Method for assisting in preparing two-dimensional phosphorene by easily removing template

Abstract

The invention discloses a method for preparing two-dimensional phosphorene with assistance of an easy-to-remove template, which comprises the following steps: necking a quartz tube, and placing a spacer at the necking position; placing a phosphorus source, a metal simple substance and a mineralizing agent at the head end of a quartz tube, and limiting the template material at the tail end of the quartz tube; carrying out vacuum melting sealing on the quartz tube, carrying out multi-stage programmed heating and cooling procedures, and enabling the quartz tube to keep horizontal and rotate at a constant speed, so as to prepare a black phosphorus-template composite material; and removing the template in the black phosphorus-template composite material to obtain the two-dimensional phosphorene. According to the method, the template grows between black phosphorus crystal layers, the original interlayer Van der Waals force of black phosphorus is weakened or damaged, due to introduction of the template, the black phosphorus cannot form clusters in the growth process of chemical vapor transport, then the template is removed, and a high-quality phosphorene product is obtained.

Description

Technical Field

[0001] The present invention belongs to the technical field of two-dimensional materials, and in particular relates to a method for preparing two-dimensional phosphorene with the assistance of an easily removable template. Background Art

[0002] Single atomic layer black phosphorus, also known as phosphorene, exhibits better performance than bulk black phosphorus due to its large specific surface area, rich active sites, and quantum confinement effect.

[0003] Currently, chemical vapor transport is a classic approach to prepare black phosphorus materials, but the black phosphorus obtained by this method is usually a large cluster crystal. Further obtaining phosphorene materials on this basis requires additional exfoliation treatment. Most of the current exfoliation methods usually involve high-energy technology, which not only destroys the interlayer forces of black phosphorus, but also reduces the lateral size of black phosphorus. This not only leads to a cumbersome operation process, but also reduces the quality and yield of phosphorene to a certain extent. For this reason, it is of great significance to develop and design a simple and high-quality phosphorene preparation method. Summary of the invention

[0004] In order to solve the above technical content, the purpose of the present invention is to provide a method for preparing two-dimensional phosphorene which is assisted by an easily removable template, is convenient to operate and has high product quality.

[0005] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing two-dimensional phosphorene with the aid of an easily removable template comprises the following steps:

[0007] The quartz tube is subjected to necking treatment, and a spacer is placed at the necking position;

[0008] Placing a phosphorus source, a metal element and a mineralizer at the head end of the quartz tube, and confining the template material at the end of the quartz tube;

[0009] After the quartz tube is vacuum sealed, a multi-stage temperature rise and fall program is performed, and the quartz tube is kept horizontal and rotated at a constant speed to obtain a black phosphorus-template composite material;

[0010] Removing the template from the black phosphorus-template composite material yields two-dimensional phosphorene.

[0011] Furthermore, the mass ratio of the phosphorus source, the metal element and the mineralizer is 5:1:1 to 60:6:1; the mass ratio of the phosphorus source to the template material is 0.1 to 10:1.

[0012] Furthermore, the phosphorus source is one of white phosphorus, red phosphorus or purple phosphorus.

[0013] Furthermore, the metal element is one or more of Cd, In, Sn, Sb, Te, Pb and Bi.

[0014] Furthermore, the mineralizer is CdI 2 ,InI 3 SnI 2 SnI 4 , SbI 3 ,TeI 4 、PbI 2 With BiI 3 One or more of .

[0015] Furthermore, the template material is a water-soluble salt, an oxide or a metal.

[0016] Furthermore, the water-soluble salt is NaCl, NaCO 3 , KCl or K 2 CO 3 The state is preferably powder or granules.

[0017] The oxide is Al 2 O 3 、MgO、SiO 2 or Cr 2 O 3 , the state is powder or flakes with a thickness of less than 100 μm;

[0018] The metal is Al, Fe or Pb, and is in the form of powder or a thin sheet with a thickness of less than 100 μm.

