wire can be by regulating cetyl trimethylammonium bromide (C
16H
33(CH
3)
3Experiment parameters such as consumption NBr), temperature of reaction, reaction times change: cetyl trimethylammonium bromide (C
16H
33(CH
3)
3When consumption NBr) strengthens, M (OH)
4 -It is sparse to distribute in inorganic-surfactant intercalated compound, reaction grow nanowire starving, and nanowire diameter reduces; When temperature of reaction raise, nanowire growth was accelerated, and diameter increases; The reaction times overtime, nanowire growth is complete, and diameter increases.
Because the exciton Bohr radius of indium phosphide InP is 20nm, so when nanowire diameter when exciton Bohr radius (20nm) is following, the diameter of nano wire is more little, quantum size effect is obvious more, the bandwidth blue shift is big more, and the bandwidth (1.42-1.59eV) of product InP nano wire can change along with its diameter (8-20nm).But the exciton Bohr radius of gallium phosphide GaP is 5.5nm, and the diameter of gained nano wire is difficult in below the exciton Bohr radius (5.5nm), so no tangible quantum size effect, the bandwidth of product GaP nano wire can not change along with its diameter.For preventing that reaction system is subjected to the autoclave material contamination to introduce impurity, the general autoclave that tetrafluoroethylene or quartz lining are arranged that adopts.
3, beneficial effect
Adopt the inventive method to prepare the metal phosphide nano wire, have the following advantages:
Because the present invention adopts the method for carrying out solid-liquid reaction in hydrothermal system, thereby can be under lower temperature, use conventional equipment to realize the preparation of metal phosphide luminescent material, and can avoid using severe toxicity, be difficult to synthetic organometallics presoma and expensive starting material.The present invention uses, and inorganic-surfactant intercalated compound is reactant and microreactor, makes products obtained therefrom particle size homogeneous.Gained indium phosphide nano linear diameter (8-20nm) and semi-conductor bandwidth (1.42-1.59eV) are adjustable, can make the luminescent material of different bandwidth.
Four, description of drawings:
Fig. 1 carries out the style that XRD analysis obtained for product GaP, the InP to the present invention's preparation:
Fig. 2 A is the photo of product 10nmGaP nano wire of the present invention; B is the photo of product 10nmInP nano wire of the present invention; C is the photo and the electron diffraction pattern of product 10nmGaP nano wire of the present invention; D is the photo and the electron diffraction pattern of product 10nmInP nano wire of the present invention;
Fig. 3 A is the photoluminescence spectrogram of product 10nmGaP nano wire of the present invention; Fig. 3 B is the photoluminescence spectrogram of product 10nmInP nano wire of the present invention; Fig. 3 C is the photoluminescence spectrogram of the InP nano wire of product different diameter of the present invention;
Fig. 4 A is the photo of product 8nmInP nano wire of the present invention; Fig. 4 B is the photo of product 15nmInP nano wire of the present invention; Fig. 4 C is the photo of product 20nmInP nanowire of the present invention.
Five, embodiment:
Embodiment 1:
In being lined with the autoclave of tetrafluoroethylene, add 12mmol NaOH and 1.5mmol Ga
2O
3Or In
2O
3, add 30mL water again; After dissolving fully to solid, add 3mmol cetyl trimethylammonium bromide (C
16H
33(CH
3)
3NBr), 3mL n-hexyl alcohol, 10mL heptane; Stir after 20 minutes, add 1g white phosphorus, 0.75g iodine (I
2), sealing autoclave was in 160 ℃ of following constant temperature 24 hours; Products therefrom is respectively washed 2 times successively with benzene, alcohol, dilute hydrochloric acid (1mol/L), water, places vacuum drying oven, 60 ℃ of dryings 4 hours, promptly gets the product powder.
Adopt commentaries on classics target X-ray powder diffraction (XRD), field emission scanning electron microscope (FE-SEM), high resolution transmission electron microscopy (HRTEM), electron diffraction (ED) and photoluminescence spectrum (PL) that the product that obtains in the foregoing description is characterized.
The product powder X-ray RD style A that Fig. 1 provides, B explanation product is GaP, the InP of zink sulphide phase;
FE-SEM photo Fig. 2 A, B show that GaP, the InP of product zink sulphide phase are diameter 10nm, the nano wire of long 6 μ m.
HRTEM photo and electron diffraction pattern Fig. 2 C, D proof product GaP, the crystallization of InP nano wire are good, along [111] and [111] oriented growth;
Photoluminescence spectrum Fig. 3 A of product, B show that the gained material has good luminous property, and bandwidth is respectively 2.79eV, and 1.55eV is excellent phosphor.
