CN108772079B - Preparation method of nano black phosphorus/graphene composite material - Google Patents
Preparation method of nano black phosphorus/graphene composite material Download PDFInfo
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- CN108772079B CN108772079B CN201810384561.4A CN201810384561A CN108772079B CN 108772079 B CN108772079 B CN 108772079B CN 201810384561 A CN201810384561 A CN 201810384561A CN 108772079 B CN108772079 B CN 108772079B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 228
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 216
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 135
- 239000007788 liquid Substances 0.000 claims abstract description 131
- 239000007787 solid Substances 0.000 claims abstract description 30
- 239000011261 inert gas Substances 0.000 claims abstract description 20
- 239000008259 solid foam Substances 0.000 claims abstract description 20
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 18
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- -1 black phosphorus alkene Chemical class 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 5
- AWSCOTJIASXILV-UHFFFAOYSA-N 1-butyl-2,4,5-trimethylimidazole Chemical compound CCCCN1C(C)=NC(C)=C1C AWSCOTJIASXILV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002127 nanobelt Substances 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 abstract description 5
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 238000004146 energy storage Methods 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 8
- 238000001069 Raman spectroscopy Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000007710 freezing Methods 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
Abstract
The invention relates to a preparation method of a nano black phosphorus/graphene composite material, and belongs to the technical field of composite materials. Mixing the nano black phosphorus dispersion liquid with the graphene oxide dispersion liquid at the temperature of 5-30 ℃, and performing ultrasonic treatment to obtain a nano black phosphorus/graphene oxide dispersion liquid; freeze-drying the nano black phosphorus/graphene oxide dispersion liquid to obtain nano black phosphorus/graphene oxide solid foam; placing the nano black phosphorus/graphene oxide solid foam in an inert gas atmosphere for ultraviolet, infrared or visible light irradiation pretreatment for 2-72 hours to obtain a nano black phosphorus/pre-reduced graphene oxide solid; and (3) placing the nano black phosphorus/pre-reduced graphene oxide solid in an inert gas atmosphere at the temperature of 50-300 ℃ and carrying out reduction treatment for 0.5-10 h under the microwave condition to obtain the nano black phosphorus/graphene composite material. The high-quality nano black phosphorus/graphene composite material is prepared by adopting a mode of combining photoreduction and microwave reduction.
Description
Technical Field
The invention relates to a preparation method of a nano black phosphorus/graphene composite material, and belongs to the technical field of composite materials.
Background
The black phosphorus is a two-dimensional layered material of a single element, and has excellent characteristics of direct band gap, good photoelectron performance, high carrier mobility and the like due to the unique crystal structure and energy band structure, so that the black phosphorus has good application prospects in black phosphorus domains of energy storage, photocatalysis and the like. In many applications of black phosphorus, people usually make the black phosphorus into nano particles to obtain the nano black phosphorus (nano black phosphorus and black phosphorus quantum dots). When applied to the field of energy storage: the phosphorus material generally has the problems of low conductivity, poor cycle performance and the like, and the nano black phosphorus is unstable in air and is easy to degrade under the action of water and oxygen in the air.
The preparation method of the existing nano black phosphorus/graphene composite material mainly comprises the following steps: (1) the nano black phosphorus and the graphene are dispersed in an organic solvent to be physically mixed, and then the nano black phosphorus/graphene composite material is obtained after drying. (2) Dispersing the nano black phosphorus and the graphene oxide in an organic solvent, carrying out vacuum filtration to obtain nano black phosphorus/graphene oxide Paper (PGO), and carrying out plasma sintering on the PGO to obtain the nano black phosphorus/graphene oxide composite material (PG-SPS). Although the composite material prepared by the method has strong binding force between the nano black phosphorus and the graphene, the obtained graphene has relatively poor conductivity.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides the preparation method of the nano black phosphorus/graphene composite material.
A preparation method of a nano black phosphorus/graphene composite material comprises the following specific steps:
(1) mixing the nano black phosphorus dispersion liquid with the graphene oxide dispersion liquid at the temperature of 5-30 ℃, and performing ultrasonic treatment to obtain a nano black phosphorus/graphene oxide dispersion liquid;
(2) freeze-drying the nano black phosphorus/graphene oxide dispersion liquid obtained in the step (1) to obtain nano black phosphorus/graphene oxide solid foam;
(3) placing the nano black phosphorus/graphene oxide solid foam obtained in the step (2) in an inert gas atmosphere for ultraviolet, infrared or visible light irradiation pretreatment for 2-72 hours to obtain a nano black phosphorus/pre-reduced graphene oxide solid;
(4) placing the nano black phosphorus/pre-reduced graphene oxide solid obtained in the step (3) in an inert gas atmosphere, reducing at the temperature of 50-300 ℃ for 0.5-10 h under the microwave condition to obtain a nano black phosphorus/graphene composite material;
the concentration of the black phosphorus in the nano black phosphorus/graphene oxide dispersion liquid in the step (1) is 0.1-5 mg/mL, and the concentration of the graphene oxide in the nano black phosphorus/graphene oxide dispersion liquid is 0.1-5 mg/mL;
the nano black phosphorus in the step (1) is black phosphorus alkene, black phosphorus quantum dots, black phosphorus nanowires, black phosphorus nanotubes or black phosphorus nanobelts; the dispersion solvent of the nano black phosphorus dispersion liquid is water, ethanol, dimethyl sulfoxide, N-methyl pyrrolidone, isopropanol, N-dimethylformamide, ethylene carbonate or 1-butyl-trimethyl imidazole dicyandiamide; the dispersion solvent of the graphene oxide dispersion liquid is water, ethanol, dimethyl sulfoxide, N-methyl pyrrolidone, isopropanol, N-dimethylformamide, ethylene carbonate or 1-butyl-trimethyl imidazole dicyandiamide;
the ultrasonic pretreatment in the step (1) is carried out by adopting an ultrasonic cell cleaner and/or a cell crusher, the power of the ultrasonic cell cleaner is 150-300W, the power of the cell crusher is 500-1500W, and the ultrasonic treatment time is 2-24 h;
the microwave power in the step (4) is 300-1000W;
the inert gas is one or more of argon, nitrogen and helium;
the nano black phosphorus dispersion liquid is obtained by adding nano black phosphorus into a dispersion solvent and carrying out ultrasonic pretreatment by an ultrasonic cell cleaner and/or a cell crusher;
the graphene oxide aqueous dispersion liquid is prepared according to the literature of Large reversible capacity of high quality graphene sheets as an inorganic material for lithium-ion batteries or the literature of Porous SnO2Prepared from @ C/graphene nanocomposite with 3D carbon conductive network as a super anode material for lithium-ion batteries';
the invention has the beneficial effects that:
(1) the method adopts a mode of combining photoreduction and microwave reduction to prepare the high-quality nano black phosphorus/graphene composite material;
(2) the method has the advantages of simple operation, energy conservation, high efficiency and mild reaction conditions;
(3) in the photoreduction process, the nano black phosphorus plays a photocatalysis role to promote the further reduction of the graphene oxide; in the microwave reduction process, under the action of microwaves (electromagnetic waves), graphene oxide can be reduced into high-quality and high-conductivity graphene; meanwhile, under the action of photoreduction and microwave reduction, the nano black phosphorus and the graphene can form a P-C chemical bond with strong interaction force, so that the stable existence of the nano black phosphorus is facilitated, and the photocatalytic capacity and the energy storage capacity are improved.
Drawings
FIG. 1 is a scanning electron microscope image of the nano black phosphorus/graphene oxide solid foam of example 1;
FIG. 2 is a scanning electron micrograph of the nano black phosphorus/pre-reduced graphene oxide solid of example 1;
FIG. 3 is a scanning electron micrograph of the nano black phosphorus/graphene composite material of example 1;
FIG. 4 is a carbon distribution diagram of the nano black phosphorus/graphene composite material of example 1;
FIG. 5 is a phosphorus distribution plot of the nano black phosphorus/graphene composite of example 1;
FIG. 6 is a Raman comparison graph of the nano black phosphorus/graphene oxide solid and the nano black phosphorus/graphene composite material in example 1;
FIG. 7 is P of the nano black phosphorus/graphene composite material of example 12PA drawing;
FIG. 8 shows C of the nano black phosphorus/graphene composite material of example 11sFigure (a).
