阅读说明：本技术 一种掺杂纳米黑磷或黑磷基混合材料的方法 (Method for doping nano black phosphorus or black phosphorus-based mixed material ) 是由 张倩 赵震霆 宋开伟 刘岚君 何路东 梅毅 廉培超 于 2020-06-19 设计创作，主要内容包括：本发明公开一种掺杂纳米黑磷或黑磷基混合材料的方法,首先,将纳米黑磷或黑磷基混合材料均匀分散于溶剂或盐溶液中得到悬浮液；其次,将悬浮液置于玻璃反应器内,在惰性气氛下,持续通入掺杂气体或不通入掺杂气体,然后在匀速搅拌下进行光化学反应；最后,对反应产物进行固液分离,并对得到的固体进行干燥,从而得到掺杂纳米黑磷或掺杂黑磷基复合材料；本发明方法具有反应条件温和、成本低、可规模化制备的特点,本方法制备的掺杂纳米黑磷/黑磷基复合材料在光电子、场效应晶体管、储能、催化及喷施肥等领域具有实用前景。(The invention discloses a method for doping a nano black phosphorus or black phosphorus-based mixed material, which comprises the following steps of firstly, uniformly dispersing the nano black phosphorus or black phosphorus-based mixed material in a solvent or a salt solution to obtain a suspension; secondly, placing the suspension in a glass reactor, continuously introducing doping gas or not introducing doping gas in an inert atmosphere, and then carrying out photochemical reaction under uniform stirring; finally, carrying out solid-liquid separation on the reaction product, and drying the obtained solid, thereby obtaining the doped nano black phosphorus or the doped black phosphorus-based composite material; the method has the characteristics of mild reaction conditions, low cost and large-scale preparation, and the doped nano black phosphorus/black phosphorus-based composite material prepared by the method has practical prospects in the fields of photoelectrons, field effect transistors, energy storage, catalysis, spray fertilization and the like.)

1. A method for doping nano black phosphorus or black phosphorus-based mixed materials is characterized by comprising the following specific steps:

(1) uniformly dispersing the nano black phosphorus or black phosphorus-based mixed material in a solvent or a salt solution to obtain a suspension;

(2) placing the suspension liquid obtained in the step (1) in a reactor, continuously introducing doping gas or not introducing doping gas in an inert atmosphere, and then carrying out photochemical reaction under the conditions of stirring and illumination;

(3) and (3) after the photochemical reaction in the step (2) is finished, carrying out solid-liquid separation on the reaction product, and drying the solid to obtain the doped nano black phosphorus or black phosphorus-based mixed material.

2. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the nano black phosphorus is one of black phosphorus quantum dots, black phosphorus nanobelts, black phosphorus alkene, black phosphorus nanotubes, perforated black phosphorus alkene and black phosphorus nanowires; the black phosphorus-based mixed material is a mixture obtained by mixing nano black phosphorus and one or more of graphene, graphene oxide, MXene, boron nitride and transition metal chalcogenide, wherein the nano black phosphorus accounts for 10-90% of the total mass of the black phosphorus-based mixed material.

3. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the concentration of the suspension of the nano black phosphorus or black phosphorus-based mixed material in the step (1) is 0.1-10 mg/mL.

4. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the solvent in the step (1) is one of water, methanol, ethanol, isopropanol, diethyl ether, cyclohexane, ethylene carbonate, benzene, hydrazine hydrate, acetone, N-methylpyrrolidone, N-dimethylformamide and dimethyl sulfoxide; the salt solution is one or more of sulfate, nitrate, chloride, phosphate, perchlorate, tungstate and tetrafluoroborate solution.

5. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the reactor in the step (1) is a quartz glass tube or a high borosilicate glass tube.

6. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the stirring mode in the step (2) is mechanical stirring, airflow stirring or jet stirring.

7. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the inert atmosphere is introduced with inert gases of nitrogen, helium, neon, argon, krypton, xenon or radon; the doping gas is one or more of methane, ethylene, ammonia gas, nitric oxide, nitrogen dioxide, sulfur trioxide, hydrogen sulfide, chlorine, hydrogen selenide, boron trichloride and diborane.

8. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 7, wherein: the doping gas accounts for 5-95% of the total volume of the doping gas and the inert gas.

9. The method of doping nano black phosphorus or black phosphorus based hybrid material as claimed in claim 1, wherein: the photochemical reaction time is 0.1-72 h.

Technical Field

The invention relates to a method for doping a nano black phosphorus or black phosphorus-based composite material, belonging to the technical field of nano materials.

Background

The nano black phosphorus is a novel two-dimensional material, and has high carrier mobility, good optical and optoelectronic properties, excellent mechanical properties and the like due to the unique crystal structure and energy band structure, so that the nano black phosphorus has attractive application prospects in the fields of energy storage, field effect transistors, solar cells, gas sensors, biomedicine, catalysis and the like. However, in practical application, the nano black phosphorus has the disadvantages of poor conductivity, poor stability and the like. In order to further promote the application of the nano black phosphorus, the nano black phosphorus is doped with heteroatoms, so that the minimum value of a conduction band of the nano black phosphorus is shifted down to be lower than O₂/O₂ ^–The oxidation-reduction potential of the nano black phosphorus increases the structural defects of the nano black phosphorus, changes the electronic characteristics of the nano black phosphorus, thereby improving the electrochemical performance and stability of the nano black phosphorus and widening the application field of the nano black phosphorus. The doping methods adopted at present mainly comprise atomic layer deposition, a ball milling method, a mineralization method, a high-temperature high-pressure method and an electrochemical method, and the composite material prepared by the methods has the defects of uneven doping, high energy consumption, long time consumption, strict equipment requirement, easiness in high-temperature sintering, high cost and the like.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a method for doping nano black phosphorus or black phosphorus-based mixed material with mild reaction conditions, high efficiency and environmental protection, the method has the characteristics of simplicity, low cost, no expensive and complicated equipment and large-scale production, and the doped material prepared by the method has better application prospect in the fields of photoelectrons, field effect transistors, energy storage, catalysis, spray fertilization and the like due to good conductivity and stability of the doped material.

The method for doping the nano black phosphorus or the black phosphorus-based mixed material comprises the following steps:

(1) uniformly dispersing the nano black phosphorus or black phosphorus-based mixed material in a solvent or a salt solution to obtain a suspension;

the nano black phosphorus is one of black phosphorus quantum dots, black phosphorus nanobelts, black phosphorus alkene, black phosphorus nanotubes, perforated black phosphorus alkene and black phosphorus nanowires; the black phosphorus-based mixed material is a mixture obtained by mixing nano black phosphorus and one or more of graphene, graphene oxide, MXene, boron nitride and transition metal chalcogenide, wherein the nano black phosphorus accounts for 10-90% of the total mass of the black phosphorus-based mixed material;

the concentration of the nano black phosphorus or black phosphorus-based mixed material suspension is 0.1-10 mg/mL;

the solvent is one of water, methanol, ethanol, isopropanol, diethyl ether, cyclohexane, ethylene carbonate, benzene, hydrazine hydrate, acetone, N-methylpyrrolidone, N-dimethylformamide and dimethyl sulfoxide; the salt solution is one or more of sulfate, nitrate, chloride, phosphate, perchlorate, tungstate and tetrafluoroborate solution in any ratio;

wherein the sulfate is one of potassium sulfate, calcium sulfate, magnesium sulfate, zinc sulfate, ferric sulfate, copper sulfate and manganese sulfate; the nitrate is one of potassium nitrate, calcium nitrate, magnesium nitrate, zinc nitrate, ferric nitrate, cupric nitrate and manganese nitrate; the chloride salt is one of potassium chloride, calcium chloride, magnesium chloride, zinc chloride, ferric chloride, cupric chloride, manganese chloride and molybdenum chloride; the phosphate is one of dipotassium hydrogen phosphate, calcium dihydrogen phosphate, calcium hydrogen phosphate, magnesium dihydrogen phosphate, zinc dihydrogen phosphate, copper phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate; the perchlorate is one of potassium perchlorate, calcium perchlorate, magnesium perchlorate, ferric perchlorate and manganese perchlorate; the tungstate is one of calcium tungstate, zinc tungstate, ferrous tungstate and ammonium tungstate; the tetrafluoroborate is one of tetrabutyl phosphine tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, tetraethyl tetrafluoroborate and 1-butyl-3-methylimidazole tetrafluoroborate;

potassium nitrate, potassium sulfate, potassium chloride, dipotassium hydrogen phosphate or potassium perchlorate in the solution are potassium sources; copper sulfate, copper nitrate or copper chloride in the solution is used as a copper source; magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium phosphate or magnesium perchlorate in the solution is used as a magnesium source; calcium nitrate, calcium chloride, calcium sulfate, calcium perchlorate, calcium dihydrogen phosphate or calcium hydrogen phosphate in the solution are used as calcium sources; ferric nitrate, ferric chloride, ferric sulfate, ferric perchlorate or ferrous tungstate in the solution are used as iron sources; manganese nitrate, manganese chloride, manganese sulfate or manganese perchlorate in the solution is taken as a manganese source; molybdenum chloride in the solution or a molybdenum source; zinc nitrate, zinc chloride, zinc sulfate, zinc dihydrogen phosphate or zinc tungstate in the solution are used as zinc sources; the tetrabutyl phosphine tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, tetraethyl tetrafluoroborate or 1-butyl-3-methylimidazole tetrafluoroborate solution in the solution is taken as a boron source;

(2) placing the suspension liquid obtained in the step (1) in a reactor, continuously introducing doping gas or not introducing doping gas in an inert atmosphere, and then carrying out photochemical reaction for 0.1-72 h under the conditions of stirring and illumination;

the reactor is a quartz glass tube or a high borosilicate glass tube;

the stirring mode is mechanical stirring, airflow stirring or jet stirring;

the inert atmosphere refers to introducing inert gases such as nitrogen, helium, neon, argon, krypton, xenon or radon; the doping gas is one or more of methane, ethylene, ammonia gas, nitric oxide, nitrogen dioxide, sulfur trioxide, hydrogen sulfide, chlorine, hydrogen selenide, boron trichloride and diborane; the doping gas accounts for 5-95% of the total volume of the doping gas and the inert gas;

(3) after the photochemical reaction in the step (2) is finished, carrying out solid-liquid separation on the reaction product, and drying the solid to obtain doped nano black phosphorus or black phosphorus-based mixed material;

the drying mode is one of freeze drying, vacuum drying and natural drying.

The invention has the beneficial effects that:

1. the method adopts a photocatalysis method, has mild reaction conditions, and has the characteristics of simplicity, controllability, no expensive and complicated equipment, environmental protection, low cost and large-scale production;

2. the method can not only improve the doping uniformity of the whole material, but also controllably adjust the doping amount of the whole material through liquid-liquid reaction or liquid-gas reaction;

3. the method adjusts the flow rate of the gas and the concentration of the solution by changing the types of the gas and the salt solution, thereby adjusting the doping source, the doping amount and the doping form;

4. the doped nano black phosphorus or doped black phosphorus-based composite material prepared by the method has good stability and can be better applied to various fields.

Drawings

FIG. 1 is a spectrum diagram of N1S of a nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material prepared in example 1 of the present invention;

fig. 2 is a fourier transform infrared spectrum of a composite material of the nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material prepared in example 1 of the present invention and a single graphene oxide (in the absence of perforated black phosphorus alkene);

FIG. 3 is a graph of the UV-vis absorption spectrum of (a) a single perforated black phospholene dispersion prepared in example 1 of the present invention; (b) a UV-vis absorption spectrogram of the nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material;

fig. 4 is a constant current charge-discharge curve of the nitrogen-doped perforated black phosphorus alkene/reduced graphene oxide composite material applied to the negative electrode material of the sodium ion battery, which is prepared in embodiment 1 of the invention.

Detailed Description

The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the above-described examples.