[0019] Furthermore, the temperature difference between the head end and the tail end of the quartz tube is 10-70° C.; the rotation speed of the quartz tube is 30-500 rpm.

[0020] Furthermore, the multi-stage heating and cooling program is as follows: at room temperature, heating for 1 to 5 hours at a heating rate of 140 to 600°C / h, and keeping at 600 to 800°C for 1 to 5 hours; cooling for 2 to 10 hours at a cooling rate of 10 to 50°C / h, and keeping at 300 to 600°C for 2 to 10 hours after cooling; and cooling for a second time to 180 to 270°C for 2 to 10 hours at a cooling rate of 30 to 70°C / h.

[0021] Furthermore, the template in the black phosphorus-template composite material is removed by water dissolution, acid dissolution or alkali dissolution.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The present invention discloses a method for preparing two-dimensional phosphorene with the aid of an easily removable template. The method uses a template to grow between black phosphorus crystal layers to weaken or destroy the original interlayer van der Waals force of black phosphorus. The introduction of the template prevents black phosphorus from forming clusters during the growth process of chemical vapor transmission. The template is then removed to obtain a high-quality phosphorene product.

[0024] Furthermore, in the present invention, by changing the rotation speed of the quartz tube and controlling the coverage area of ​​the template on the black phosphorus sheet, the lateral size of the two-dimensional phosphorene can be regulated.

[0025] Furthermore, taking advantage of the easy-to-remove property of the template, two-dimensional phosphorene is separated from the template using simple methods such as dissolution and pyrolysis that do not damage the black phosphorus structure, avoiding the impact of high-energy stripping methods such as ultrasound and ball milling on phosphorene. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The accompanying drawings are used to provide a further understanding of the invention and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the invention but do not constitute a limitation of the invention. In the accompanying drawings:

[0027] Figure 1 This is a schematic diagram of the quartz tube after loading and vacuum sealing;

[0028] Figure 2 This is a schematic diagram of the method for preparing two-dimensional phosphorene with the assistance of a water-soluble template in Example 1;

[0029] Figure 3 is a SEM image of the black phosphorus-potassium carbonate layered composite obtained in Example 1;

[0030] Figure 4 The K removal obtained in Example 1 2 CO 3 SEM image of the thin layer of black phosphorus after template formation. DETAILED DESCRIPTION

[0031] In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present invention are given in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly and comprehensively understood.

[0032] A method for preparing two-dimensional phosphorene with the aid of an easily removable template according to the present invention comprises the following steps:

[0033] 1) Use high temperature flame to shrink the quartz tube and place a spacer at the neck.

[0034] 2) Weigh a certain amount of phosphorus source, metal element and mineralizer and place them at one end of the quartz tube (raw material end), and confine the template material at the other end of the quartz tube (end).

[0035] 3) See Figure 1 After the above quartz tube is vacuum sealed, it is placed horizontally in a heating device, with the raw material end located at the hot end of the heating device and the terminal end located at the cold end of the heating device.

[0036] 4) Black phosphorus is prepared by multi-stage programmed heating and cooling, and a stable temperature difference is maintained between the hot end and the cold end. The multi-stage heating and cooling program is: programmed heating - insulation - programmed cooling - insulation - secondary programmed cooling - natural cooling, to obtain a black phosphorus-template composite material.

[0037] 5) During the multi-stage programmed temperature rise and fall process for preparing black phosphorus, the quartz tube was kept horizontal and rotated at a constant speed of 80 rpm.

[0038] 6) Under vacuum conditions, the template is removed from the initially prepared black phosphorus-template composite material.

[0039] 7) After removing the template, the black phosphorus material is washed, filtered and dried to obtain two-dimensional phosphorene.

[0040] Furthermore, the phosphorus source is one of white phosphorus, red phosphorus or purple phosphorus.

