CN111101192A - Method for preparing single crystal black phosphorus nanowire by using template method - Google Patents
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 233
- 239000002070 nanowire Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000013078 crystal Substances 0.000 title claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- 238000002791 soaking Methods 0.000 claims abstract description 41
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 67
- 238000001035 drying Methods 0.000 claims description 63
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 40
- 239000010453 quartz Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 32
- 229910052782 aluminium Inorganic materials 0.000 description 32
- 238000007789 sealing Methods 0.000 description 18
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 17
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 17
- 238000011049 filling Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- 244000298903 Basella rubra Species 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- 206010034962 Photopsia Diseases 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000065 phosphene Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
Abstract
The invention relates to a method for preparing a single crystal black phosphorus nanowire by using a template method, which comprises the steps of preparing an anodic aluminum oxide template AAO by using an anodic oxidation method, soaking the anodic aluminum oxide template AAO in a copper chloride solution to remove a substrate, mixing the anodic aluminum oxide template AAO with red phosphorus to react, converting the red phosphorus in a cavity into molten white phosphorus, injecting the molten white phosphorus into holes of the AAO, converting the white phosphorus in the holes of the AAO into black phosphorus, and finally dissolving the AAO template by using a NaOH solution to obtain the black phosphorus nanowire. The size of the black phosphorus nanowire is controlled by controlling the hole diameter of the AAO template, the black phosphorus nanowire with different sizes and good uniformity, high crystallinity and stability is synthesized, and the adopted high-temperature and high-pressure technology has the advantages of short time consumption, good controllability, high repeatability, high yield, cleanness, environmental protection, low cost and the like. Not only opens up a new dimension for exploring new characteristics of the black phosphorus material, but also provides a one-dimensional structure engineering strategy for rapid and efficient large-scale manufacturing.
Description
Technical Field
The invention belongs to the field of advanced material synthesis, and relates to a method for preparing a single crystal black phosphorus nanowire by using a template method, in particular to a high-temperature and high-pressure technology for preparing the single crystal black phosphorus nanowire by using a simple, controllable and efficient template.
Background
Two-dimensional layered materials are highly regarded by the research field of semiconductor materials because of their superior and unique properties. In recent years, black phosphenes, which are novel successors of two-dimensional materials, have been obtained from bulk black phosphorus by a lift-off method, and have been widely used in the fields of solar cells, transistors, photodetectors, photocatalysis, supercapacitors, chemical sensors, etc. due to their direct band gap adjustable with the number of layers, high mobility, large specific surface area, and excellent in-plane anisotropy. Meanwhile, the research on black phosphorus is not limited to two-dimensional angles, and researchers have developed other forms of black phosphorus nanostructures, for example, Lee et al successfully prepared black phosphorus nanoparticles with blue and green fluorescent cell imaging effects, see documents: h.u.lee, s.y.park, s.c.lee, s.choi, s.seo, h.kim, j.won, k.choi, k.s.kang, h.g.park, h.s.kim, h.r.an, k.h.jeong, y.c.lee, j.lee, Small 2016,12,214. Zhang et al realized a breakthrough in the preparation of black phosphorus quantum dots, which exhibited more attractive characteristics due to strong quantum confinement and edge effects, see literature: x.zhang, h.xie, z.liu, c.tan, z.luo, h.li, j.lin, l.sun, w.chen, z.xu, l.xie, w.huang, h.zhang, angelw.chem.int.ed.2015, 54,3653. However, the instability of zero-dimensional and two-dimensional black phosphorus prevents the wider practical application of the black phosphorus, and therefore, the development of a novel nano structure of a black phosphorus material with extremely high stability is very important.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of zero-dimensional and two-dimensional black phosphorus instability in practical application, the invention provides the method for preparing the one-dimensional single-crystal black phosphorus nanowire with good stability, high crystallization quality and good uniformity.