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1: a preparation method of a nano black phosphorus/graphene composite material comprises the following specific steps:
(1) mixing a nano black phosphorus dispersion liquid (the nano black phosphorus dispersion liquid is nano black phosphorus alkene/water dispersion liquid) and a graphene oxide dispersion liquid (the graphene oxide dispersion liquid is graphene oxide/water dispersion liquid) at the temperature of 15 ℃, and performing ultrasonic treatment to obtain the nano black phosphorus/graphene oxide dispersion liquid; the concentration of the nano black phosphorus dispersion liquid (nano black phosphorus/water dispersion liquid) is 2 mg/mL, the concentration of the graphene oxide dispersion liquid (graphene oxide/water dispersion liquid) is 2 mg/mL, the volume ratio of the nano black phosphorus dispersion liquid (nano black phosphorus/water dispersion liquid) to the graphene oxide dispersion liquid (graphene oxide/water dispersion liquid) is 1:1, the concentration of nano black phosphorus in the nano black phosphorus/graphene oxide dispersion liquid is 1 mg/mL, and the concentration of graphene oxide in the nano black phosphorus/graphene oxide dispersion liquid is 1 mg/mL; the ultrasonic treatment is that ultrasonic pretreatment is carried out by sequentially adopting an ultrasonic cell cleaner and a cell crusher, the power of the ultrasonic cell cleaner is 150W, the treatment time of the ultrasonic cell cleaner is 1h, the power of the cell crusher is 500W, and the treatment time of the cell crusher is 1 h;
(2) freezing the nano black phosphorus/graphene oxide dispersion liquid obtained in the step (1) at the temperature of-80 ℃ for 5 hours to form a nano black phosphorus/graphene oxide ice solid, and then carrying out freeze drying to obtain nano black phosphorus/graphene oxide solid foam;
(3) placing the nano black phosphorus/graphene oxide solid foam obtained in the step (2) in an inert gas (argon) atmosphere for ultraviolet irradiation pretreatment for 48 hours to obtain a nano black phosphorus/pre-reduced graphene oxide solid;
(4) placing the nano black phosphorus/pre-reduced graphene oxide solid obtained in the step (3) in an inert gas (argon) atmosphere, reducing for 4 hours at the temperature of 200 ℃ under the microwave condition to obtain a nano black phosphorus/graphene composite material;
the scanning electron microscope image of the nano black phosphorus/graphene oxide solid foam obtained in the embodiment is shown in fig. 1, the scanning electron microscope image of the nano black phosphorus/pre-reduced graphene oxide solid obtained in the embodiment is shown in fig. 2, the scanning electron microscope image of the nano black phosphorus/graphene composite material obtained in the embodiment is shown in fig. 3, and as can be seen from fig. 1 to 3, the graphene maintains a good fold structure in the process of preparing the nano black phosphorus/graphene composite material in the embodiment;
the phosphorus distribution diagram of the nano black phosphorus/graphene composite material obtained in the embodiment is shown in fig. 4, the carbon distribution diagram of the nano black phosphorus/graphene composite material obtained in the embodiment is shown in fig. 5, and as can be seen from fig. 4 to 5, the phosphorus and carbon in the nano phosphorus/graphene composite material prepared in the embodiment are uniformly distributed;
a raman contrast graph of the nano black phosphorus/graphene oxide solid and the nano black phosphorus/graphene composite material obtained in this example is shown in fig. 6, and it can be seen from fig. 6 that both the nano black phosphorus/graphene oxide solid and the nano black phosphorus/graphene composite material have a characteristic peak a of nano black phosphorusg 1、B2gAnd Ag 2The results show that the structure of the nano black phosphorus is not damaged in the process of preparing the nano black phosphorus/graphene composite material; the characteristic peaks D, G and 2D of graphene oxide and graphene appear in the nano black phosphorus/graphene oxide solid and nano black phosphorus/graphene composite material, and the nano black phosphorus/graphene composite material obtained after illumination and microwave treatment has a relatively sharp 2D peak, which indicates that the composite material obtained after illumination and microwave treatment has higher graphitization degree and better conductivity;
spectrograms of P2P and C1S of the nano black phosphorus/graphene composite material obtained in the embodiment are shown in FIGS. 7 to 8, and it can be seen from FIGS. 7 to 8 that the nano phosphorus/graphene composite material prepared by the method of the present invention contains P-C bonds and P-O-C bonds, which indicates that the nano phosphorus/graphene composite material prepared in the embodiment has higher stability;
the nano-phosphorus/graphene composite material has high conductivity and stability; the nano phosphorus/graphene composite material can be applied to the fields of energy storage, photocatalysis and the like.
Example 2: a preparation method of a nano black phosphorus/graphene composite material comprises the following specific steps:
(1) mixing the nano black phosphorus dispersion liquid (the nano black phosphorus dispersion liquid is nano black phosphorus alkene/dimethyl sulfoxide dispersion liquid) and the graphene oxide dispersion liquid (the graphene oxide dispersion liquid is graphene oxide/N-methyl pyrrolidone dispersion liquid) at the temperature of 15 ℃, and performing ultrasonic treatment to obtain the nano black phosphorus/graphene oxide dispersion liquid; the concentration of the nano black phosphorus dispersion liquid (nano black phosphorus/dimethyl sulfoxide dispersion liquid) is 2 mg/mL, the concentration of the graphene oxide dispersion liquid (graphene oxide/N-methyl pyrrolidone dispersion liquid) is 2 mg/mL, the volume ratio of the nano black phosphorus dispersion liquid (nano black phosphorus/dimethyl sulfoxide dispersion liquid) to the graphene oxide dispersion liquid (graphene oxide/N-methyl pyrrolidone dispersion liquid) is 1:2, the concentration of nano black phosphorus in the nano black phosphorus/graphene oxide dispersion liquid is 0.67 mg/mL, and the concentration of graphene oxide in the nano black phosphorus/graphene oxide dispersion liquid is 1.33 mg/mL; the ultrasonic treatment is ultrasonic pretreatment by adopting an ultrasonic cell cleaner, the power of the ultrasonic cell cleaner is 200W, and the treatment time of the ultrasonic cell cleaner is 5 h;
(2) freezing the nano black phosphorus/graphene oxide dispersion liquid obtained in the step (1) under the condition of liquid nitrogen to form a nano black phosphorus/graphene oxide ice solid, and then carrying out freeze drying to obtain nano black phosphorus/graphene oxide solid foam;
(3) placing the nano black phosphorus/graphene oxide solid foam obtained in the step (2) in an inert gas (nitrogen) atmosphere for carrying out infrared light irradiation pretreatment for 40h to obtain a nano black phosphorus/pre-reduced graphene oxide solid;
(4) placing the nano black phosphorus/pre-reduced graphene oxide solid obtained in the step (3) in an inert gas (nitrogen) atmosphere, reducing for 3 hours at the temperature of 250 ℃ under the microwave condition to obtain a nano black phosphorus/graphene composite material;
the nano black phosphorus/graphene composite material prepared by the embodiment is characterized by a scanning electron microscope, Raman and XPS, and detection and analysis show that the composite material forms a P-C bond and a P-O-C bond, so that the composite material has good stability and conductivity; therefore, the composite material has good application prospects in the fields of energy storage, photocatalysis and the like.
Example 3: a preparation method of a nano black phosphorus/graphene composite material comprises the following specific steps:
(1) mixing a nano black phosphorus dispersion liquid (the nano black phosphorus dispersion liquid is a nano black phosphorus alkene/ethylene carbonate dispersion liquid) and a graphene oxide dispersion liquid (the graphene oxide dispersion liquid is a graphene oxide/N, N-dimethylformamide dispersion liquid) at the temperature of 30 ℃, and performing ultrasonic treatment to obtain the nano black phosphorus/graphene oxide dispersion liquid; the concentration of the nano black phosphorus dispersion liquid (nano black phosphorus/ethylene carbonate dispersion liquid) is 2 mg/mL, the concentration of the graphene oxide dispersion liquid (graphene oxide/N, N-dimethylformamide dispersion liquid) is 2 mg/mL, the volume ratio of the nano black phosphorus dispersion liquid (nano black phosphorus/ethylene carbonate dispersion liquid) to the graphene oxide dispersion liquid (graphene oxide/N, N-dimethylformamide dispersion liquid) is 1:4, the concentration of nano black phosphorus in the nano black phosphorus/graphene oxide dispersion liquid is 0.4 mg/mL, and the concentration of graphene oxide in the nano black phosphorus/graphene oxide dispersion liquid is 1.6 mg/mL; the ultrasonic treatment is ultrasonic pretreatment by adopting a cell crusher, the power of the cell crusher is 1000W, and the treatment time of the cell crusher is 3 h;
(2) freezing the nano black phosphorus/graphene oxide dispersion liquid obtained in the step (1) at the temperature of-80 ℃ for 10h to form a nano black phosphorus/graphene oxide ice solid, and then carrying out freeze drying to obtain nano black phosphorus/graphene oxide solid foam;
(3) placing the nano black phosphorus/graphene oxide solid foam obtained in the step (2) in an inert gas (nitrogen) atmosphere for visible light irradiation pretreatment for 72h to obtain a nano black phosphorus/pre-reduced graphene oxide solid;
(4) placing the nano black phosphorus/pre-reduced graphene oxide solid obtained in the step (3) in an inert gas (nitrogen) atmosphere, reducing for 2 hours at the temperature of 50 ℃ under the microwave condition to obtain a nano black phosphorus/graphene composite material;
the nano black phosphorus/graphene composite material prepared by the embodiment is characterized by a scanning electron microscope, Raman and XPS, and detection and analysis show that the composite material forms a P-C bond and a P-O-C bond, so that the composite material has good stability and conductivity; the nano phosphorus/graphene composite material can be applied to the fields of energy storage, photocatalysis and the like.
Example 4: a preparation method of a nano black phosphorus/graphene composite material comprises the following specific steps:
(1) mixing a nano black phosphorus dispersion liquid (the nano black phosphorus dispersion liquid is a nano black phosphorus alkene/ethylene carbonate dispersion liquid) and a graphene oxide dispersion liquid (the graphene oxide dispersion liquid is a graphene oxide/N, N-dimethylformamide dispersion liquid) at the temperature of 30 ℃, and performing ultrasonic treatment to obtain the nano black phosphorus/graphene oxide dispersion liquid; the concentration of the nano black phosphorus dispersion liquid (nano black phosphorus/ethylene carbonate dispersion liquid) is 3mg/mL, the concentration of the graphene oxide dispersion liquid (graphene oxide/N, N-dimethylformamide dispersion liquid) is 3mg/mL, the volume ratio of the nano black phosphorus dispersion liquid (nano black phosphorus/ethylene carbonate dispersion liquid) to the graphene oxide dispersion liquid (graphene oxide/N, N-dimethylformamide dispersion liquid) is 1:1, the concentration of nano black phosphorus in the nano black phosphorus/graphene oxide dispersion liquid is 1.5mg/mL, and the concentration of graphene oxide in the nano black phosphorus/graphene oxide dispersion liquid is 1.5 mg/mL; the ultrasonic treatment is ultrasonic pretreatment by adopting a cell crusher, the power of the cell crusher is 1000W, and the treatment time of the cell crusher is 3 h;
(2) freezing the nano black phosphorus/graphene oxide dispersion liquid obtained in the step (1) at the temperature of-80 ℃ for 10h to form a nano black phosphorus/graphene oxide ice solid, and then carrying out freeze drying to obtain nano black phosphorus/graphene oxide solid foam;
(3) placing the nano black phosphorus/graphene oxide solid foam obtained in the step (2) in an inert gas (nitrogen) atmosphere for visible light irradiation pretreatment for 72h to obtain a nano black phosphorus/pre-reduced graphene oxide solid;
(4) placing the nano black phosphorus/pre-reduced graphene oxide solid obtained in the step (3) in an inert gas (nitrogen) atmosphere, reducing for 2 hours at the temperature of 150 ℃ under the microwave condition to obtain a nano black phosphorus/graphene composite material;
the nano black phosphorus/graphene composite material prepared by the embodiment is characterized by a scanning electron microscope, Raman and XPS, and detection and analysis show that the composite material forms a P-C bond and a P-O-C bond, so that the nano black phosphorus/graphene composite material has good stability and conductivity, and can be applied to the fields of energy storage, photocatalysis and the like.
Example 5: a preparation method of a nano black phosphorus/graphene composite material comprises the following specific steps:
(1) mixing a nano black phosphorus dispersion liquid (the nano black phosphorus dispersion liquid is a nano black phosphorus alkene/ethylene carbonate dispersion liquid) and a graphene oxide dispersion liquid (the graphene oxide dispersion liquid is a graphene oxide/N, N-dimethylformamide dispersion liquid) at the temperature of 30 ℃, and performing ultrasonic treatment to obtain the nano black phosphorus/graphene oxide dispersion liquid; the concentration of the nano black phosphorus dispersion liquid (nano black phosphorus/ethylene carbonate dispersion liquid) is 5mg/mL, the concentration of the graphene oxide dispersion liquid (graphene oxide/N, N-dimethylformamide dispersion liquid) is 5mg/mL, the volume ratio of the nano black phosphorus dispersion liquid (nano black phosphorus/ethylene carbonate dispersion liquid) to the graphene oxide dispersion liquid (graphene oxide/N, N-dimethylformamide dispersion liquid) is 1:1, the concentration of nano black phosphorus in the nano black phosphorus/graphene oxide dispersion liquid is 2.5mg/mL, and the concentration of graphene oxide in the nano black phosphorus/graphene oxide dispersion liquid is 2.5 mg/mL; the ultrasonic treatment is ultrasonic pretreatment by adopting a cell crusher, the power of the cell crusher is 1000W, and the treatment time of the cell crusher is 3 h;
(2) freezing the nano black phosphorus/graphene oxide dispersion liquid obtained in the step (1) at the temperature of-80 ℃ for 10h to form a nano black phosphorus/graphene oxide ice solid, and then carrying out freeze drying to obtain nano black phosphorus/graphene oxide solid foam;
(3) placing the nano black phosphorus/graphene oxide solid foam obtained in the step (2) in an inert gas (nitrogen) atmosphere for visible light irradiation pretreatment for 2h to obtain a nano black phosphorus/pre-reduced graphene oxide solid;
(4) placing the nano black phosphorus/pre-reduced graphene oxide solid obtained in the step (3) in an inert gas (nitrogen) atmosphere, reducing for 10 hours at the temperature of 50 ℃ under the microwave condition to obtain a nano black phosphorus/graphene composite material;
the nano black phosphorus/graphene composite material prepared by the embodiment is characterized by a scanning electron microscope, Raman and XPS, and detection and analysis show that the composite material forms a P-C bond and a P-O-C bond, so that the nano black phosphorus/graphene composite material has good stability and conductivity, and can be applied to the fields of energy storage, photocatalysis and the like.
Example 6: a preparation method of a nano black phosphorus/graphene composite material comprises the following specific steps:
(1) mixing a nano black phosphorus dispersion liquid (the nano black phosphorus dispersion liquid is a nano black phosphorus alkene/ethylene carbonate dispersion liquid) and a graphene oxide dispersion liquid (the graphene oxide dispersion liquid is a graphene oxide/N, N-dimethylformamide dispersion liquid) at the temperature of 30 ℃, and performing ultrasonic treatment to obtain the nano black phosphorus/graphene oxide dispersion liquid; the concentration of the nano black phosphorus dispersion liquid (nano black phosphorus/ethylene carbonate dispersion liquid) is 0.1 mg/mL, the concentration of the graphene oxide dispersion liquid (graphene oxide/N, N-dimethylformamide dispersion liquid) is 0.1 mg/mL, the volume ratio of the nano black phosphorus dispersion liquid (nano black phosphorus/ethylene carbonate dispersion liquid) to the graphene oxide dispersion liquid (graphene oxide/N, N-dimethylformamide dispersion liquid) is 1:1, the concentration of nano black phosphorus in the nano black phosphorus/graphene oxide dispersion liquid is 0.05 mg/mL, and the concentration of graphene oxide in the nano black phosphorus/graphene oxide dispersion liquid is 0.05 mg/mL; the ultrasonic treatment is ultrasonic pretreatment by adopting a cell crusher, the power of the cell crusher is 1000W, and the treatment time of the cell crusher is 3 h;
(2) freezing the nano black phosphorus/graphene oxide dispersion liquid obtained in the step (1) at the temperature of-80 ℃ for 10h to form a nano black phosphorus/graphene oxide ice solid, and then carrying out freeze drying to obtain nano black phosphorus/graphene oxide solid foam;
(3) placing the nano black phosphorus/graphene oxide solid foam obtained in the step (2) in an inert gas (nitrogen) atmosphere for visible light irradiation pretreatment for 12h to obtain a nano black phosphorus/pre-reduced graphene oxide solid;
(4) placing the nano black phosphorus/pre-reduced graphene oxide solid obtained in the step (3) in an inert gas (nitrogen) atmosphere, reducing for 5 hours at the temperature of 100 ℃ under the microwave condition to obtain a nano black phosphorus/graphene composite material;
the nano black phosphorus/graphene composite material prepared by the embodiment is characterized by a scanning electron microscope, Raman and XPS, and detection and analysis show that the composite material forms a P-C bond and a P-O-C bond, so that the nano black phosphorus/graphene composite material has good stability and conductivity, and can be applied to the fields of energy storage, photocatalysis and the like.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (6)
1. A preparation method of a nano black phosphorus/graphene composite material is characterized by comprising the following specific steps:
(1) mixing the nano black phosphorus dispersion liquid with the graphene oxide dispersion liquid at the temperature of 5-30 ℃, and performing ultrasonic treatment to obtain a nano black phosphorus/graphene oxide dispersion liquid;
(2) freeze-drying the nano black phosphorus/graphene oxide dispersion liquid obtained in the step (1) to obtain nano black phosphorus/graphene oxide solid foam;
(3) placing the nano black phosphorus/graphene oxide solid foam obtained in the step (2) in an inert gas atmosphere for ultraviolet, infrared or visible light irradiation pretreatment for 2-72 hours to obtain a nano black phosphorus/pre-reduced graphene oxide solid;
(4) and (3) placing the nano black phosphorus/pre-reduced graphene oxide solid obtained in the step (3) in an inert gas atmosphere, reducing at the temperature of 50-300 ℃ for 0.5-10 h under the microwave condition to obtain the nano black phosphorus/graphene composite material.
2. The preparation method of the nano black phosphorus/graphene composite material according to claim 1, wherein the preparation method comprises the following steps: the concentration of the black phosphorus in the nano black phosphorus/graphene oxide dispersion liquid in the step (1) is 0.1-5 mg/mL, and the concentration of the graphene oxide in the nano black phosphorus/graphene oxide dispersion liquid is 0.1-5 mg/mL.
3. The preparation method of the nano black phosphorus/graphene composite material according to claim 1, wherein the preparation method comprises the following steps: the nano black phosphorus in the step (1) is black phosphorus alkene, black phosphorus quantum dots, black phosphorus nanowires, black phosphorus nanotubes or black phosphorus nanobelts; the dispersion solvent of the nano black phosphorus dispersion liquid is water, ethanol, dimethyl sulfoxide, N-methyl pyrrolidone, isopropanol, N-dimethylformamide, ethylene carbonate or 1-butyl-trimethyl imidazole dicyandiamide; the dispersion solvent of the graphene oxide dispersion liquid is water, ethanol, dimethyl sulfoxide, N-methyl pyrrolidone, isopropanol, N-dimethylformamide, ethylene carbonate or 1-butyl-trimethyl imidazole dicyandiamide.
4. The preparation method of the nano black phosphorus/graphene composite material according to claim 1, wherein the preparation method comprises the following steps: and (2) carrying out ultrasonic pretreatment by adopting an ultrasonic cell cleaner and/or a cell crusher in the ultrasonic treatment in the step (1), wherein the power of the ultrasonic cell cleaner is 150-300W, the power of the cell crusher is 500-1500W, and the ultrasonic treatment time is 2-24 h.
5. The preparation method of the nano black phosphorus/graphene composite material according to claim 1, wherein the preparation method comprises the following steps: in the step (4), the microwave power is 300-1000W.
6. The preparation method of the nano black phosphorus/graphene composite material according to claim 1, wherein the preparation method comprises the following steps: the inert gas is one or more of argon, nitrogen and helium.
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| CN110627029A (en) * | 2019-10-29 | 2019-12-31 | 陕西科技大学 | Black phosphorus quantum dot/nanosheet composite material and preparation method thereof |
| CN111646439B (en) * | 2020-06-19 | 2022-08-19 | 昆明理工大学 | Method for doping nano black phosphorus or black phosphorus-based mixed material |
| CN112162024A (en) * | 2020-09-18 | 2021-01-01 | 苏州科技大学 | Black phosphorus/hemin composite material, preparation method thereof and electrochemical biosensor |
| CN112340714B (en) * | 2020-11-13 | 2023-09-05 | 陕西科技大学 | Flower-like and chain-like black phosphorus material and preparation method thereof |
| CN113150234B (en) * | 2021-05-10 | 2022-06-24 | 慕思健康睡眠股份有限公司 | Wear-resistant graphene polyurethane composite sponge material and preparation method and application thereof |
| CN113354856B (en) * | 2021-06-21 | 2021-12-28 | 深圳市恒康泰医疗科技有限公司 | Preparation method of graphene and phosphorus composite chip |
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