CN111101192B - A method for preparing single crystal black phosphorus nanowires by template method - Google Patents
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Abstract
Translated fromChinese
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 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 thestep 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 thestep 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 thestep 3 is 0-2 mol/L.
And the drying time of thestep 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 a substrate, mixing the substrate with cheap and nontoxic red phosphorus according to a certain proportion, placing the mixture in a sealed high-temperature high-pressure cavity for reaction, firstly setting a temperature and a pressure to convert the red phosphorus in the cavity into molten white phosphorus, then increasing a certain pressure to inject the molten white phosphorus into AAO holes, then increasing the temperature to a certain degree to convert the white phosphorus in the AAO holes into black phosphorus, and finally dissolving the AAO template by using a NaOH solution with a certain concentration 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 a phosphoric acid solution with the mass fraction of 6%, heating at the water bath temperature of 30 ℃ for 60min for hole expanding, finally cleaning the anodic alumina template AAO obtained by hole expanding with distilled water for 8 times, placing in a drying oven, and drying at the temperature of 60 ℃ for 10h 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 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 a phosphoric acid solution with the mass fraction of 4%, heating at 60 ℃ for 90min 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 50 ℃ for 10h 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 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 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, placing in a drying oven, and drying at 80 deg.CDrying for 10h to obtain the spare anode 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 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% phosphoric acid solution, heating at 60 deg.C for 60min for reaming, washing the anodized aluminum template AAO with distilled water for 8 times, placing in a drying oven, and drying at 60 deg.C for 8h 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 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 6 wt% phosphoric acid solution, heating at 60 deg.C for 60min for reaming, and oxidizing the anodeAnd washing the aluminum template AAO with distilled water for 10 times, placing the aluminum template AAO in a drying box, and drying the aluminum template AAO at 80 ℃ for 2 hours 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 1.2h 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, soaking in 9 mass percent phosphoric acid solution, heating at 50 ℃ for 50min for reaming, finally, washing the anodized aluminum template AAO obtained by reaming with distilled water for 10 times, placing 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 percent phosphoric acid solution by mass, and setting the water bath temperatureHeating 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 2 hr to obtain the final product.
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.
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