Technical scheme
A method for preparing single crystal black phosphorus nanowires by using a template method is characterized by comprising the following steps:
step 1: preparing the anode by adopting an anodic oxidation methodAlumina template AAO with cupric chloride solution CuCl2·5H2Removing the substrate, soaking in phosphoric acid solution, heating in water bath at 0-60 deg.C for less than 100min, reaming, washing the obtained anodic alumina template AAO with distilled water for several times, and drying in a drying oven;
step 2: mixing an anodic alumina template AAO and red phosphorus in a ratio of 1-100: 1, grinding, placing in a sealed quartz tube, and placing in a high-temperature high-pressure instrument for reaction;
1. the reaction time is less than 2 hours at the pressure of 0-4 GPa and the temperature of 200-1200 ℃, so that the red phosphorus in the high-pressure cavity is converted into molten white phosphorus;
2. injecting the molten white phosphorus into the AAO holes of the anodic alumina template under the conditions that the pressure is 0-4 GPa, the temperature is 400-1800 ℃ and the reaction time is less than 2 hours, increasing the temperature to a certain value, and converting the molten white phosphorus in the AAO holes of the anodic alumina template into black phosphorus after reacting for several hours;
and step 3: soaking the amorphous anodic alumina template AAO obtained in the step 2 in NaOH solution for dissolving, wherein the soaking time is 1-100 h; and washing and drying to obtain the black phosphorus nanowire.
The copper chloride solution CuCl2·5H2The concentration of O is 0 to 1 mol/L.
The mass fraction of the phosphoric acid solution is 0-10%.
And the washing times with distilled water in the step 1 are 1-10 times.
And (2) drying in the drying oven in the step (1) at a temperature of less than 100 ℃ for 1-30 h.
The concentration of the NaOH solution in the step 3 is 0-2 mol/L.
And the drying time of the step 3 is 1-10 h.
Advantageous effects
The invention provides a method for preparing a single crystal black phosphorus nanowire by using a template method2·5H2O) removing the substrate, and mixing with cheap and nontoxic redPhosphorus is mixed according to a certain proportion and placed in a sealed high-temperature high-pressure cavity for reaction, a temperature and a pressure are set firstly, so that red phosphorus in the cavity is converted into molten white phosphorus, then a certain pressure is increased to enable the molten white phosphorus to be injected into AAO holes, then a certain temperature is increased to enable the white phosphorus in the AAO holes to be converted into black phosphorus, and finally NaOH solution with a certain concentration is used for dissolving the AAO template so as to obtain the black phosphorus nanowire. The method controls the size of the black phosphorus nanowire by controlling the hole diameter of the AAO template, can synthesize the black phosphorus nanowires with different sizes, and has the advantages of good uniformity, high crystallinity and good stability, and the adopted high-temperature and high-pressure technology has the advantages of short time consumption, good controllability, high repeatability, high yield, cleanness, environmental protection, low cost and the like. The work not only opens up a new dimension for exploring new characteristics of the black phosphorus material, but also provides a one-dimensional structure engineering strategy for rapid and efficient large-scale manufacturing, thereby endowing the traditional two-dimensional material with novel characteristics for practical application.
According to the preparation method, cheap and nontoxic red phosphorus and an anodic alumina template are adopted for high-temperature high-pressure sealing reaction, and the reaction has the advantages of short time consumption, good controllability, high repeatability, high yield, cleanness, environmental protection, low cost and the like. The black phosphorus nanowire prepared by the invention has good crystallinity and high stability, so that the black phosphorus nanowire can be widely applied to the fields of solar cells, transistors, photoelectric detectors, photocatalysis, supercapacitors, chemical sensors and the like.
Drawings
FIG. 1 is an SEM image of black phosphorus nanowires prepared in example 1, wherein (a) the image is at a low magnification and (b) the image is at a high magnification;
FIG. 2 is a TEM image of the black phosphorus nanowires prepared in example 1, wherein (a) the image is an HRTEM image, and (b) the image is a SAED image;
FIG. 3 is an XRD pattern of the black phosphorus nanowire prepared in example 1;
FIG. 4 is a Raman diagram of the black phosphorus nanowire prepared in example 1;
FIG. 5 is an XPS plot of black phosphorus nanowires prepared in example 1;
fig. 6 is an EDX diagram of the black phosphorus nanowire prepared in example 1.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.5mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in a phosphoric acid solution with the mass fraction of 6%, heating at 30 ℃ for 60min for reaming, finally washing the anodized aluminum template AAO obtained by reaming with distilled water for 10 times, placing in a drying oven, and drying at 60 ℃ for 2h to obtain the standby anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding an anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa, the temperature to 1000 ℃, reacting for 50min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into holes of the AAO, increasing the temperature to 600 ℃, reacting for 1h to convert the white phosphorus in the holes of the anodic alumina template AAO into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire for 5h at 80 ℃ to obtain the black phosphorus nanowire.