Embodiment 2:
In being lined with the autoclave of tetrafluoroethylene, add .12mmol NaOH and 1.Smmol In
2O
3, add 30mL water again; After dissolving fully to solid, add 6mmol cetyl trimethylammonium bromide (C
16H
33(CH
3)
3NBr), 3mL n-hexyl alcohol, 10mL heptane; Stir after 20 minutes, add 0.5g white phosphorus, 0.37g iodine (I
2), sealing autoclave was in 160 ℃ of following constant temperature 24 hours; Products therefrom is respectively washed 2 times successively with benzene, ethanol, dilute hydrochloric acid (1mol/L), water, places vacuum drying oven, 60 ℃ of dryings 4 hours, promptly gets the product powder.
Adopt commentaries on classics target X-ray powder diffraction (XRD), transmission electron microscope (TEM) and photoluminescence spectrum (PL) that the product that obtains in the foregoing description is characterized.
Product powder X-ray RD style is consistent with Figure 1B, illustrates that product is the InP of zink sulphide phase;
TEM photo Fig. 4 A shows that the InP of product zink sulphide phase is the nano wire of diameter 8nm.
Photoluminescence spectrum Fig. 3 C of product shows that the gained material has good luminous property, and bandwidth is 1.59eV, is excellent phosphor.
Embodiment 3:
In being lined with the autoclave of tetrafluoroethylene, add 12mmol NaOH and 1.5mmol In
2O
3, add 30mL water again; After dissolving fully to solid, add 3mmol cetyl trimethylammonium bromide (C
16H
33(CH
3)
3NBr), 3mL n-hexyl alcohol, 10mL heptane; Stir after 20 minutes, add 1g white phosphorus, 0.75g iodine (I
2), sealing autoclave was in 160 ℃ of following constant temperature 48 hours; Products therefrom is respectively washed 2 times successively with benzene, alcohol, dilute hydrochloric acid (1mol/L), water, places vacuum drying oven, 60 ℃ of dryings 4 hours, promptly gets the product powder.
Adopt commentaries on classics target X-ray powder diffraction (XRD), field emission scanning electron microscope (FE-SEM) and photoluminescence spectrum (PL) that the product that obtains in the foregoing description is characterized.
Product powder X-ray RD style is consistent with Figure 1B, illustrates that product is the InP of zink sulphide phase;
FE-SEM photo Fig. 4 B shows that the InP of product zink sulphide phase is the nano wire of diameter 15nm.
Photoluminescence spectrum Fig. 3 C of product shows that the gained material has good luminous property, and bandwidth is 1.46eV, is excellent phosphor.
Embodiment 4:
In being lined with the autoclave of tetrafluoroethylene, add 12mmol NaOH and 1.5mmol In
2O
3, add 30mL water again; After dissolving fully to solid, add 3mmol cetyl trimethylammonium bromide (C
16H
33(CH
3)
3NBr), 3mL n-hexyl alcohol, 10mL heptane; Stir after 20 minutes, add 1g white phosphorus, 0.75g iodine (I
2), sealing autoclave was in 200 ℃ of following constant temperature 24 hours; Products therefrom is respectively washed 2 times successively with benzene, ethanol, dilute hydrochloric acid (1mol/L), water, places vacuum drying oven, 60 ℃ of dryings 4 hours, promptly gets the product powder.
Adopt commentaries on classics target X-ray powder diffraction (XRD), field emission scanning electron microscope (FE-SEM) and photoluminescence spectrum (PL) that the product that obtains in the foregoing description is characterized.
Product powder X-ray RD style is consistent with Figure 1B, illustrates that product is the InP of zink sulphide phase;
FE-SEM photo Fig. 4 C shows that the InP of product zink sulphide phase is the nano wire of diameter 20nm.
Photoluminescence spectrum Fig. 3 C of product shows that the gained material has good luminous property, and bandwidth is 1.42eV, is excellent phosphor.
The result of above embodiment proves that the diameter of InP nano wire (8-20nm) can be by regulating cetyl trimethylammonium bromide (C
16H
33(CH
3)
3Experiment parameters such as consumption NBr), temperature of reaction, reaction times change, and the semi-conductor bandwidth (1.42-1.59eV) of gained indium phosphide nano line can change along with diameter (8-20nm).The present invention is also applicable to other metal phosphide.
