CN110330000A - A kind of preparation method of nanometer of red phosphorus - Google Patents
A kind of preparation method of nanometer of red phosphorus Download PDFInfo
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- CN110330000A CN110330000A CN201910256271.6A CN201910256271A CN110330000A CN 110330000 A CN110330000 A CN 110330000A CN 201910256271 A CN201910256271 A CN 201910256271A CN 110330000 A CN110330000 A CN 110330000A
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- red phosphorus
- phosphorus
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- hydrochloric acid
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- 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
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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
- C01B25/023—Preparation of phosphorus of red phosphorus
Abstract
The invention belongs to technical field of material, specially a kind of nanometer of red phosphorus preparation method.The method of the present invention includes: the amine aqueous solution for preparing phosphorus；Prepare nanometer red phosphorus.Wherein, by adjusting the concentration of dilute hydrochloric acid, control the grain diameter of nanometer red phosphorus: dilute hydrochloric acid concentration is 0-1.0 mol/L, and the grain diameter of nanometer red phosphorus is 20-50 nm.Present invention process is simple, and synthesis is convenient；The impurity that reaction process generates is highly soluble in water and ethyl alcohol, it is easy to be removed；Low energy consumption, sustainable, the time is short, at low cost；Yield is high, easy scale；It may be used as the universal synthesis method of red phosphorus based composites.
Description
Technical field
The invention belongs to technical field of material, and in particular to the preparation method of nanometer red phosphorus.
Background technique
With carbon phase ratio, phosphorus has similar structure, such as stratiform black phosphorus, phosphorus alkene, red phosphorus, phosphorus alkene nanotube and phosphorus alkenyl fullerene
It is similar to graphite, graphene, amorphous carbon, carbon nanotube and fullerene difference.[1]Therefore, phosphorus is the best replacer of carbon material.
And phosphorus content is abundant, is widely present in nature.There are three types of isomers, i.e. white phosphorus, red phosphorus, black phosphorus and blue phosphorus for phosphorus.
White phosphorus has severe toxicity, and easy spontaneous combustion in air, should not apply.Red phosphorus and black phosphorus all have stable chemical property, extensive
Applied to PETs and optoelectronic device, electro-catalysis, thermoelectric device, battery, photocatalysis, flexible electronic, supercapacitor and other answer
Use field.But the preparation of black phosphorus needs high temperature and pressure mostly, and red phosphorus not only has chemical stability, and business is commercially available
It arrives, it is resourceful, therefore red phosphorus is widely studied in many applications.In most applications, it is both needed to red phosphorus nanosizing.Red phosphorus
The method of nanosizing is usually ball-milling method and vaporization condensation process.Both methods is simple, can be used as the general system of phosphorous-based materials
Preparation Method.[2, 3] But both methods energy consumption is high, the particle size for the phosphorus for not continuing, and preparing is uneven, vaporization condensation process
White phosphorus is inevitably generated during phase transition.
Wet chemistry method, which prepares red phosphorus, can effectively control the particle size of phosphorus, such as Zhu et al.[4] Pass through NaN3With PCl5
Between solvent thermal reaction (10 NaN3+ 2PCl5→2P+10NaCl+15N2) it is prepared for evengranular red phosphorus hollow nano-sphere；
Bian et al.[5] Pass through PI as additive in CTAB3Red phosphorus is prepared for oxidation of glycol reduction reaction and later period boiling process
Hollow porous nanosphere.But in both the above method, the impurity for reacting generation is difficult to remove, and the reagent of reaction is all Gao Yi
Explosive substance, and severe toxicity are fired, the actual production of red phosphorus based nano-material is not suitable for.
The wet chemistry method of comparatively ideal synthesis nanometer red phosphorus should be simple, and complete at room temperature.The change of reaction
Learning reagent should be business red phosphorus or other environmental-friendly, safety materials, answer free from admixture during synthesis nanometer red phosphorus
It generates or impurity easily removes.
Initiative of the invention is prepared for a nanometer red phosphorus, using business red phosphorus as raw material, at room temperature, and reacts
The impurity that process generates is highly soluble in water and ethyl alcohol, it is easy to be removed.Compared with ball milling, vaporization condensation process, this method energy consumption
It is low, sustainable, the time is short, at low cost.Compared with above two wet chemistry method, this method yield is high, easy scale.It is prior
It is that this method may be used as the universal synthesis method of red phosphorus based composites.
Bibliography:
[1] Y. Segawa, H. Ito, K. Itami, Nat. Rev. Mater. 2016, 1, 15002.
[2] Y. Q. Fu, Q. L. Wei, G. X. Zhang, S. H. Sun. Adv. Energy Mater.2018,
1702849.
[3] W. L. Liu, H. Q. Zhi, X. B. Yu, Energy Storage Mater.2019, 16, 290-
322.
[4] J. B. Zhou, X. Y. Liu, W. L. Cai, Y. C. Zhu, J. W. Liang, K. L.