[0041] Furthermore, the metal element is one or more of Cd, In, Sn, Sb, Te, Pb and Bi, and is preferably in the form of powder with a size of less than 200 mesh.

[0042] Furthermore, the mineralizer is CdI 2 ,InI 3 SnI 2 SnI 4 , SbI 3 ,TeI 4 、PbI 2 With BiI 3 One or more of the above, preferably in the form of powder or granules.

[0043] Furthermore, the mass ratio of the phosphorus source, the metal element and the mineralizer is 5:1:1 to 60:6:1.

[0044] Furthermore, the template can stably exist during the multi-stage heating and cooling process of black phosphorus growth.

[0045] Furthermore, the template material includes but is not limited to water-soluble salts, oxides, metals and other substances that can be removed without changing the structural properties of black phosphorus.

[0046] Furthermore, the water-soluble salts include but are not limited to NaCl, NaCO 3 , KCl or K 2 CO 3 The state is preferably powder or granules.

[0047] Furthermore, the oxide includes but is not limited to Al 2 O 3 、MgO、SiO 2 or Cr 2 O 3 The state is preferably powder or flakes with a thickness of less than 100 μm.

[0048] Furthermore, the metal includes but is not limited to Al, Fe or Pb, and is preferably in the form of powder or a thin sheet with a thickness of less than 100 μm.

[0049] Furthermore, the mass ratio of the phosphorus source to the template material is 0.1 to 10:1.

[0050] Furthermore, the phosphorus source, metal element and mineralizer are placed at one end (raw material end) of the quartz tube, and the template material is placed at the other end (terminal end) of the quartz tube.

[0051] Furthermore, the heating device has two or more heating zones, including but not limited to a tube furnace, a crystal furnace or an electromagnetic heater.

[0052] Furthermore, the quartz tube rotates at a speed of 30 to 500 rpm.

[0053] Furthermore, the temperature difference maintained between the hot end and the cold end of the heating device is 10-70°C.

[0054] Furthermore, the multi-stage heating and cooling program is specifically as follows: at room temperature, heating for 1 to 5 hours at a heating rate of 140 to 600°C / h, and keeping at 600 to 800°C for 1 to 5 hours after heating; cooling for 2 to 10 hours at a cooling rate of 10 to 50°C / h, and keeping at 300 to 600°C for 2 to 10 hours after cooling; and cooling for a second time to 180 to 270°C for 2 to 10 hours at a cooling rate of 30 to 70°C / h.

[0055] Furthermore, the template is grown between black phosphorus layers after a multi-stage temperature rise and fall process.

[0056] Furthermore, the template removal method includes but is not limited to water dissolution, acid dissolution or alkali dissolution, etc., which can destroy the template but do not change the structure and properties of black phosphorus.

[0057] The following are specific embodiments.

[0058] Example 1

[0059] See also Figure 2 , a method for preparing two-dimensional phosphorene with the assistance of an easily removable template, the specific preparation method is as follows:

[0060] 1) Use high temperature flame to shrink the quartz tube and place a spacer at the neck.

[0061] 2) Weigh 500 mg white phosphorus, 100 mg Sb powder, 100 mg SbI 3 Placed at one end of the quartz tube (raw material end), and 200 mg K 2 CO 3 The powder is confined at the other end (terminal) of the quartz tube.

[0062] 3) After the above quartz tube is vacuum sealed, it is placed horizontally in a double-temperature zone tubular furnace, with the raw material end located at the hot end of the tubular furnace and the terminal end located at the cold end of the tubular furnace.

[0063] 4) Black phosphorus was prepared by multi-stage programmed heating and cooling, and the temperature difference between the hot end and the cold end was controlled to be stable at 30°C.

[0064] Hot end temperature control program: heating from 25℃ for 4h at a heating rate of 160℃ / h, keeping at 665℃ for 2.5h; cooling for 4h at a cooling rate of 30℃ / h, keeping at 545℃ for 7h; cooling for a second time to 220℃ for 5h at a cooling rate of 65℃ / h, and then naturally cooling to room temperature.