Claims (1)
1, a kind of hydro-thermal synthetic preparation method of phosphide nano wire is characterized in that: the mol ratio according to 1: 8 in autoclave adds metal oxide and sodium hydroxide, adds entry again and makes concentration sodium hydroxide reach 0.4mol/L; After dissolving fully to solid, add 2 times of cetyl trimethylammonium bromides to 4 times of mol ratios of metal oxide, adding with water volume ratio is 30: 3: 10 n-hexyl alcohol and heptane again; After stirring, add the white phosphorus of 5 times of mol ratios of metal oxide, the iodine of 2 times of mol ratios, make in confined conditions to be reflected at and carried out under 160-200 ℃ 24-48 hour, filter and obtain crude product; Crude product is carried out routine washing, drying successively with benzene, ethanol, 15mol/L dilute hydrochloric acid, water, and wherein the error of each ratio and multiple is 10%, and described metal oxide is gallium oxide or Indium sesquioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03131771 CN1203155C (en) | 2003-07-28 | 2003-07-28 | Water heat systhesis method for preparing phosphide nanometre wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03131771 CN1203155C (en) | 2003-07-28 | 2003-07-28 | Water heat systhesis method for preparing phosphide nanometre wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1482207A CN1482207A (en) | 2004-03-17 |
| CN1203155C true CN1203155C (en) | 2005-05-25 |
Family
ID=34153866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03131771 Expired - Fee Related CN1203155C (en) | 2003-07-28 | 2003-07-28 | Water heat systhesis method for preparing phosphide nanometre wire |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1203155C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268543C (en) | 2004-05-11 | 2006-08-09 | 湖南大学 | Method for preparing self assembled growth silicon nano-tube and silicon nano-line by hydrothermal method |
| CN100357023C (en) * | 2005-07-28 | 2007-12-26 | 中国科学院大连化学物理研究所 | Method for preparing metal ruthenium nano-wire |
| CN113363464A (en) * | 2021-06-08 | 2021-09-07 | 广东工业大学 | Gallium-silicon-phosphorus composite negative electrode active material, lithium ion battery, and preparation method and application thereof |
-
2003
- 2003-07-28 CN CN 03131771 patent/CN1203155C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1482207A (en) | 2004-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1263677C (en) | Preparation for composite material with nanometal or metal oxide distributed on surface of carbon nanotube uniformly | |
| CN1182038C (en) | Synthesis process of nanostring and nanopowder of RE hydroxide or oxide | |
| Chen et al. | Facile synthesis of CdS/C core–shell nanospheres with ultrathin carbon layer for enhanced photocatalytic properties and stability | |
| CN1817799A (en) | Synthesis of TiO2 nanometer particles and bars | |
| CN1903728A (en) | Preparation method of high purity aluminium oxide powder | |
| Cai et al. | Solvothermal synthesis and characterization of zinc indium sulfide microspheres | |
| CN101607689B (en) | Zinc oxide and zinc sulfide nano-belt composite heterogenous junction material and preparation method | |
| CN1203155C (en) | Water heat systhesis method for preparing phosphide nanometre wire | |
| Qian et al. | Controlled synthesis of light rare-earth hydroxide nanorods via a simple solution route | |
| CN110681395A (en) | Cu with adjustable appearance and size+Doping with W18O49Composite material and preparation method thereof | |
| Yu et al. | Precursor induced synthesis of hierarchical nanostructured ZnO | |
| CN107840366B (en) | BiOX micron rod with exposed (110) crystal face and synthesis method thereof | |
| Liu et al. | Control to synthesize Bi2S3 nanowires by a simple inorganic-surfactant-assisted solvothermal process | |
| Xie et al. | Solvothermal preparation of tin phosphide nanorods | |
| CN1235808C (en) | Method for preparing zine sulfide nanometer material with orientation arrangement nano-tubes | |
| CN1673091A (en) | Prepn process of nano copper iodide powder | |
| CN1256274C (en) | Nano phosphide semconductor material hydrothermal synthesis preparing method | |
| Lu et al. | “Scission–template–transportation” route to controllably synthesize CdIn 2 S 4 nanorods | |
| Jiang et al. | Room temperature preparation of novel Cu2− xSe nanotubes in organic solvent | |
| CN1287012C (en) | Large scale in situ preparation method of ternary NaV6O15 single crystal nanometer needle | |
| CN1171797C (en) | Process for synthesizing alpha, beta type lead dioxide and leadleaden oxide naon crystal | |
| CN1291909C (en) | Hot synthetic preparation of metastable rock salt phase nano gallium nitride in solvent | |
| CN115974130B (en) | Samarium hydroxychloride nano material and preparation method thereof | |
| Villalobos et al. | Synthesis and characterization of 1D metal oxide nano-structures: titanium dioxide nanotubes (TNTs) and zinc oxide nanobars (ZNBs) | |
| CN102220641B (en) | Synthesis method of monoclinic crystal phase rare-earth iso-oxy-sulfur superfine nanowire and wire-based superstructure |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |