CN109368607B - Black phosphorus nanosheet and preparation method and application thereof - Google Patents
Black phosphorus nanosheet and preparation method and application thereof Download PDFInfo
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- CN109368607B CN109368607B CN201811359020.2A CN201811359020A CN109368607B CN 109368607 B CN109368607 B CN 109368607B CN 201811359020 A CN201811359020 A CN 201811359020A CN 109368607 B CN109368607 B CN 109368607B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 264
- 239000002135 nanosheet Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002002 slurry Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 37
- 239000011593 sulfur Substances 0.000 claims abstract description 37
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 239000005416 organic matter Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 15
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002608 ionic liquid Substances 0.000 claims abstract description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 239000002055 nanoplate Substances 0.000 claims description 28
- -1 tetrafluoroborate Chemical compound 0.000 claims description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 13
- 230000005669 field effect Effects 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims description 4
- ZIFRMAZAZSOSSD-UHFFFAOYSA-N 1,2-diethyl-3-methyl-2H-imidazole trifluoromethanesulfonic acid Chemical compound FC(S(=O)(=O)O)(F)F.C(C)N1C(N(C=C1)C)CC ZIFRMAZAZSOSSD-UHFFFAOYSA-N 0.000 claims description 3
- VOLTVCQZCOMDKW-UHFFFAOYSA-N 1-ethyl-2,3-dimethyl-2H-imidazole trifluoromethanesulfonic acid Chemical compound FC(S(=O)(=O)O)(F)F.CN1C(N(C=C1)CC)C VOLTVCQZCOMDKW-UHFFFAOYSA-N 0.000 claims description 3
- YQBXBUCEYLAOMF-UHFFFAOYSA-N P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+] Chemical compound P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.P(=O)([O-])([O-])F.C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+].C(CCC)[NH3+] YQBXBUCEYLAOMF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004299 exfoliation Methods 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- DAZZKDSMRZVTRH-UHFFFAOYSA-N 1-ethyl-11h-benzo[a]carbazole Chemical compound C1=CC=C2NC3=C4C(CC)=CC=CC4=CC=C3C2=C1 DAZZKDSMRZVTRH-UHFFFAOYSA-N 0.000 claims description 2
- YSTQDJNWDMBAOZ-UHFFFAOYSA-N [Br].C(C)N1CN(C=C1)C Chemical compound [Br].C(C)N1CN(C=C1)C YSTQDJNWDMBAOZ-UHFFFAOYSA-N 0.000 claims description 2
- GFMONIFLQHLPLM-UHFFFAOYSA-N [Br].CN1C(N(C=C1)CC)C Chemical compound [Br].CN1C(N(C=C1)CC)C GFMONIFLQHLPLM-UHFFFAOYSA-N 0.000 claims description 2
- WFYJISLZGVEJAE-UHFFFAOYSA-N [Cl].C(C)N1CN(C=C1)C Chemical compound [Cl].C(C)N1CN(C=C1)C WFYJISLZGVEJAE-UHFFFAOYSA-N 0.000 claims description 2
- RHFVGOIQQLSDSD-UHFFFAOYSA-N [Cl].CN1C(N(C=C1)CC)C Chemical compound [Cl].CN1C(N(C=C1)CC)C RHFVGOIQQLSDSD-UHFFFAOYSA-N 0.000 claims description 2
- LLTNLMDJCYJOOR-UHFFFAOYSA-N [I].C(C)N1CN(C=C1)C Chemical compound [I].C(C)N1CN(C=C1)C LLTNLMDJCYJOOR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims 6
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001069 Raman spectroscopy Methods 0.000 description 6
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- 239000000758 substrate Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002524 electron diffraction data Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
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- PFWZRULJVRDQJQ-UHFFFAOYSA-N 1-butyl-11h-benzo[a]carbazole Chemical compound C1=CC=C2NC3=C4C(CCCC)=CC=CC4=CC=C3C2=C1 PFWZRULJVRDQJQ-UHFFFAOYSA-N 0.000 description 1
- CHTWEZNDVKTUAJ-UHFFFAOYSA-N 1-ethyl-2,3-dimethyl-1,2-dihydroimidazol-1-ium chloride Chemical compound [Cl-].CC[NH+]1C=CN(C)C1C CHTWEZNDVKTUAJ-UHFFFAOYSA-N 0.000 description 1
- SMYRLQDRZXALMO-UHFFFAOYSA-N 1-ethyl-2,3-dimethyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCN1C=CN(C)C1C SMYRLQDRZXALMO-UHFFFAOYSA-N 0.000 description 1
- WWFKDEYBOOGHKL-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCN1CN(C)C=C1 WWFKDEYBOOGHKL-UHFFFAOYSA-N 0.000 description 1
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 description 1
- COELWDHEVBNFLF-UHFFFAOYSA-N 1-ethyl-3-methyl-2H-imidazole hydroiodide Chemical compound I.CCN1CN(C)C=C1 COELWDHEVBNFLF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
Abstract
The invention relates to a black phosphorus nanosheet and a preparation method and application thereof. The preparation method of the black phosphorus nanosheet comprises the following steps: black phosphorus is used as a cathode, the black phosphorus and an anode are placed in electrolyte, and the black phosphorus and the anode are electrified to carry out electrochemical reaction to obtain expanded black phosphorus, wherein the electrolyte is ionic liquid or quaternary ammonium salt solution; mixing the expanded black phosphorus and an oil-soluble solvent for ultrasonic stripping to obtain stripping slurry; and mixing the stripping slurry with a heterocyclic organic matter containing sulfur and nitrogen for reaction to obtain the black phosphorus nanosheet. The black phosphorus nanosheet prepared by the method is relatively stable in structure and relatively good in dispersity.
Description
Technical Field
The invention relates to the field of material chemistry, in particular to a black phosphorus nanosheet and a preparation method and application thereof.
Background
Two-dimensional black phosphorus having excellent carrier mobility: (>1000cm2Vs-1) The continuous band gap structure (0.3-2.1 eV) related to the number of layers, and the black phosphorus with any number of layers has direct energy level band gaps, so that the black phosphorus has an extremely thick structural advantage when being applied to the field of photoelectric devices. However, the current research based on two-dimensional black phosphorus is mainly focused on the basic theory research with the mechanical stripping method as the core, and many problems of the properties and the application of black phosphorus still need to be solved. At present, poor structural stability and dispersibility are one of the core bottleneck problems limiting black phosphorus application.
Disclosure of Invention
Therefore, it is necessary to provide a method for preparing black phosphorus nanosheets with relatively stable structures and relatively good dispersibility.
In addition, a black phosphorus nanosheet and applications thereof are also provided.
A preparation method of black phosphorus nanosheets comprises the following steps:
black phosphorus is taken as a cathode, the black phosphorus and an anode are placed in electrolyte, the black phosphorus and the anode are electrified to carry out electrochemical reaction to obtain expanded black phosphorus, the electrolyte is ionic liquid, or the electrolyte is a quaternary ammonium salt solution, and the ionic liquid is at least one selected from 1-ethyl-3-methylimidazole bromine salt, 1-ethyl-3-methylimidazole chlorine salt, 1-ethyl-3-methylimidazole iodine salt, 1-ethyl-2, 3-dimethylimidazole trifluoromethanesulfonate, 1, 2-diethyl-3-methylimidazole trifluoromethanesulfonate, 1, 2-dimethyl-3-ethylimidazole bromine salt, 1, 2-dimethyl-3-ethylimidazole chlorine salt and 1, -dimethyl-3-ethylimidazole tetrafluoroborate; the solute of the quaternary ammonium salt solution is selected from at least one of 1-ethyl-3-methyl ammonium tetrafluoroborate, n-butyl ammonium tetrachlorochlorate, n-butyl ammonium tetrafluoroborate and n-butyl ammonium tetrafluorophosphate;
mixing the expanded black phosphorus and an oil-soluble solvent for ultrasonic stripping to obtain stripping slurry; and
and mixing and reacting the stripping slurry with a heterocyclic organic matter containing sulfur and nitrogen to obtain the black phosphorus nanosheet.
In one embodiment, the step of energizing the black phosphorus and the anode to perform the electrochemical reaction is: and applying a voltage of 1V-10V to the black phosphorus and the anode to perform an electrochemical reaction.
In one embodiment, the step of energizing the black phosphorus and the anode to perform the electrochemical reaction is: applying a density of 1mA/cm to the black phosphorus and the anode2~100mA/cm2To carry out an electrochemical reaction.
In one embodiment, the step of mixing the expanded black phosphorus and the oil-soluble solvent for ultrasonic stripping further comprises a step of separating and purifying the expanded black phosphorus, and the step of separating and purifying comprises: and removing the anode in the reaction system, carrying out centrifugal separation on the reaction system to obtain filter residue, and cleaning the filter residue to obtain the purified expanded black phosphorus.
In one embodiment, the step of electrifying the black phosphorus and the anode to perform the electrochemical reaction, the step of mixing the expanded black phosphorus and the oil-soluble solvent to perform the ultrasonic stripping, and the step of mixing the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen to react are performed under the condition of air.
In one embodiment, the molar ratio of the expanded black phosphorus to the sulfur-and nitrogen-containing heterocyclic organic compound is 0.1:1 to 10: 1.
In one embodiment, the oil-soluble solvent is selected from at least one of N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and tetrahydrofuran; and/or the concentration of the solute of the quaternary ammonium salt solution is 0.05 g/mL-10 g/mL; and/or the solvent of the quaternary ammonium salt solution is one selected from N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran.
In one embodiment, the anode is selected from one of platinum, graphite carbon rod and graphene paper.
The black phosphorus nanosheet is prepared by the preparation method of the black phosphorus nanosheet.
The black phosphorus nanosheet is applied to the preparation of a field effect transistor.