Example 2:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 1mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in 10% phosphoric acid solution, heating at 30 deg.C for 90min for reaming, washing the anodized aluminum template AAO with distilled water for 10 times, drying in a drying oven at 80 deg.C for 2h to obtain the anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding an anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa, the temperature to 1000 ℃, reacting for 50min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into holes of the AAO, increasing the temperature to 600 ℃, reacting for 1h to convert the white phosphorus in the holes of the anodic alumina template AAO into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire at 80 ℃ for 6h to obtain the black phosphorus nanowire.
Example 3:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.3mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in 8% phosphoric acid solution, heating at 20 deg.C for 100min for reaming, washing the anodized aluminum template AAO with distilled water for 1 time, drying in a drying oven at 40 deg.C for 30h to obtain the anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding an anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa, the temperature to 1000 ℃, reacting for 50min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into holes of the AAO, increasing the temperature to 600 ℃, reacting for 1h to convert the white phosphorus in the holes of the anodic alumina template AAO into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire at 80 ℃ for 3h to obtain the black phosphorus nanowire.
Example 4:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.3mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in 8% phosphoric acid solution, heating at 50 deg.C for 60min for reaming, washing the anodized aluminum template AAO with distilled water for 3 times, drying in a drying oven at 80 deg.C for 10h to obtain the anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding an anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa, the temperature to 1000 ℃, reacting for 50min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into holes of the AAO, increasing the temperature to 600 ℃, reacting for 1h to convert the white phosphorus in the holes of the anodic alumina template AAO into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire for 4h at 80 ℃ to obtain the black phosphorus nanowire.
Example 5:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.5mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in 10% phosphoric acid solution, heating at 60 deg.C for 90min for reaming, washing the anodized aluminum template AAO with distilled water for 10 times, drying in a drying oven at 30 deg.C for 20h to obtain the anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding the anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa, the temperature to 1000 ℃, reacting for 50min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into the AAO holes, increasing the temperature to 600 ℃, reacting for 1h to convert the white phosphorus in the AAO holes of the anodic alumina template into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire for 1h at 80 ℃ to obtain the black phosphorus nanowire.
Example 6:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.5mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in a phosphoric acid solution with the mass fraction of 6%, heating at 60 ℃ for 100min for reaming, finally washing the anodized aluminum template AAO obtained by reaming with distilled water for 5 times, placing in a drying oven, and drying at 100 ℃ for 1h to obtain the standby anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding an anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa and the temperature to 1000 ℃, reacting for 30min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into holes of the AAO, increasing the temperature to 600 ℃, reacting for 1h to convert the white phosphorus in the holes of the anodic alumina template AAO into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire at 80 ℃ for 10h to obtain the black phosphorus nanowire.
Example 7:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 1mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in 2% phosphoric acid solution, heating at 40 deg.C for 60min for reaming, washing the anodized aluminum template AAO with distilled water for 6 times, drying in a drying oven at 80 deg.C for 4h to obtain the anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding an anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa and the temperature to 1000 ℃, reacting for 20min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into holes of the AAO, increasing the temperature to 600 ℃, reacting for 2h to convert the white phosphorus in the holes of the anodic alumina template AAO into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire for 5h at 80 ℃ to obtain the black phosphorus nanowire.
Example 8:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.8mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in 8% phosphoric acid solution, heating at 50 deg.C for 90min for reaming, washing the anodized aluminum template AAO with distilled water for 7 times, drying in a drying oven at 80 deg.C for 10h to obtain the anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding the anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa and the temperature to 1000 ℃, reacting for 10min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into the AAO holes, increasing the temperature to 600 ℃, reacting for 20min to convert the white phosphorus in the AAO holes of the anodic alumina template into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire for 5h at 80 ℃ to obtain the black phosphorus nanowire.
Example 9:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.7mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in 7 mass percent phosphoric acid solution, heating at 60 ℃ for 60min for reaming, finally cleaning the anodized aluminum template AAO obtained by reaming with distilled water for 1 time, placing in a drying oven, and drying at 60 ℃ for 2h to obtain the standby anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding the anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa, the temperature to 1000 ℃, reacting for 15min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into the AAO holes, increasing the temperature to 600 ℃, reacting for 10min to convert the white phosphorus in the AAO holes of the anodic alumina template into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire at 80 ℃ for 8h to obtain the black phosphorus nanowire.