[0065] Cold end temperature control program: heating from 25℃ for 4h, heating rate of 152.5℃ / h, keeping at 635℃ for 2.5h; cooling for 4h, cooling rate of 30℃ / h, keeping at 515℃ for 7h; cooling for a second time to 190℃ for 5h, cooling rate of 65℃ / h, and then naturally cooling to room temperature.

[0066] 5) During the multi-stage programmed temperature rise and fall process for preparing black phosphorus, the quartz tube was kept horizontal and rotated at a constant speed of 50 rpm.

[0067] 6) Under vacuum conditions, the preliminarily prepared black phosphorus-potassium carbonate layered composite was placed in deionized water after deoxygenation and stirred for 3 minutes to allow K 2 CO 3 Dissolve thoroughly.

[0068] 7) Wash the black phosphorus material to remove residual K 2 CO 3 After filtering and drying under vacuum conditions, two-dimensional phosphorene is obtained.

[0069] Figure 3is a SEM image of the black phosphorus-potassium carbonate layered composite obtained in Example 1; Figure 3 It can be seen that the potassium carbonate template is embedded in the interlayer of the composite, in which the black phosphorus as a whole can still maintain layered structure growth.

[0070] Figure 4 The K removal obtained in Example 1 2 CO 3 SEM image of thin layer black phosphorus after template. Figure 4 It can be seen that the width of black phosphorus is less than 200nm, the length is about 2.4μm, and the number of layers is less than 5.

[0071] Example 2

[0072] A method for preparing two-dimensional phosphorene with the aid of an easily removable template, the specific preparation method is as follows:

[0073] 1) Use high temperature flame to shrink the quartz tube and place a spacer at the neck.

[0074] 2) Weigh 2g red phosphorus, 300mg Sn powder, 180mg SnI 2 Placed at one end of the quartz tube (raw material end), and 1.6gAl 2 O 3 The powder is confined at the other end (terminal) of the quartz tube.

[0075] 3) After the above quartz tube is vacuum sealed, it is placed horizontally in a double-temperature zone tubular furnace, with the raw material end located at the hot end of the tubular furnace and the terminal end located at the cold end of the tubular furnace.

[0076] 4) Black phosphorus was prepared by multi-stage programmed heating and cooling, and the temperature difference between the hot end and the cold end was controlled to be stable at 60°C.

[0077] Hot end temperature control program: heating from 30℃ for 3h, heating rate of 300℃ / h, keeping at 780℃ for 4h; cooling for 6h, cooling rate of 30℃ / h, keeping at 600℃ for 5h; cooling for the second time to 250℃ for 10h, cooling rate of 35℃ / h, and then naturally cooling to room temperature.

[0078] Cold end temperature control program: from 30℃ for 3h, heating rate is 230℃ / h, keep at 720℃ for 4h after heating; cool down for 6h, cooling rate is 30℃ / h, keep at 540℃ for 5h after cooling; cool down to 190℃ for the second time for 10h, cooling rate is 35℃ / h, and then cool naturally to room temperature.

[0079] 5) During the multi-stage programmed heating and cooling process for preparing black phosphorus, the quartz tube was kept horizontal and rotated at a constant speed of 420 rpm.

[0080] 6) Under vacuum conditions, the preliminarily prepared black phosphorus-alumina layered composite was placed in a deoxygenated 1 mol / L KOH solution and stirred for 10 min to allow Al 2 O 3 Reacts fully with KOH.

[0081] 7) The black phosphorus material is washed to remove residual KOH and other impurities, filtered and dried under vacuum conditions to obtain two-dimensional phosphorene.

[0082] Example 3

[0083] 1) Use high temperature flame to shrink the quartz tube and place a spacer at the neck.

[0084] 2) Weigh 50 mg red phosphorus, 7 mg Bi powder, 5 mg BiI 3 placed at one end of the quartz tube (the raw material end), while 100 mg of iron filings were confined at the other end of the quartz tube (the end).

[0085] 3) After the above quartz tube is vacuum sealed, it is placed horizontally in a double-temperature zone tubular furnace, with the raw material end located at the hot end of the tubular furnace and the terminal end located at the cold end of the tubular furnace.

[0086] 4) Black phosphorus was prepared by multi-stage programmed heating and cooling, and the temperature difference between the hot end and the cold end was controlled to be stable at 45°C.

[0087] Hot end temperature control program: heating from 25℃ for 2h at a heating rate of 320℃ / h, keeping at 665℃ for 3.5h after heating; cooling for 10h at a cooling rate of 10℃ / h, keeping at 565℃ for 6.5h after cooling; cooling for a second time for 6h at a cooling rate of 50℃ / h to 265℃, and then naturally cooling to room temperature.

[0088] Cold end temperature control program: heating from 25℃ for 2h, heating rate is 297.5℃ / h, keeping at 620℃ for 3.5h after heating; cooling for 10h, cooling rate is 10℃ / h, keeping at 520℃ for 6.5h after cooling; cooling for the second time to 220℃ for 6h, cooling rate is 50℃ / h, and then naturally cooling to room temperature.

[0089] 5) During the multi-stage programmed heating and cooling process for preparing black phosphorus, the quartz tube was kept horizontal and rotated at a constant speed of 210 rpm.

[0090] 6) Under vacuum conditions, the initially prepared black phosphorus-iron layered composite was placed in a deoxygenated 0.5 mol / L H 2 SO 4 The solution was stirred for 10 min to allow Fe and H 2 SO 4Fully respond.

[0091] 7) Wash the black phosphorus material to remove residual H 2 SO 4 After filtering and drying under vacuum conditions, two-dimensional phosphorene is obtained.

[0092] Example 4

[0093] 1) Use high temperature flame to shrink the quartz tube and place a spacer at the neck.

[0094] 2) Weigh 500 mg purple phosphorus, 100 mg Pb powder, 100 mg PbI 2 was placed at one end of a quartz tube (the feed end), while 5000 mg of NaCl particles were confined at the other end of the quartz tube (the end).

[0095] 3) After the above quartz tube is vacuum sealed, it is placed horizontally in a double-temperature zone tubular furnace, with the raw material end located at the hot end of the tubular furnace and the terminal end located at the cold end of the tubular furnace.

[0096] 4) Black phosphorus was prepared by multi-stage programmed heating and cooling, and the temperature difference between the hot end and the cold end was controlled to be stable at 10°C.

[0097] Hot end temperature control program: heating from 10℃ for 1h, heating rate of 600℃ / h, keeping at 610℃ for 2h after heating; cooling for 6h, cooling rate of 50℃ / h, keeping at 310℃ for 4h after cooling; cooling for a second time to 210℃ for 2h, cooling rate of 50℃ / h, and then naturally cooling to room temperature.

[0098] Cold-end temperature control program: heating from 10℃ for 1h at a heating rate of 590℃ / h, keeping at 600℃ for 2h after heating; cooling for 6h at a cooling rate of 50℃ / h, keeping at 300℃ for 4h after cooling; cooling for a second time to 200℃ for 2h at a cooling rate of 50℃ / h, and then naturally cooling to room temperature.

[0099] 5) During the multi-stage programmed heating and cooling process for preparing black phosphorus, the quartz tube was kept horizontal and rotated at a constant speed of 30 rpm.

[0100] 6) Under vacuum conditions, the initially prepared black phosphorus-iron layered composite was placed in a deoxygenated 0.5 mol / L H 2 SO 4 The solution was stirred for 10 min to allow Fe and H 2 SO 4 Fully respond.

[0101] 7) Wash the black phosphorus material to remove residual H 2 SO4 After filtering and drying under vacuum conditions, two-dimensional phosphorene is obtained.

[0102] Example 5

[0103] 1) Use high temperature flame to shrink the quartz tube and place a spacer at the neck.

[0104] 2) Weigh 36000 mg white phosphorus, 600 mg In powder, 1 mg InI 3 placed at one end of a quartz tube (the feedstock end), while 3600 mg of MgO flakes with a thickness of less than 100 μm were confined at the other end of the quartz tube (the terminal end).

[0105] 3) After the above quartz tube is vacuum sealed, it is placed horizontally in a double-temperature zone tubular furnace, with the raw material end located at the hot end of the tubular furnace and the terminal end located at the cold end of the tubular furnace.

[0106] 4) Black phosphorus was prepared by multi-stage programmed heating and cooling, and the temperature difference between the hot end and the cold end was controlled to be stable at 70°C.

[0107] Hot end temperature control program: heating from 20℃ for 5h, heating rate of 156℃ / h, keeping at 800℃ for 1h after heating; cooling for 8h, cooling rate of 30℃ / h, keeping at 560℃ for 10h after cooling; cooling for a second time to 260℃ for 10h, cooling rate of 30℃ / h, and then naturally cooling to room temperature.

[0108] Cold end temperature control program: heating from 20℃ for 5h, heating rate of 142℃ / h, keeping at 730℃ for 1h after heating; cooling for 8h, cooling rate of 30℃ / h, keeping at 490℃ for 10h after cooling; cooling for the second time to 180℃ for 10h, cooling rate of 31℃ / h, and then naturally cooling to room temperature.

[0109] 5) During the multi-stage programmed temperature rise and fall process for preparing black phosphorus, the quartz tube was kept horizontal and rotated at a constant speed of 500 rpm.

[0110] 6) Under vacuum conditions, the initially prepared black phosphorus-iron layered composite was placed in a deoxygenated 0.5 mol / L H 2 SO 4 The solution was stirred for 10 min to allow Fe and H 2 SO 4 Fully respond.

[0111] 7) Wash the black phosphorus material to remove residual H 2 SO 4 After filtering and drying under vacuum conditions, two-dimensional phosphorene is obtained.

[0112] Example 6

[0113] 1) Use high temperature flame to shrink the quartz tube and place a spacer at the neck.

[0114] 2) Weigh 6000 mg red phosphorus, 300 mg Cd powder, 1 mg CdI 2 was placed at one end of the quartz tube (the feedstock end), while 6000 mg of Pb powder was confined at the other end of the quartz tube (the end).

[0115] 3) After the above quartz tube is vacuum sealed, it is placed horizontally in a double-temperature zone tubular furnace, with the raw material end located at the hot end of the tubular furnace and the terminal end located at the cold end of the tubular furnace.

[0116] 4) Black phosphorus was prepared by multi-stage programmed heating and cooling, and the temperature difference between the hot end and the cold end was controlled to be stable at 30°C.

[0117] Hot end temperature control program: heating from 20℃ for 1.5h at a heating rate of 450℃ / h, keeping at 695℃ for 5h after heating; cooling for 5h at a cooling rate of 50℃ / h, keeping at 445℃ for 2h after cooling; cooling for a second time to 230℃ for another 5h at a cooling rate of 43℃ / h, and then naturally cooling to room temperature.

[0118] Cold end temperature control program: heating from 20℃ for 1.5h at a heating rate of 430℃ / h, keeping at 665℃ for 5h after heating; cooling for 5h at a cooling rate of 50℃ / h, keeping at 415℃ for 2h after cooling; cooling for a second time to 270℃ for 3h at a cooling rate of 55℃ / h, and then naturally cooling to room temperature.

[0119] 5) During the multi-stage programmed temperature rise and fall process for preparing black phosphorus, the quartz tube was kept horizontal and rotated at a constant speed of 300 rpm.