According to the preparation method of the black phosphorus nanosheet, black phosphorus is used as a cathode, the ionic liquid or the quaternary ammonium salt solution is used as an electrolyte, the anode is electrified for electrochemical reaction to obtain expanded graphite, the expanded black phosphorus and an oil-soluble solvent are mixed for ultrasonic stripping to obtain stripping slurry, the stripping slurry is mixed with a heterocyclic organic matter containing sulfur and nitrogen for reaction, and the ionic salt covalently modified black phosphorus nanosheet is obtained.
Drawings
FIG. 1 is a Raman (Raman) spectrum of a black phosphorus nanosheet prepared in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the black phosphorus nanosheet prepared in example 1;
FIG. 3 is an electron diffraction pattern of a corresponding selected area of FIG. 1;
FIG. 4 is an enlarged view of FIG. 2 at 1000 times magnification;
fig. 5 is a bar graph of hole mobility of a field effect transistor prepared from the black phosphorus nanosheets of example 1.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
A method of preparing a black phosphorus nanoplate of an embodiment, comprising the steps of:
step S110: black phosphorus is used as a cathode, the black phosphorus and an anode are placed in electrolyte, and the black phosphorus and the anode are electrified to carry out electrochemical reaction, so that the expanded black phosphorus is obtained.
In one embodiment, the step of energizing the black phosphorus and the anode to perform the electrochemical reaction is: applying a voltage of 1V to 10V to the black phosphorus and the anode to perform an electrochemical reaction. Too low a voltage (less than 1V) can drive the reaction, but the reaction rate is too slow; if the voltage is too high (more than 10V), the reaction solvent may be decomposed and deteriorated by the electric field.
In another embodiment, the step of energizing the black phosphorus and the anode to perform the electrochemical reaction is: the cathode and the anode were applied at a density of 1mA/cm2~100mA/cm2To carry out an electrochemical reaction. Excessively low current density (less than 1 mA/cm)2) Lower, the stripping rate is too slow; the current density is too high (more than 100 mA/cm)2) If the reaction is too fast, the incompletely peeled material may fall off the electrode, resulting in an unsatisfactory peeling effect.
Specifically, the electrolyte is an ionic liquid or a quaternary ammonium salt solution; more specifically, the ionic liquid is selected from at least one of 1-ethyl-3-methylimidazole bromide, 1-ethyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole iodide, 1-ethyl-2, 3-dimethylimidazole trifluoromethanesulfonate, 1, 2-diethyl-3-methylimidazole trifluoromethanesulfonate, 1, 2-dimethyl-3-ethylimidazole bromide, 1, 2-dimethyl-3-ethylimidazole chloride and 1, -dimethyl-3-ethylimidazole tetrafluoroborate; the solute of the quaternary ammonium salt solution is at least one selected from the group consisting of 1-ethyl-3-methylammonium tetrafluoroborate, n-butyl ammonium tetrachlorochlorate, n-butyl ammonium tetrafluoroborate and n-butyl ammonium tetrafluorophosphate.
Specifically, the concentration of the solute in the quaternary ammonium salt solution is 0.05g/mL to 10 g/mL. The solvent of the quaternary ammonium salt solution is at least one selected from the group consisting of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and Tetrahydrofuran (THF).
Specifically, the anode is selected from one of platinum, a graphite carbon rod and graphene paper. Wherein, the platinum is a platinum wire or a platinum sheet.
Step S120: and mixing the expanded black phosphorus and the oil-soluble solvent for ultrasonic stripping to obtain stripping slurry.
Specifically, the mass-volume ratio of the expanded black phosphorus to the oily solvent is 1mg:1000 mL-10 mg:1mL, the ratio is good in stripping effect, the ultrasonic stripping effect of too much black phosphorus is poor, and the production efficiency is low due to too little black phosphorus. The power for ultrasonic stripping is 5W-50W, and the stripping time is 5 minutes-60 minutes.
Specifically, the step of mixing the expanded black phosphorus and the oil-soluble solvent for ultrasonic stripping further comprises a step of separating and purifying the expanded black phosphorus, wherein the step of separating and purifying comprises the following steps: and removing the anode in the reaction system, carrying out centrifugal separation on the reaction system to obtain filter residue, and cleaning the filter residue to obtain the purified expanded black phosphorus. Wherein, in the step of cleaning the filter residue, the filter residue is cleaned by using an organic solvent; the organic solvent is at least one selected from the group consisting of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP) and Tetrahydrofuran (THF).
Specifically, the oil-soluble solvent is at least one selected from the group consisting of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and Tetrahydrofuran (THF). More specifically, the oil-soluble solvent is the same as the organic solvent for cleaning the filter residue, which is beneficial to material analysis and is also convenient for experimental operation. It will be appreciated that the oil-soluble solvent may also be different from the organic solvent used to wash the filter residue.
Step S130: and mixing the stripping slurry with a heterocyclic organic matter containing sulfur and nitrogen for reaction to obtain the black phosphorus nanosheet.
The black phosphorus nanosheet obtained in the step S130 is a black phosphorus nanosheet covalently modified with an ionic salt. Specifically, the mixed reaction step of the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen comprises the following steps: and stirring and reacting the stripping slurry and the heterocyclic organic matters containing sulfur and nitrogen at normal temperature and normal pressure. Further, the stirring reaction time is 2 to 10 hours.
Specifically, the molar ratio of the expanded black phosphorus to the sulfur-and nitrogen-containing heterocyclic organic matter is 0.1: 1-10: 1.
Specifically, the sulfur-and nitrogen-containing heterocyclic organic compound is selected from one of 1, 3-bis (2,4, 6-trimethylphenyl) benzothiazolyl chloride, N-methyl-N-sulfonic acid butyl benzocarbazole and N-methyl-N-carboxylic acid ethyl benzocarbazole.
Specifically, step S110, step S120, and step S130 are performed under the air condition.
According to the preparation method of the black phosphorus nanosheet, black phosphorus is used as a cathode, the ionic liquid or the quaternary ammonium salt solution is used as an electrolyte, the anode is electrified for electrochemical reaction to obtain expanded graphite, the expanded black phosphorus and an oil-soluble solvent are mixed for ultrasonic stripping to obtain stripping slurry, the stripping slurry is mixed with a heterocyclic organic matter containing sulfur and nitrogen for reaction, and the ionic salt covalently modified black phosphorus nanosheet is obtained.
The black phosphorus nanosheet prepared by the preparation method of the black phosphorus nanosheet according to the embodiment has a stable structure and good dispersibility.
The black phosphorus nanosheet is applied to the field effect transistor. The black phosphorus nanosheet has the characteristics of excellent dispersibility and structural stability, and is beneficial to high-speed hole migration under the action of an electric field, so that the field effect transistor has high-sensitivity photoresponse capability when the black phosphorus nanosheet is applied to the field effect transistor.
The following are specific examples (the following examples, unless otherwise specified, contain no other components not specifically indicated except for unavoidable impurities):
examples 1 to 3
The preparation process of the black phosphorus nanosheet of embodiments 1-3 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in electrolyte according to the table 1, a certain voltage is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, the reaction system is subjected to centrifugal separation to obtain filter residue, and DMF is used for cleaning the filter residue to obtain the expanded black phosphorus.
(2) According to the table 1, the expanded black phosphorus and DMF in a mass-to-volume ratio of M: a were mixed under air conditions and ultrasonically stripped at a power of 25W for 10 minutes to obtain a stripping slurry.
(3) According to the table 1, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen are stirred and reacted for 6 hours under the condition of air at normal temperature and normal pressure to obtain the black phosphorus nanosheet. In Table 1, M: N is the molar ratio of the expanded black phosphorus to the sulfur and nitrogen containing heterocyclic organic compound.
TABLE 1
Example 4 and example 5
The preparation process of the black phosphorus nanosheets of examples 4 and 5 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, the black phosphorus and an anode are placed in electrolyte according to the table 1, a certain voltage is applied to the black phosphorus and the anode to carry out electrochemical reaction, a reaction system is obtained, the anode is taken away, then the reaction system is subjected to centrifugal separation, filter residue is obtained, and DMSO is used for cleaning the filter residue, so that the expanded black phosphorus is obtained.
(2) According to the table 1, the expanded black phosphorus and DMSO in the mass-to-volume ratio of M: a were mixed under air conditions and ultrasonically stripped at a power of 5W for 60 minutes to obtain a stripping slurry.
(3) According to the table 1, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen are stirred and reacted for 10 hours under the condition of air at normal temperature and normal pressure to obtain the black phosphorus nanosheet.
Example 6 and example 7
The preparation of the black phosphorus nanoplates of example 6 and example 7 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in electrolyte according to the table 1, a certain voltage is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, the reaction system is subjected to centrifugal separation to obtain filter residue, and the filter residue is cleaned by NMP to obtain the expanded black phosphorus.
(2) According to table 1, expanded black phosphorus and NMP in a mass-to-volume ratio of M: a were mixed under air conditions and ultrasonically stripped at a power of 50W for 5 minutes to obtain a stripping slurry.
(3) According to the table 1, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen are stirred and reacted for 2 hours under the condition of air at normal temperature and normal pressure to obtain the black phosphorus nanosheet.
Examples 8 to 9
The preparation process of the black phosphorus nanosheets of examples 8-9 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in electrolyte according to the table 1, a certain voltage is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, the reaction system is subjected to centrifugal separation to obtain filter residue, and THF is used for cleaning the filter residue to obtain the expanded black phosphorus.
(2) According to the table 1, the expanded black phosphorus and THF in a mass-to-volume ratio of M: a were mixed under air conditions and ultrasonically stripped at a power of 30W for 20 minutes to obtain a stripping slurry.
(3) According to the table 1, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen are stirred and reacted for 8 hours under the condition of air at normal temperature and normal pressure to obtain the black phosphorus nanosheet.
Example 10
The process for producing black phosphorus nanoplates of example 10 was substantially the same as that of example 3 except that the voltage was different and that of example 10 was 12V.
Example 11
The process for preparing black phosphorus nanoplates of example 11 was substantially the same as example 2 except that the voltage was different, and example 11 had a voltage of 0.8V.
Examples 12 to 14
The preparation process of the black phosphorus nanosheets of examples 12-14 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in electrolyte according to the table 2, a certain voltage is applied to the black phosphorus and the anode to carry out electrochemical reaction, a reaction system is obtained, the anode is taken away, then the reaction system is subjected to centrifugal separation, filter residue is obtained, and DMF is used for cleaning the filter residue, so that the expanded black phosphorus is obtained.
(2) According to table 2, expanded black phosphorus and DMF in a mass to volume ratio of M: a were mixed under air conditions and ultrasonically peeled at a power of 25W for 10 minutes to obtain a peeling slurry.
(3) According to the table 2, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen are stirred and reacted for 6 hours under the condition of air at normal temperature and normal pressure to obtain the black phosphorus nanosheet. In Table 2, M: N is the molar ratio of the expanded black phosphorus to the sulfur and nitrogen containing heterocyclic organic compounds.
TABLE 2
Example 15 and example 16
The preparation process of the black phosphorus nanoplates of examples 15 and 16 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, the black phosphorus and an anode are placed in electrolyte according to the table 2, a certain voltage is applied to the black phosphorus and the anode to carry out electrochemical reaction, a reaction system is obtained, the anode is taken away, then the reaction system is subjected to centrifugal separation, filter residue is obtained, and DMSO is used for cleaning the filter residue, so that the expanded black phosphorus is obtained.
(2) According to table 2, expanded black phosphorus and DMSO in a mass-to-volume ratio of M: a were mixed under air conditions and ultrasonically stripped at a power of 50W for 5 minutes to obtain a stripping slurry. Wherein, M: A in the table 2 is the mass-volume ratio of the expanded black phosphorus to the oil-soluble solvent.
(3) According to the table 2, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen are stirred and reacted for 10 hours under the condition of air at normal temperature and normal pressure to obtain the black phosphorus nanosheet. In Table 2, M: N is the molar ratio of the expanded black phosphorus to the sulfur and nitrogen containing heterocyclic organic compounds.
Example 17 and example 18
The preparation of black phosphorus nanoplates of example 17 and example 18 was as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in an electrolyte according to the table 2, a certain voltage is applied to the black phosphorus and the anode to carry out an electrochemical reaction to obtain a reaction system, the anode is taken away, the reaction system is subjected to centrifugal separation to obtain filter residue, and the filter residue is cleaned by NMP to obtain expanded black phosphorus.
(2) According to table 2, expanded black phosphorus and NMP in a mass-to-volume ratio of M: a were mixed under air conditions and ultrasonically stripped at a power of 5W for 60 minutes to obtain a stripping slurry.
(3) According to the table 2, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen are stirred and reacted for 2 hours under the condition of air at normal temperature and normal pressure to obtain the black phosphorus nanosheet.
Examples 19 to 20
The preparation process of the black phosphorus nanosheets of examples 19-20 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, the black phosphorus and an anode are placed in electrolyte according to the table 2, a certain voltage is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, the reaction system is subjected to centrifugal separation to obtain filter residue, and THF is used for cleaning the filter residue to obtain the expanded black phosphorus.
(2) According to Table 2, expanded black phosphorus and THF in a mass-to-volume ratio of M: A were mixed under air conditions and ultrasonically peeled at a power of 20W for 40 minutes to obtain a peeling slurry.
(3) According to the table 2, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen are stirred and reacted for 8 hours under the condition of air at normal temperature and normal pressure to obtain the black phosphorus nanosheet.
Example 21
The process for producing black phosphorus nanoplates of the present example was substantially the same as that of example 12 except that the solute concentration of the electrolyte was 11 g/mL.
Examples 22 and 23
The preparation of black phosphorus nanoplates of example 22 and example 23 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in an electrolyte according to the table 3, current with certain density is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, then the reaction system is subjected to centrifugal separation to obtain filter residue, and the filter residue is washed by DMF to obtain expanded black phosphorus.
(2) According to Table 3, expanded black phosphorus and DMF in a mass to volume ratio of M: A were mixed and ultrasonically peeled at a power of 25W for 10 minutes to obtain a peeling slurry.
(3) According to the table 3, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen were stirred and reacted for 4 hours at normal temperature and normal pressure under the air condition, so as to obtain the black phosphorus nanosheet. Wherein M: N in Table 3 is the molar ratio of expanded black phosphorus to sulfur and nitrogen containing heterocyclic organic compounds.
TABLE 3
Example 24 and example 25
The preparation processes of the black phosphorus nanoplates of example 24 and example 25 are as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in an electrolyte according to the table 3, current with certain density is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, then the reaction system is subjected to centrifugal separation to obtain filter residue, and the filter residue is cleaned by DMSO to obtain the expanded black phosphorus.