Example 10:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.6mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in 6 wt% phosphoric acid solution, heating at 30 deg.C for 60min for reaming, washing the anodized aluminum template AAO with distilled water for 8 times, drying in a drying oven at 60 deg.C for 10 hr to obtain anodized aluminum template AAO。
2. Preparing black phosphorus nanowires: mixing and grinding the anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa, the temperature to 1000 ℃, reacting for 5min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into the AAO holes, increasing the temperature to 600 ℃, reacting for 10min to convert the white phosphorus in the AAO holes of the anodic alumina template into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire at 80 ℃ for 7h to obtain the black phosphorus nanowire.
Example 11:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.5mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in a phosphoric acid solution with the mass fraction of 6%, heating at 60 ℃ for 90min for reaming, finally cleaning the anodized aluminum template AAO obtained by reaming with distilled water for 6 times, placing in a drying oven, and drying at 80 ℃ for 2h to obtain the standby anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding the anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa and the temperature to 1000 ℃, reacting for 30min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into the AAO holes, increasing the temperature to 600 ℃, reacting for 10min to convert the white phosphorus in the AAO holes of the anodic alumina template into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire for 5h at 80 ℃ to obtain the black phosphorus nanowire.
Example 12:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.5mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in 4 wt% phosphoric acid solution, heating at 60 deg.C for 90min for reaming, washing the anodized aluminum template AAO with distilled water for 10 times, and standingAnd drying for 10 hours at 50 ℃ in a drying box to obtain the spare anode alumina template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding an anodic alumina template AAO and red phosphorus according to a mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa and the temperature to 1000 ℃, reacting for 30min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into holes of the AAO, increasing the temperature to 600 ℃, reacting for 20min to convert the white phosphorus in the holes of the anodic alumina template AAO into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire for 4h at 80 ℃ to obtain the black phosphorus nanowire.
Example 13:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 1mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in a phosphoric acid solution with the mass fraction of 6%, heating at 30 ℃ for 60min for reaming, finally washing the anodized aluminum template AAO obtained by reaming with distilled water for 8 times, placing in a drying oven, and drying at 80 ℃ for 10h to obtain the standby anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding the anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa and the temperature to 1000 ℃, reacting for 50min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into the holes of the AAO, increasing the temperature to 600 ℃, reacting for 1.5h to convert the white phosphorus in the holes of the anodic alumina template AAO into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire at 80 ℃ for 3h to obtain the black phosphorus nanowire.
Example 14:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.6mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in 8 wt% phosphoric acid solution, heating at 60 deg.C for 60min for reaming, and removing the substrateAnd (3) cleaning the anodic alumina template AAO obtained by reaming for 8 times by using distilled water, placing the anodic alumina template AAO in a drying box, and drying for 8 hours at the temperature of 60 ℃ to obtain the standby anodic alumina template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding the anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa, the temperature to 1000 ℃, reacting for 1.5h to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into the AAO holes, increasing the temperature to 600 ℃, reacting for 30min to convert the white phosphorus in the AAO holes of the anodic alumina template into black phosphorus, relieving the pressure, soaking for 60h with 0.5mol/L NaOH solution, and drying for 2h at 80 ℃ to obtain the black phosphorus nanowire.
Example 15:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.9mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in a phosphoric acid solution with the mass fraction of 6%, heating at 60 ℃ for 60min for reaming, finally washing the anodized aluminum template AAO obtained by reaming with distilled water for 10 times, placing in a drying oven, and drying at 80 ℃ for 2h to obtain the standby anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding the anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa, the temperature to 1000 ℃, reacting for 1.2h to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into the AAO holes, increasing the temperature to 600 ℃, reacting for 50min to convert the white phosphorus in the AAO holes of the anodic alumina template into black phosphorus, relieving the pressure, soaking for 60h with 0.5mol/L NaOH solution, and drying for 1h at 80 ℃ to obtain the black phosphorus nanowire.