[0120] 6) Under vacuum conditions, the initially prepared black phosphorus-iron layered composite was placed in a deoxygenated 0.5 mol / L H 2 SO 4 The solution was stirred for 10 min to allow Fe and H 2 SO 4 Fully respond.

[0121] 7) Wash the black phosphorus material to remove residual H 2 SO 4 After filtering and drying under vacuum conditions, two-dimensional phosphorene is obtained.

[0122] The above description is only for the best embodiment of the present invention, but it should not be understood as limiting the claims. The present invention is not limited to the above embodiments, and its specific structure is allowed to be changed. However, all changes made within the protection scope of the independent claims of the present invention are within the protection scope of the present invention.

[0123] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

Claims

1. A method for preparing two-dimensional phosphorene with the aid of an easily removable template, characterized in that: The following steps are involved: The quartz tube is subjected to necking treatment, and a spacer is placed at the necking position; Placing a phosphorus source, a metal element and a mineralizer at the head end of the quartz tube, and confining the template material at the end of the quartz tube; After the quartz tube is vacuum sealed, a multi-stage temperature rise and fall program is performed, and the quartz tube is kept horizontal and rotated at a constant speed to obtain a black phosphorus-template composite material; Removing the template from the black phosphorus-template composite material yields two-dimensional phosphorene.

2. The method for preparing two-dimensional phosphorene with the aid of an easily removable template according to claim 1, characterized in that: The mass ratio of the phosphorus source, the metal element and the mineralizer is 5:1:1 to 60:6:1; the mass ratio of the phosphorus source to the template material is 0.1 to 10:

1.

3. The method for preparing two-dimensional phosphorene with the aid of an easily removable template according to claim 1, characterized in that: The phosphorus source is one of white phosphorus, red phosphorus or violet phosphorus.

4. The method for preparing two-dimensional phosphorene with the aid of an easily removable template according to claim 1, characterized in that: The metal element is one or more of Cd, In, Sn, Sb, Te, Pb and Bi.

5. The method for preparing two-dimensional phosphorene with the aid of an easily removable template according to claim 1, characterized in that: The mineralizer is one or more of CdI2, InI3, SnI2, SnI4, SbI3, TeI4, PbI2 and BiI3.

6. The method for preparing two-dimensional phosphorene with the aid of an easily removable template according to claim 1, characterized in that: The template material is a water-soluble salt, oxide or metal.

7. The method for preparing two-dimensional phosphorene with the aid of an easily removable template according to claim 1, characterized in that: The water-soluble salt is NaCl, NaCO3, KCl or K2CO3, and is in the form of powder or granules; The oxide is Al2O3, MgO, SiO2 or Cr2O3, and is in the form of powder or a thin sheet with a thickness of less than 100 μm; The metal is Al, Fe or Pb, and is in the form of powder or a thin sheet with a thickness of less than 100 μm.

8. The method for preparing two-dimensional phosphorene with the aid of an easily removable template according to claim 1, characterized in that: The temperature difference between the front end and the rear end of the quartz tube is 10-70° C.; the rotation speed of the quartz tube is 30-500 rpm.

9. The method for preparing two-dimensional phosphorene with the aid of an easily removable template according to claim 1, characterized in that: The multi-stage heating and cooling program is as follows: at room temperature, heating for 1 to 5 hours at a heating rate of 140 to 600°C / h, and keeping at 600 to 800°C for 1 to 5 hours; cooling for 2 to 10 hours at a cooling rate of 10 to 50°C / h, and keeping at 300 to 600°C for 2 to 10 hours after cooling; and cooling for a second time to 180 to 270°C for 2 to 10 hours at a cooling rate of 30 to 70°C / h.

10. The method for preparing two-dimensional phosphorene with the aid of an easily removable template according to claim 1, characterized in that: The template in the black phosphorus-template composite material is removed by water dissolution, acid dissolution or alkali dissolution.

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