(2) According to table 3, under air conditions, expanded black phosphorus and DMSO were mixed at a mass to volume ratio of M: a, and ultrasonically stripped at a power of 30W for 20 minutes to obtain a stripping slurry.
(3) According to table 3, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen were stirred and reacted for 10 hours at normal temperature and normal pressure under the air condition, so as to obtain the black phosphorus nanosheet. In Table 3, M: N is the molar ratio of the expanded black phosphorus to the sulfur and nitrogen containing heterocyclic organic compound.
Example 26 and example 27
The preparation of black phosphorus nanoplates of example 26 and example 27 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in an electrolyte according to the table 3, current with certain density is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, then the reaction system is subjected to centrifugal separation to obtain filter residue, and the filter residue is cleaned by NMP to obtain the expanded black phosphorus.
(2) According to table 3, expanded black phosphorus and NMP in a mass-to-volume ratio of M: a were mixed under air conditions and ultrasonically peeled at a power of 5W for 60 minutes to obtain a peeling slurry.
(3) According to the table 3, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen were stirred and reacted for 2 hours at normal temperature and normal pressure under the air condition, so as to obtain the black phosphorus nanosheet. In Table 3, M: N is the molar ratio of the expanded black phosphorus to the sulfur and nitrogen containing heterocyclic organic compound.
Example 28 and example 29
The preparation of black phosphorus nanoplates of example 28 and example 29 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in an electrolyte according to the table 3, current with certain density is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, then the reaction system is subjected to centrifugal separation to obtain filter residue, and THF is used for cleaning the filter residue to obtain the expanded black phosphorus.
(2) According to Table 3, expanded black phosphorus and THF in a mass-to-volume ratio of M: A were mixed under air conditions and ultrasonically peeled at a power of 50W for 5 minutes to obtain a peeling slurry.
(3) According to the table 3, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen are stirred and reacted for 8 hours under the condition of air at normal temperature and normal pressure to obtain the black phosphorus nanosheet.
Example 30
The process for producing black phosphorus nanoplates of example 30 was substantially the same as that of example 23, except that the current density of example 30 was 0.8mA/cm2。
Example 31
The process for producing black phosphorus nanosheets of example 31 is substantially the same as that for example 24, except that the current density of example 31 is 105mA/cm2。
Example 32 and example 33
The preparation of black phosphorus nanoplates of example 32 and example 33 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in an electrolyte according to the table 4, current with certain density is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, then the reaction system is subjected to centrifugal separation to obtain filter residue, and the filter residue is washed by DMF to obtain the expanded black phosphorus.
(2) According to Table 4, expanded black phosphorus and DMF in a mass-to-volume ratio of M: A were mixed under air conditions and ultrasonically peeled at a power of 25W for 10 minutes to obtain a peeling slurry.
(3) According to table 4, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen were stirred and reacted for 4 hours at normal temperature and normal pressure under the air condition, so as to obtain the black phosphorus nanosheet. Wherein M: N in Table 4 is the molar ratio of expanded black phosphorus to sulfur and nitrogen containing heterocyclic organic compounds.
TABLE 4
Examples 34 and 35
The preparation process of the black phosphorus nanoplates of example 34 and example 35 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in an electrolyte according to the table 4, current with certain density is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, then the reaction system is subjected to centrifugal separation to obtain filter residue, and the filter residue is cleaned by DMSO to obtain the expanded black phosphorus.
(2) According to table 4, under air conditions, expanded black phosphorus and DMSO were mixed at a mass to volume ratio of M: a, and ultrasonically stripped at a power of 25W for 30 minutes to obtain a stripping slurry.
(3) According to table 4, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen were stirred and reacted for 10 hours at normal temperature and normal pressure under the air condition, so as to obtain the black phosphorus nanosheet. In Table 4, M: N is the molar ratio of the expanded black phosphorus to the sulfur and nitrogen containing heterocyclic organic compound.
Examples 36 and 37
The preparation of black phosphorus nanoplates of example 36 and example 37 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in an electrolyte according to the table 4, current with certain density is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, then the reaction system is subjected to centrifugal separation to obtain filter residue, and the filter residue is cleaned by NMP to obtain the expanded black phosphorus.
(2) According to Table 4, expanded black phosphorus and NMP in a mass-to-volume ratio of M: A were mixed and ultrasonically peeled at a power of 25W for 15 minutes to obtain a peeling slurry.
(3) According to table 4, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen were stirred and reacted for 2 hours at normal temperature and normal pressure under the air condition, so as to obtain the black phosphorus nanosheet. In Table 4, M: N is the molar ratio of the expanded black phosphorus to the sulfur and nitrogen containing heterocyclic organic compound.