Example 16:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.5mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, and soaking in 9 wt% phosphoric acidAnd (3) setting the water bath temperature in the solution to be 50 ℃, heating for 50min for reaming, finally, washing the anodized aluminum template AAO obtained by reaming with distilled water for 10 times, placing the anodized aluminum template AAO in a drying box, and drying at 60 ℃ for 4h to obtain the standby anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding the anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa and the temperature to 1000 ℃, reacting for 20min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into the holes of the AAO, increasing the temperature to 600 ℃, reacting for 1.2h to convert the white phosphorus in the holes of the anodic alumina template AAO into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire at 80 ℃ for 10h to obtain the black phosphorus nanowire.
Example 17:
AAO template treatment: firstly, preparing an anodic alumina template AAO by an anodic oxidation method, and then using 0.5mol/L copper chloride solution (CuCl)2·5H2O) removing the substrate, soaking in 10% phosphoric acid solution, heating at 50 deg.C for 60min for reaming, washing the anodized aluminum template AAO with distilled water for 10 times, drying in a drying oven at 80 deg.C for 2h to obtain the anodized aluminum template AAO.
2. Preparing black phosphorus nanowires: mixing and grinding an anodic alumina template AAO and red phosphorus according to the mass ratio of 10:1, sealing the mixture in a quartz tube, filling the quartz tube into a high-temperature high-pressure cavity, increasing the pressure to 1GPa and the temperature to 1000 ℃, reacting for 40min to convert the red phosphorus into white phosphorus, increasing the pressure to 3GPa to inject the molten white phosphorus into the AAO holes, increasing the temperature to 600 ℃, reacting for 1h to convert the white phosphorus in the AAO holes of the anodic alumina template into black phosphorus, releasing the pressure, soaking the black phosphorus in 0.5mol/L NaOH solution for 60h, and drying the black phosphorus nanowire at 80 ℃ for 6h to obtain the black phosphorus nanowire.
Claims (7)
1.A method for preparing single crystal black phosphorus nanowires by using a template method is characterized by comprising the following steps:
step 1: preparing an anodic alumina template AAO by an anodic oxidation method and using a copper chloride solution CuCl2·5H2Removing the substrate, soaking in phosphoric acid solution, heating in water bath at 0-60 deg.C for less than 100min, reaming, washing the obtained anodic alumina template AAO with distilled water for several times, and drying in a drying oven;
step 2: mixing an anodic alumina template AAO and red phosphorus in a ratio of 1-100: 1, grinding, placing in a sealed quartz tube, and placing in a high-temperature high-pressure instrument for reaction;
1. the reaction time is less than 2 hours at the pressure of 0-4 GPa and the temperature of 200-1200 ℃, so that the red phosphorus in the high-pressure cavity is converted into molten white phosphorus;
2. injecting the molten white phosphorus into the AAO holes of the anodic alumina template under the conditions that the pressure is 0-4 GPa, the temperature is 400-1800 ℃ and the reaction time is less than 2 hours, increasing the temperature to a certain value, and converting the molten white phosphorus in the AAO holes of the anodic alumina template into black phosphorus after reacting for several hours;
and step 3: soaking the amorphous anodic alumina template AAO obtained in the step 2 in NaOH solution for dissolving, wherein the soaking time is 1-100 h; and washing and drying to obtain the black phosphorus nanowire.
2. The method for preparing single-crystal black phosphorus nanowires by using the template method according to claim 1, wherein: the copper chloride solution CuCl2·5H2The concentration of O is 0 to 1 mol/L.
3. The method for preparing single-crystal black phosphorus nanowires by using the template method according to claim 1, wherein: the mass fraction of the phosphoric acid solution is 0-10%.
4. The method for preparing single-crystal black phosphorus nanowires by using the template method according to claim 1, wherein: and the washing times with distilled water in the step 1 are 1-10 times.
5. The method for preparing single-crystal black phosphorus nanowires by using the template method according to claim 1, wherein: and (2) drying in the drying oven in the step (1) at a temperature of less than 100 ℃ for 1-30 h.
6. The method for preparing single-crystal black phosphorus nanowires by using the template method according to claim 1, wherein: the concentration of the NaOH solution in the step 3 is 0-2 mol/L.
7. The method for preparing single-crystal black phosphorus nanowires by using the template method according to claim 1, wherein: and the drying time of the step 3 is 1-10 h.
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| CN103255374A (en) * | 2012-09-19 | 2013-08-21 | 苏州大学 | Method for preparing ordered one-dimensional organic nano wire array |
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