CN108772079A - A kind of preparation method of nanometer of black phosphorus/graphene composite material - Google Patents

A kind of preparation method of nanometer of black phosphorus/graphene composite material Download PDF

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CN108772079A
CN108772079A CN201810384561.4A CN201810384561A CN108772079A CN 108772079 A CN108772079 A CN 108772079A CN 201810384561 A CN201810384561 A CN 201810384561A CN 108772079 A CN108772079 A CN 108772079A
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black phosphorus
nanometer
graphene oxide
nanometer black
graphene
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CN108772079B (en
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廉培超
刘红红
梅毅
汤永威
王倩
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20Carbon compounds
    • B01J35/39
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16Reducing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation 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
    • B01J37/343Irradiation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation 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
    • B01J37/344Irradiation 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
    • B01J37/346Irradiation 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 present invention relates to the preparation methods of a kind of nanometer of black phosphorus/graphene composite material, belong to technical field of composite materials.The present invention mixes nanometer black phosphorus dispersion liquid with graphene oxide dispersion under the conditions of temperature is 5 ~ 30 DEG C, sonicated to obtain a nanometer black phosphorus/graphene oxide dispersion;Nanometer black phosphorus/graphene oxide dispersion is freeze-dried to obtain a nanometer black phosphorus/graphene oxide solid foam;Nanometer black phosphorus/graphene oxide solid foam is placed in atmosphere of inert gases and carries out ultraviolet, infrared or radiation of visible light and pre-process 2 ~ 72h obtaining a nanometer black phosphorus/prereduction graphene oxide solid;Nanometer black phosphorus/prereduction graphene oxide solid is placed in atmosphere of inert gases, temperature is 50 ~ 300 DEG C, under microwave condition 0.5 ~ 10h of reduction treatment up to nanometer black phosphorus/graphene composite material.The present invention prepares nanometer black phosphorus/graphene composite material of high quality in such a way that photo-reduction and microwave reduction are combined.

Description

A kind of preparation method of nanometer of black phosphorus/graphene composite material
Technical field
The present invention relates to the preparation methods of a kind of nanometer of black phosphorus/graphene composite material, belong to technical field of composite materials.
Background technology
Black phosphorus is a kind of two-dimensional layer material of single element, because its unique crystal structure and band structure make it have directly The excellent specific properties such as tape splicing gap, good photoelectron performance, high carrier mobility so that black phosphorus is in necks such as energy storage, photocatalysis Black phosphorus domain has good application prospect.In many applications of black phosphorus, people are typically by its nanosizing to get to nano black Phosphorus(Nanometer black phosphorus, black phosphorus quantum dot).When applied to energy storage field:Phosphorus based material generally existing electric conductivity is not high, cyclicity Can be poor the problems such as, and nanometer black phosphorus is unstable in air, easily degrades with the water in air, oxygen effect.
The preparation method of nanometer black phosphorus/graphene composite material mainly has at present:(1)By nanometer black phosphorus, graphene dispersion Physical mixed is carried out in organic solvent, then through being dried to obtain a nanometer black phosphorus/graphene composite material, this method is prepared compound Nanometer black phosphorus is only combined by faint Van der Waals force with graphene in material, therefore cannot thoroughly be solved above-mentioned nanometer black phosphorus and be existed Unstable problem in air, and organic solvent pollution environment are difficult to remove in application process.(2)By nanometer black phosphorus, oxidation Graphene dispersion obtains a nanometer black phosphorus/graphene oxide paper in organic solvent, by vacuum filtration(PGO), then to PGO through etc. Gas ions are sintered to obtain a nanometer black phosphorus/graphene composite material(PG-SPS).Nanometer black phosphorus in composite material prepared by this method Although there is stronger binding force between graphene, obtained graphene conductive is comparatively poor.
Invention content
The problem of existing for the above-mentioned prior art and deficiency, the present invention provide a kind of nanometer of black phosphorus/graphene composite wood The preparation method of material, the present invention prepare nanometer black phosphorus/stone of high quality in such a way that photo-reduction and microwave reduction are combined Black alkene composite material, the method for the present invention is easy to operate, energy saving, efficient, and reaction condition is mild.
The preparation method of a kind of nanometer of black phosphorus/graphene composite material, is as follows:
(1)Under the conditions of temperature is 5 ~ 30 DEG C, nanometer black phosphorus dispersion liquid is mixed with graphene oxide dispersion, it is sonicated Obtain a nanometer black phosphorus/graphene oxide dispersion;
(2)By step(1)Gained nanometer black phosphorus/graphene oxide dispersion is freeze-dried to obtain a nanometer black phosphorus/graphene oxide Solid foam;
(3)By step(2)Nanometer black phosphorus/graphene oxide solid foam be placed in atmosphere of inert gases carry out it is ultraviolet, infrared Or radiation of visible light pre-processes 2 ~ 72h and obtains a nanometer black phosphorus/prereduction graphene oxide solid;
(4)By step(3)Gained nanometer black phosphorus/prereduction graphene oxide solid be placed in atmosphere of inert gases, temperature be 50 ~ 300 DEG C, under microwave condition 0.5 ~ 10h of reduction treatment up to nanometer black phosphorus/graphene composite material;
The step(1)A concentration of 0.1 ~ 5mg/mL of nanometer black phosphorus, nano black in nanometer black phosphorus/graphene oxide dispersion A concentration of 0.1 ~ 5mg/mL of graphene oxide in phosphorus/graphene oxide dispersion;
The step(1)Nanometer black phosphorus is black phosphorus alkene, black phosphorus quantum dot, black phosphorus nano wire, black phosphorus nanotube or black phosphorus nanobelt; The dispersion solvent of nanometer black phosphorus dispersion liquid is water, ethyl alcohol, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, isopropanol, N, N- dimethyl Formamide, ethylene carbonate or 1- butyl-tri-methylimidazolium cdicynanmide;The dispersion solvent of graphene oxide dispersion is water, second Alcohol, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, isopropanol, N,N-dimethylformamide, ethylene carbonate or 1- butyl-front three Base imidazoles cdicynanmide;
The step(1)It is ultrasonically treated and ultrasonic pretreatment, ultrasound is carried out using supersonic cell washer and/or cell disruptor The power of wave cell washer is 150W ~ 300W, and the power of cell disruptor is 500 ~ 1500W, sonication treatment time is 2 ~ 24h;
The step(4)Middle microwave power is 300 ~ 1000W;
The inert gas be argon gas, nitrogen, helium it is one or more;
The nanometer black phosphorus dispersion liquid is that nanometer black phosphorus is added in dispersion solvent, through supersonic cell washer and/or carefully Born of the same parents' pulverizer carries out ultrasound pretreatment and obtains;
The graphene oxide aqueous dispersions are according to document " Large reversible capacity of high quality Graphene sheets as an anode material for lithium-ion batteries " or document " Porous SnO2@C/graphene nanocomposite with 3D carbon conductive network as a superior Anode material for lithium-ion batteries " are prepared;
The beneficial effects of the invention are as follows:
(1)Nanometer black phosphorus/graphene that the present invention prepares high quality in such a way that photo-reduction and microwave reduction are combined is multiple Condensation material;
(2)The method of the present invention is easy to operate, energy saving, efficient, and reaction condition is mild;
(3)For the present invention during photo-reduction, nanometer black phosphorus plays photocatalysis, promotes further going back for graphene oxide It is former;During microwave reduction, in microwave(Electromagnetic wave)Under the action of, graphene oxide can be reduced to high quality, high conductivity Graphene;Meanwhile under the action of photo-reduction and microwave reduction, nanometer black phosphorus and graphene can be formed with stronger mutual The P-C chemical bonds of active force improve photo-catalysis capability and energy storage capacity to be conducive to being stabilized for nanometer black phosphorus.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of 1 nanometer of black phosphorus of embodiment/graphene oxide solid foam;
Fig. 2 is the scanning electron microscope (SEM) photograph of 1 nanometer of black phosphorus of embodiment/prereduction graphene oxide solid;
Fig. 3 is the scanning electron microscope (SEM) photograph of 1 nanometer of black phosphorus/graphene composite material of embodiment;
Fig. 4 is the carbon distribution map of 1 nanometer of black phosphorus/graphene composite material of embodiment;
Fig. 5 is the phosphorus distribution map of 1 nanometer of black phosphorus/graphene composite material of embodiment;
Fig. 6 is 1 nanometer of black phosphorus of embodiment/graphene oxide solid and nanometer black phosphorus/graphene composite material Raman comparison diagram;
Fig. 7 is the P of 1 nanometer of black phosphorus/graphene composite material of embodiment2PFigure;
Fig. 8 is the C of 1 nanometer of black phosphorus/graphene composite material of embodiment1sFigure.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1:The preparation method of a kind of nanometer of black phosphorus/graphene composite material, is as follows:
(1)Under the conditions of temperature is 15 DEG C, by nanometer black phosphorus dispersion liquid(Nanometer black phosphorus dispersion liquid is nanometer black phosphorus alkene/water-dispersed Liquid)With graphene oxide dispersion(Graphene oxide dispersion is graphene oxide/aqueous dispersions)Mixing, sonicated To nanometer black phosphorus/graphene oxide dispersion;Wherein nanometer black phosphorus dispersion liquid(Nanometer black phosphorus alkene/aqueous dispersions)A concentration of 2 Mg/mL, graphene oxide dispersion(Graphene oxide/aqueous dispersions)A concentration of 2 mg/mL, nanometer black phosphorus dispersion liquid(It receives Rice black phosphorus alkene/aqueous dispersions)With graphene oxide dispersion(Graphene oxide/aqueous dispersions)Volume ratio be 1:1, nano black A concentration of 1 mg/mL of nanometer black phosphorus in phosphorus/graphene oxide dispersion is aoxidized in nanometer black phosphorus/graphene oxide dispersion A concentration of 1 mg/mL of graphene;It is ultrasonically treated ultrasonic pre- to use supersonic cell washer, cell disruptor to carry out successively The power of processing, supersonic cell washer is 150W, and the processing time of supersonic cell washer is 1h, cell disruptor Power is 500 W, and the processing time of cell disruptor is 1h;
(2)By step(1)Gained nanometer black phosphorus/graphene oxide dispersion is placed in freezing 5h under the conditions of temperature is -80 DEG C and is formed Nanometer black phosphorus/graphene oxide ice solid, is then freeze-dried to obtain a nanometer black phosphorus/graphene oxide solid foam again;
(3)By step(2)Nanometer black phosphorus/graphene oxide solid foam be placed in inert gas(Argon gas)It is carried out in atmosphere ultraviolet Light irradiation pretreatment 48h obtains a nanometer black phosphorus/prereduction graphene oxide solid;
(4)By step(3)Gained nanometer black phosphorus/prereduction graphene oxide solid is placed in inert gas(Argon gas)Atmosphere, temperature It is reduction treatment 4h under 200 DEG C, microwave condition up to nanometer black phosphorus/graphene composite material;
The scanning electron microscope (SEM) photograph of nanometer black phosphorus/graphene oxide solid foam obtained by the present embodiment is as shown in Figure 1, obtained by the present embodiment The scanning electron microscope (SEM) photograph of nanometer black phosphorus/prereduction graphene oxide solid is as shown in Fig. 2, nanometer black phosphorus/graphite obtained by the present embodiment The scanning electron microscope (SEM) photograph of alkene composite material is as shown in figure 3, from Fig. 1 ~ 3 it is found that the present embodiment prepares nanometer black phosphorus/graphene composite wood Graphene maintains preferable pleated structure during material;
The phosphorus distribution map of nanometer black phosphorus/graphene composite material obtained by the present embodiment is as shown in figure 4, nano black obtained by the present embodiment The carbon distribution map of phosphorus/graphene composite material is as shown in figure 5, from Fig. 4 ~ 5 it is found that nanometer manufactured in the present embodiment phosphorus/graphene Phosphorus, carbon, which realize, in composite material is uniformly distributed;
Nanometer black phosphorus/graphene oxide solid and nanometer black phosphorus/graphene composite material Raman comparison diagram obtained by the present embodiment are such as Shown in Fig. 6, as can be seen from Figure 6, there is nanometer in nanometer black phosphorus/graphene oxide solid and nanometer black phosphorus/graphene composite material The characteristic peak A of black phosphorusg 1、B2gAnd Ag 2, illustrating nanometer black phosphorus, structure is simultaneously during preparing nanometer black phosphorus/graphene composite material It is not corrupted;Nanometer black phosphorus/graphene oxide solid and nanometer black phosphorus/graphene composite material in occur graphene oxide and The peaks characteristic peak D, the peaks G and the peaks 2D of graphene, and the nanometer black phosphorus/graphene composite wood obtained after illumination and microwave treatment There are the more sharp peaks 2D in material, illustrates the composite material degree of graphitization higher obtained after illumination and microwave treatment, has There is better electric conductivity;
P2P the and C1S spectrograms of nanometer black phosphorus/graphene composite material obtained by the present embodiment as shown in Fig. 7 ~ 8, from Fig. 7 ~ 8 it is found that Contained P-C keys and P-O-C keys in the nanometer phosphorus/graphene composite material prepared by the method for the present invention, illustrates prepared by the present embodiment Nanometer phosphorus/graphene composite material will have higher stability;
The present embodiment nanometer phosphorus/graphene composite material has high electric conductivity and stability;Nanometer phosphorus/graphene composite material It can be applied to the fields such as energy storage and photocatalysis.
Embodiment 2:The preparation method of a kind of nanometer of black phosphorus/graphene composite material, is as follows:
(1)Under the conditions of temperature is 15 DEG C, by nanometer black phosphorus dispersion liquid(Nanometer black phosphorus dispersion liquid is nanometer black phosphorus alkene/dimethyl Sulfoxide dispersion liquid)With graphene oxide dispersion(Graphene oxide dispersion is graphene oxide/N-Methyl pyrrolidone point Dispersion liquid)Mixing, it is sonicated to obtain a nanometer black phosphorus/graphene oxide dispersion;Wherein nanometer black phosphorus dispersion liquid(Nanometer black phosphorus Alkene/dimethyl sulfoxide (DMSO) dispersion liquid)A concentration of 2 mg/mL, graphene oxide dispersion(Graphene oxide/N- crassitudes Ketone dispersion liquid)A concentration of 2 mg/mL, nanometer black phosphorus dispersion liquid(Nanometer black phosphorus alkene/dimethyl sulfoxide (DMSO) dispersion liquid)With oxidation stone Black alkene dispersion liquid(Graphene oxide/N-Methyl pyrrolidone dispersion liquid)Volume ratio be 1:2, nanometer black phosphorus/graphene oxide A concentration of 0.67 mg/mL of nanometer black phosphorus in dispersion liquid, graphene oxide is dense in nanometer black phosphorus/graphene oxide dispersion Degree is 1.33 mg/mL;It is ultrasonically treated to carry out ultrasonic pretreatment, supersonic cell washer using supersonic cell washer Power be 200W, processing time of supersonic cell washer is 5h;
(2)By step(1)Gained nanometer black phosphorus/graphene oxide dispersion be placed in freezing under the conditions of liquid nitrogen formed nanometer black phosphorus/ Then graphene oxide ice solid is freeze-dried to obtain a nanometer black phosphorus/graphene oxide solid foam again;
(3)By step(2)Nanometer black phosphorus/graphene oxide solid foam be placed in inert gas(Nitrogen)It is carried out in atmosphere infrared Light irradiation pretreatment 40h obtains a nanometer black phosphorus/prereduction graphene oxide solid;
(4)By step(3)Gained nanometer black phosphorus/prereduction graphene oxide solid is placed in inert gas(Nitrogen)Atmosphere, temperature It is reduction treatment 3h under 250 DEG C, microwave condition up to nanometer black phosphorus/graphene composite material;
Electronic Speculum, Raman, XPS characterizations, detection and analysis are scanned to nanometer black phosphorus/graphene composite material made from the present embodiment Know and forms P-C keys and P-O-C keys in the composite material, with good stability and electric conductivity;Therefore, which exists The fields such as energy storage, photocatalysis have good application prospect.
Embodiment 3:The preparation method of a kind of nanometer of black phosphorus/graphene composite material, is as follows:
(1)Under the conditions of temperature is 30 DEG C, by nanometer black phosphorus dispersion liquid(Nanometer black phosphorus dispersion liquid is nanometer black phosphorus alkene/carbonic acid second Enester dispersion liquid)With graphene oxide dispersion(Graphene oxide dispersion is graphene oxide/N,N-dimethylformamide point Dispersion liquid)Mixing, it is sonicated to obtain a nanometer black phosphorus/graphene oxide dispersion;Wherein nanometer black phosphorus dispersion liquid(Nanometer black phosphorus Alkene/ethylene carbonate dispersion liquid)A concentration of 2 mg/mL, graphene oxide dispersion(Graphene oxide/N, N- dimethyl methyls Amide dispersion liquid)A concentration of 2 mg/mL, nanometer black phosphorus dispersion liquid(Nanometer black phosphorus alkene/ethylene carbonate dispersion liquid)With oxidation Graphene dispersing solution(Graphene oxide/N,N-dimethylformamide dispersion liquid)Volume ratio be 1:4, nanometer black phosphorus/oxidation stone A concentration of 0.4 mg/mL of nanometer black phosphorus in black alkene dispersion liquid, graphene oxide in nanometer black phosphorus/graphene oxide dispersion A concentration of 1.6mg/mL;It is ultrasonically treated to carry out ultrasonic pretreatment using cell disruptor, the power of cell disruptor is 1000 The processing time of W, cell disruptor are 3h;
(2)By step(1)Gained nanometer black phosphorus/graphene oxide dispersion is placed in freezing 10h under the conditions of temperature is -80 DEG C and is formed Nanometer black phosphorus/graphene oxide ice solid, is then freeze-dried to obtain a nanometer black phosphorus/graphene oxide solid foam again;
(3)By step(2)Nanometer black phosphorus/graphene oxide solid foam be placed in inert gas(Nitrogen)It is carried out in atmosphere visible Light irradiation pretreatment 72h obtains a nanometer black phosphorus/prereduction graphene oxide solid;
(4)By step(3)Gained nanometer black phosphorus/prereduction graphene oxide solid is placed in inert gas(Nitrogen)Atmosphere, temperature It is reduction treatment 2h under 50 DEG C, microwave condition up to nanometer black phosphorus/graphene composite material;
Electronic Speculum, Raman, XPS characterizations, detection and analysis are scanned to nanometer black phosphorus/graphene composite material made from the present embodiment Know and forms P-C keys and P-O-C keys in the composite material, with good stability and electric conductivity;Nanometer phosphorus/graphene is compound Material can be applied to the fields such as energy storage and photocatalysis.
Embodiment 4:The preparation method of a kind of nanometer of black phosphorus/graphene composite material, is as follows:
(1)Under the conditions of temperature is 30 DEG C, by nanometer black phosphorus dispersion liquid(Nanometer black phosphorus dispersion liquid is nanometer black phosphorus alkene/carbonic acid second Enester dispersion liquid)With graphene oxide dispersion(Graphene oxide dispersion is graphene oxide/N,N-dimethylformamide point Dispersion liquid)Mixing, it is sonicated to obtain a nanometer black phosphorus/graphene oxide dispersion;Wherein nanometer black phosphorus dispersion liquid(Nanometer black phosphorus Alkene/ethylene carbonate dispersion liquid)A concentration of 3mg/mL, graphene oxide dispersion(Graphene oxide/N, N- dimethyl formyls Amine dispersion liquid)A concentration of 3mg/mL, nanometer black phosphorus dispersion liquid(Nanometer black phosphorus alkene/ethylene carbonate dispersion liquid)With graphite oxide Alkene dispersion liquid(Graphene oxide/N,N-dimethylformamide dispersion liquid)Volume ratio be 1:1, nanometer black phosphorus/graphene oxide A concentration of 1.5mg/mL of nanometer black phosphorus in dispersion liquid, the concentration of graphene oxide in nanometer black phosphorus/graphene oxide dispersion For 1.5mg/mL;It is ultrasonically treated to carry out ultrasonic pretreatment using cell disruptor, the power of cell disruptor is 1000 W, carefully The processing time of born of the same parents' pulverizer is 3h;
(2)By step(1)Gained nanometer black phosphorus/graphene oxide dispersion is placed in freezing 10h under the conditions of temperature is -80 DEG C and is formed Nanometer black phosphorus/graphene oxide ice solid, is then freeze-dried to obtain a nanometer black phosphorus/graphene oxide solid foam again;
(3)By step(2)Nanometer black phosphorus/graphene oxide solid foam be placed in inert gas(Nitrogen)It is carried out in atmosphere visible Light irradiation pretreatment 72h obtains a nanometer black phosphorus/prereduction graphene oxide solid;
(4)By step(3)Gained nanometer black phosphorus/prereduction graphene oxide solid is placed in inert gas(Nitrogen)Atmosphere, temperature It is reduction treatment 2h under 150 DEG C, microwave condition up to nanometer black phosphorus/graphene composite material;
Electronic Speculum, Raman, XPS characterizations, detection and analysis are scanned to nanometer black phosphorus/graphene composite material made from the present embodiment Know and form P-C keys and P-O-C keys in the composite material, with good stability and electric conductivity, nanometer phosphorus/graphene is compound Material can be applied to the fields such as energy storage and photocatalysis.
Embodiment 5:The preparation method of a kind of nanometer of black phosphorus/graphene composite material, is as follows:
(1)Under the conditions of temperature is 30 DEG C, by nanometer black phosphorus dispersion liquid(Nanometer black phosphorus dispersion liquid is nanometer black phosphorus alkene/carbonic acid second Enester dispersion liquid)With graphene oxide dispersion(Graphene oxide dispersion is graphene oxide/N,N-dimethylformamide point Dispersion liquid)Mixing, it is sonicated to obtain a nanometer black phosphorus/graphene oxide dispersion;Wherein nanometer black phosphorus dispersion liquid(Nanometer black phosphorus Alkene/ethylene carbonate dispersion liquid)A concentration of 5 mg/mL, graphene oxide dispersion(Graphene oxide/N, N- dimethyl methyls Amide dispersion liquid)A concentration of 5 mg/mL, nanometer black phosphorus dispersion liquid(Nanometer black phosphorus alkene/ethylene carbonate dispersion liquid)With oxidation Graphene dispersing solution(Graphene oxide/N,N-dimethylformamide dispersion liquid)Volume ratio be 1:1, nanometer black phosphorus/oxidation stone A concentration of 2.5 mg/mL of nanometer black phosphorus in black alkene dispersion liquid, graphene oxide in nanometer black phosphorus/graphene oxide dispersion A concentration of 2.5mg/mL;It is ultrasonically treated to carry out ultrasonic pretreatment using cell disruptor, the power of cell disruptor is 1000 The processing time of W, cell disruptor are 3h;
(2)By step(1)Gained nanometer black phosphorus/graphene oxide dispersion is placed in freezing 10h under the conditions of temperature is -80 DEG C and is formed Nanometer black phosphorus/graphene oxide ice solid, is then freeze-dried to obtain a nanometer black phosphorus/graphene oxide solid foam again;
(3)By step(2)Nanometer black phosphorus/graphene oxide solid foam be placed in inert gas(Nitrogen)It is carried out in atmosphere visible Light irradiation pretreatment 2h obtains a nanometer black phosphorus/prereduction graphene oxide solid;
(4)By step(3)Gained nanometer black phosphorus/prereduction graphene oxide solid is placed in inert gas(Nitrogen)Atmosphere, temperature It is reduction treatment 10h under 50 DEG C, microwave condition up to nanometer black phosphorus/graphene composite material;
Electronic Speculum, Raman, XPS characterizations, detection and analysis are scanned to nanometer black phosphorus/graphene composite material made from the present embodiment Know and form P-C keys and P-O-C keys in the composite material, with good stability and electric conductivity, nanometer phosphorus/graphene is compound Material can be applied to the fields such as energy storage and photocatalysis.
Embodiment 6:The preparation method of a kind of nanometer of black phosphorus/graphene composite material, is as follows:
(1)Under the conditions of temperature is 30 DEG C, by nanometer black phosphorus dispersion liquid(Nanometer black phosphorus dispersion liquid is nanometer black phosphorus alkene/carbonic acid second Enester dispersion liquid)With graphene oxide dispersion(Graphene oxide dispersion is graphene oxide/N,N-dimethylformamide point Dispersion liquid)Mixing, it is sonicated to obtain a nanometer black phosphorus/graphene oxide dispersion;Wherein nanometer black phosphorus dispersion liquid(Nanometer black phosphorus Alkene/ethylene carbonate dispersion liquid)A concentration of 0.1 mg/mL, graphene oxide dispersion(Graphene oxide/N, N- dimethyl Formamide dispersion liquid)A concentration of 0.1 mg/mL, nanometer black phosphorus dispersion liquid(Nanometer black phosphorus alkene/ethylene carbonate dispersion liquid)With Graphene oxide dispersion(Graphene oxide/N,N-dimethylformamide dispersion liquid)Volume ratio be 1:1, nanometer black phosphorus/oxygen A concentration of 0.05 mg/mL of nanometer black phosphorus in graphite alkene dispersion liquid aoxidizes stone in nanometer black phosphorus/graphene oxide dispersion A concentration of 0.05 mg/mL of black alkene;It is ultrasonically treated to carry out ultrasonic pretreatment, the work(of cell disruptor using cell disruptor Rate is 1000 W, and the processing time of cell disruptor is 3h;
(2)By step(1)Gained nanometer black phosphorus/graphene oxide dispersion is placed in freezing 10h under the conditions of temperature is -80 DEG C and is formed Nanometer black phosphorus/graphene oxide ice solid, is then freeze-dried to obtain a nanometer black phosphorus/graphene oxide solid foam again;
(3)By step(2)Nanometer black phosphorus/graphene oxide solid foam be placed in inert gas(Nitrogen)It is carried out in atmosphere visible Light irradiation pretreatment 12h obtains a nanometer black phosphorus/prereduction graphene oxide solid;
(4)By step(3)Gained nanometer black phosphorus/prereduction graphene oxide solid is placed in inert gas(Nitrogen)Atmosphere, temperature It is reduction treatment 5h under 100 DEG C, microwave condition up to nanometer black phosphorus/graphene composite material;
Electronic Speculum, Raman, XPS characterizations, detection and analysis are scanned to nanometer black phosphorus/graphene composite material made from the present embodiment Know and form P-C keys and P-O-C keys in the composite material, with good stability and electric conductivity, nanometer phosphorus/graphene is compound Material can be applied to the fields such as energy storage and photocatalysis.