Examples 38 and 39
The preparation of black phosphorus nanoplates of example 38 and example 39 is as follows:
(1) under the condition of air, black phosphorus is used as a cathode, black phosphorus and an anode are placed in an electrolyte according to the table 4, current with certain density is applied to the black phosphorus and the anode to carry out electrochemical reaction to obtain a reaction system, the anode is taken away, then the reaction system is subjected to centrifugal separation to obtain filter residue, and THF is used for cleaning the filter residue to obtain the expanded black phosphorus.
(2) According to Table 4, expanded black phosphorus and THF in a mass-to-volume ratio of M: A were mixed under air conditions and ultrasonically peeled at a power of 25W for 12 minutes to obtain a peeling slurry.
(3) According to table 4, the stripping slurry and the heterocyclic organic matter containing sulfur and nitrogen were stirred and reacted for 8 hours at normal temperature and normal pressure under the air condition, so as to obtain the black phosphorus nanosheet.
Example 40
The process for the preparation of black phosphorus nanoplates of this example is substantially the same as example 35 except that the molar ratio of expanded black phosphorus to sulfur and nitrogen containing heterocyclic organic compound, M: N, is different and M: N of this example is 11: 1.
Comparative example 1
Comparative example 1 is a conventional direct ultrasonic stripped two dimensional black phosphorus.
And (3) testing:
fig. 1 is a Raman (Raman) spectrum of the black phosphorus nanosheet prepared in example 1 (523 nm laser light source is used in the test), in which bulk, IL, 2L, 3L, 4L and 5L respectively represent the black phosphorus that is not peeled off, and the black phosphorus nanosheet that has a thickness of one layer, a thickness of two layers, a thickness of three layers, a thickness of four layers and a thickness of five layers after peeling off. In the figure, Si is a substrate used in Raman spectrum test, and the obtained peeled nano sheet material must be loaded on a silicon substrate which cannot generate interference to play a supporting role. The results of the experiment can be seen in FIG. 1The black phosphorus nano-sheet is from single layer to multilayer and is positioned at 361.2cm in the figure-1、439.5cm-1And 468.6cm-1Three typical raman characteristic peaks correspond to three phonon modes in the black phosphorus structure: out-of-plane Ag 1In-plane B2gAnd Ag 2The three lattice vibration modes show that the black phosphorus nanosheet obtained by stripping has high crystallinity and good crystallinity.
Fig. 2 is a Transmission (TEM) electron micrograph of the black phosphorus nanoplate prepared in example 1, illustrating that the prepared black phosphorus material is of a nanoplate structure. Fig. 3 is an electron diffraction pattern of a selected area corresponding to fig. 2, and clear spots illustrate the single crystal state of the material, further illustrating that the black phosphorus nanosheet obtained by exfoliation is highly crystalline. FIG. 4 is an enlarged view magnified 1000 times of FIG. 2, from which it can be seen that the black phosphorus nanosheet has clear lattice fringes and interplanar spacings, no visible lattice defects and stable structure, and the interplanar spacings of two interplanar planes (021) and (041) of the black phosphorus nanosheet are respectivelyAnd
the black phosphorus nanosheets of embodiments 2 to 40 have raman spectrograms, electron diffraction patterns and transmission electron microscopy patterns similar to those of the black phosphorus nanosheets prepared in embodiment 1, which are not described herein again, wherein the crystallization condition and the structure stability condition of the black phosphorus nanosheets of embodiments 1 to 40 are shown in table 5.
And (3) testing the dispersibility: respectively dispersing the black phosphorus nanosheets prepared in the examples 1 to 40 in methyl pyrrolidone according to the mass-to-volume ratio of 10mg:40mL by ultrasonic for 0.5 hour to respectively obtain the dispersion liquid of the black phosphorus nanosheets in the examples 1 to 40 and the dispersion liquid of the two-dimensional black phosphorus in the comparative example 1, standing for 12 hours, directly observing whether the bottom is precipitated, and if the bottom is not precipitated, obtaining good dispersibility. The dispersibility of the black phosphorus nanosheets of examples 1-40 and the conventional two-dimensional black phosphorus of comparative example 1 is shown in table 5.
Hole transportAnd (3) rate testing: spin coating the dispersions of black phosphorus nanoplates of examples 1-40 and the dispersion of two-dimensional black phosphorus of comparative example 1 to SiO2On a/Si substrate, the thickness is about 300 nanometers, a copper mesh is covered on the substrate, a Cr/Au thin film is used as a corresponding electrode (wherein, the thickness of the Cr layer is 3nm, the thickness of the Au layer is 50nm), field effect transistors are respectively manufactured, and the black phosphorus nanosheets of examples 1-40 and the field effect transistors corresponding to the two-dimensional black phosphorus of comparative example 1 are connected to a Keithly 4200 semiconductor analyzer to test the hole mobility of each field effect transistor. Wherein, fig. 5 is a bar graph of the hole mobility of the field effect transistor corresponding to the black phosphorus nano-sheet of the example 1, and the average hole mobility of the field effect transistor of the example 1 is calculated to be 60cm2·V-1·s-1Wherein the average hole mobility of the field effect transistors corresponding to the black phosphorus nanosheets of examples 2-40 and the conventional two-dimensional black phosphorus of comparative example 1 are shown in table 5.