The specific implementation mode of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art Go out various change.

Claims (6)

1. the preparation method of a kind of nanometer of black phosphorus/graphene composite material, which is characterized in that be as follows:
(1)Under the conditions of temperature is 5 ~ 30 DEG C, nanometer black phosphorus dispersion liquid is mixed with graphene oxide dispersion, it is sonicated Obtain a nanometer black phosphorus/graphene oxide dispersion;
(2)By step(1)Gained nanometer black phosphorus/graphene oxide dispersion is freeze-dried to obtain a nanometer black phosphorus/graphene oxide Solid foam;
(3)By step(2)Nanometer black phosphorus/graphene oxide solid foam be placed in atmosphere of inert gases carry out it is ultraviolet, infrared Or radiation of visible light pre-processes 2 ~ 72h and obtains a nanometer black phosphorus/prereduction graphene oxide solid;
(4)By step(3)Gained nanometer black phosphorus/prereduction graphene oxide solid be placed in atmosphere of inert gases, temperature be 50 ~ 300 DEG C, under microwave condition 0.5 ~ 10h of reduction treatment up to nanometer black phosphorus/graphene composite material.
2. the preparation method of nanometer black phosphorus/graphene composite material according to claim 1, it is characterised in that:Step(1)It receives A concentration of 0.1 ~ 5mg/mL of nanometer black phosphorus, nanometer black phosphorus/graphene oxide dispersion in rice black phosphorus/graphene oxide dispersion A concentration of 0.1 ~ 5mg/mL of middle graphene oxide.
3. the preparation method of nanometer black phosphorus/graphene composite material according to claim 1, it is characterised in that:Step(1)It receives Rice black phosphorus is black phosphorus alkene, black phosphorus quantum dot, black phosphorus nano wire, black phosphorus nanotube or black phosphorus nanobelt;Nanometer black phosphorus dispersion liquid Dispersion solvent is water, ethyl alcohol, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, isopropanol, N,N-dimethylformamide, ethylene carbonate Ester or 1- butyl-tri-methylimidazolium cdicynanmide;The dispersion solvent of graphene oxide dispersion is water, ethyl alcohol, dimethyl sulfoxide (DMSO), N- Methyl pyrrolidone, isopropanol, N,N-dimethylformamide, ethylene carbonate or 1- butyl-tri-methylimidazolium cdicynanmide.
4. the preparation method of nanometer black phosphorus/graphene composite material according to claim 1, it is characterised in that:Step(1)It is super Sonication carries out ultrasonic pretreatment, the work(of supersonic cell washer using supersonic cell washer and/or cell disruptor Rate is 150W ~ 300W, and the power of cell disruptor is 500 ~ 1500W, sonication treatment time is 2 ~ for 24 hours.
5. the preparation method of nanometer black phosphorus/graphene composite material according to claim 1, it is characterised in that:Step(4)In Microwave power is 300 ~ 1000W.
6. the preparation method of nanometer black phosphorus/graphene composite material according to claim 1, it is characterised in that:Inert gas For argon gas, nitrogen, helium it is one or more.
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