Wherein, the yield of the black phosphorus nanosheets of examples 1-40 is also reported in Table 5.
TABLE 5
As can be seen from Table 5, the black phosphorus nanoplates of examples 1 to 40 have high crystallinity and better dispersibility than the two-dimensional black phosphorus of comparative example 1, and the field effect transistors corresponding to the black phosphorus nanoplates of examples 1 to 40 have an average hole mobility of at least 20cm2·V-1·s-1And has higher average hole mobility.
Among them, the black phosphorus nanoplates of examples 1 to 9, 12 to 20, 22 to 29, and 32 to 39 have better dispersibility and higher average hole mobility than the black phosphorus nanoplates of examples 10, 11, 21, 30, 31, and 40.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of black phosphorus nanosheets is characterized by comprising the following steps:
black phosphorus is taken as a cathode, the black phosphorus and an anode are placed in electrolyte, the black phosphorus and the anode are electrified to carry out electrochemical reaction to obtain expanded black phosphorus, the electrolyte is ionic liquid, or the electrolyte is a quaternary ammonium salt solution, and the ionic liquid is at least one selected from 1-ethyl-3-methylimidazole bromine salt, 1-ethyl-3-methylimidazole chlorine salt, 1-ethyl-3-methylimidazole iodine salt, 1-ethyl-2, 3-dimethylimidazole trifluoromethanesulfonate, 1, 2-diethyl-3-methylimidazole trifluoromethanesulfonate, 1, 2-dimethyl-3-ethylimidazole bromine salt, 1, 2-dimethyl-3-ethylimidazole chlorine salt and 1, -dimethyl-3-ethylimidazole tetrafluoroborate; the solute of the quaternary ammonium salt solution is selected from at least one of 1-ethyl-3-methyl ammonium tetrafluoroborate, n-butyl ammonium tetrachlorochlorate, n-butyl ammonium tetrafluoroborate and n-butyl ammonium tetrafluorophosphate;
mixing the expanded black phosphorus and an oil-soluble solvent for ultrasonic stripping to obtain stripping slurry; and
mixing and reacting the stripping slurry with a heterocyclic organic matter containing sulfur and nitrogen to obtain the black phosphorus nanosheet; the heterocyclic organic matter containing sulfur and nitrogen is selected from one of 1, 3-bis (2,4, 6-trimethylphenyl) benzothiazole chloride, N-methyl-N-sulfobutyl benzocarbazole and N-methyl-N-carboxylic acid ethylbenzocarbazole.
2. A method of making black phosphorus nanoplates as in claim 1, wherein the step of energizing the black phosphorus and the anode to perform an electrochemical reaction is: and applying a voltage of 1V-10V to the black phosphorus and the anode to perform an electrochemical reaction.
3. A method of making black phosphorus nanoplates as in claim 1, wherein the step of energizing the black phosphorus and the anode to perform an electrochemical reaction is: applying a density of 1mA/cm to the black phosphorus and the anode2~100mA/cm2To carry out an electrochemical reaction.
4. A method of making black phosphorus nanoplatelets as in claim 1 wherein the step of mixing the expanded black phosphorus with an oil soluble solvent for ultrasonic exfoliation further comprises a step of separating and purifying the expanded black phosphorus, the step of separating and purifying comprising: and removing the anode in the reaction system, carrying out centrifugal separation on the reaction system to obtain filter residue, and cleaning the filter residue to obtain the purified expanded black phosphorus.
5. A method for producing black phosphorus nanoplatelets as in claim 1 wherein the step of energizing the black phosphorus and the anode for electrochemical reaction, the step of mixing the expanded black phosphorus and an oil-soluble solvent for ultrasonic exfoliation, and the step of mixing the exfoliated slurry with a sulfur-and nitrogen-containing heterocyclic organic compound are all performed under air conditions.
6. A method of making black phosphorus nanoplatelets according to any of the claims 1-5 wherein the molar ratio of the expanded black phosphorus to the sulfur and nitrogen containing heterocyclic organic compound is 0.1:1 to 10: 1.
7. A method of producing black phosphorus nanoplatelets according to any of the claims 1 to 5 wherein the oil-soluble solvent is selected from at least one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran; and/or the concentration of the solute of the quaternary ammonium salt solution is 0.05 g/mL-10 g/mL; and/or the solvent of the quaternary ammonium salt solution is one selected from N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran.
8. A method for preparing black phosphorus nanoplatelets according to any of claims 1 to 5 wherein the anode is selected from one of platinum, graphite carbon rod and graphene paper.
9. A black phosphorus nanoplate prepared by the method of preparing a black phosphorus nanoplate according to any one of claims 1 to 8.
10. Use of the black phosphorus nanoplatelet of claim 9 in the preparation of a field effect transistor.
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