Zhang, Y. Lan, Z. H. Jiang, G. M. Wang, Y. T. Qian, Adv. Mater. 2017,
1700214.
[5] S. Liu, H. Xu, X. F. Bian, J. K. Feng, J. Liu, Y. H. Yang, C. Yuan,
Y. L. An, R. H. Fan, L. J. Ci. ACS Nano 2018, 12 (7), 7380-7387。
Summary of the invention
It is an object of the present invention to provide a kind of simple processes, the nanometer red phosphorus preparation method of easy scale, practical raw to meet
Demand is ground by obstetrics.
The principle of the preparation method of nanometer red phosphorus provided by the invention, reaction is:
R-CH2-CH2-NH2+Pn→(R-CH2-CH2-NH3 +)( R-CH2-CH2-NH-Pn -) (1)
(2).
The specific steps of preparation are as follows:
(1) preparation of the amine aqueous solution of phosphorus: red phosphorus is added in ethylenediamine, and red phosphorus concentration in amine aqueous solution can be 0.001 g/
Then ml-10 g/ml stirs 2-36 h at a temperature of 25-150 DEG C；
(2) preparation of nanometer red phosphorus: measuring the amine aqueous solution of the phosphorus of certain volume, and it is 0-1 mol/L that concentration is then added dropwise thereto
Dilute hydrochloric acid, rate of addition is 0.5-1000 ml/h, and the amine aqueous solution of phosphorus and dilute hydrochloric acid volumetric ratio are 1-1/50；Finally spend from
Sub- water eccentric cleaning, then be freeze-dried.
In the present invention, by adjusting the concentration of dilute hydrochloric acid, control the grain diameter size of nanometer red phosphorus: dilute hydrochloric acid concentration is
0-1 mol/L, the grain diameter of nanometer red phosphorus are 20-50 nm.
In the present invention, the solvent can be using amine solvents such as ethylenediamine, butylamine, triethylamines.
The present invention has the following aspects remarkable advantage:
(1) using business red phosphorus as raw material；
(2) at room temperature, simple process, synthesis are convenient；
(3) impurity that reaction process generates is highly soluble in water and ethyl alcohol, it is easy to be removed；
(4) ball milling and evaporation are compared, this method energy consumption reduction 70%-90%, sustainable, time foreshortened to 1-60 by tens hours
Minute, it is at low cost；
(5) other two wet chemistry method is compared, this method yield is increased to 80-100%, easy scale；
(6) it may be used as the universal synthesis method of red phosphorus based composites.
Detailed description of the invention
Fig. 1 is that the SEM of 1 gained sample of embodiment schemes.
Fig. 2 is the XRD spectra of 1 gained sample of embodiment.
Fig. 3 is that the SEM of 2 gained sample of embodiment schemes.
Specific embodiment
1. partial size of embodiment is the preparation of 50 nm nanometers of red phosphorus
Red phosphorus is added in ethylenediamine solution, red phosphorus concentration in ethylenediamine solution is 10 g/ml, then in 25 DEG C of temperature
36 h of lower stirring.Then the ethylenediamine solution of the phosphorus of a constant volume is measured, it is the dilute of 0.1 mol/L that concentration is then added dropwise thereto
Hydrochloric acid, rate of addition is the ethylenediamine solution of 1000 ml/h phosphorus and dilute hydrochloric acid volumetric ratio is 1.Last deionized water eccentric cleaning,
It is freeze-dried again.Compared to ball milling and evaporation, this method energy consumption reduction by 90%, sustainable, time foreshortened to 1 point by tens hours
It is clock, at low cost；Compared to other two wet chemistry method, this method yield is increased to 100%, easy scale.
2. partial size of embodiment is the preparation of 20 nm nanometers of red phosphorus
Red phosphorus is added in butylamine solution, red phosphorus concentration in butylamine solution is 0.1g/ml, is then stirred at a temperature of 100 DEG C
Mix 36 h.Then the butylamine solution of the phosphorus of a constant volume is measured, the dilute hydrochloric acid that concentration is 0 mol/L, drop are then added dropwise thereto
Acceleration is the butylamine solution of 100 ml/h phosphorus and dilute hydrochloric acid volumetric ratio is 1/25.Last deionized water eccentric cleaning, it is then cold
It is lyophilized dry.Compared to ball milling and evaporation, this method energy consumption reduce by 80%, sustainable, time by foreshorten within tens hours 30 minutes,
It is at low cost；Compared to other two wet chemistry method, this method yield is increased to 90%, easy scale.
3. partial size of embodiment is the preparation of 35 nm nanometers of red phosphorus
Red phosphorus is added in triethylamine solution, red phosphorus concentration in triethylamine solution is 0.001g/ml, then in 150 DEG C of temperature
Degree is lower to stir 36 h.Then the ethylenediamine solution of the phosphorus of a constant volume is measured, it is 0.05 mol/L that concentration is then added dropwise thereto
Dilute hydrochloric acid, rate of addition is the ethylenediamine solution of 10 ml/h phosphorus and dilute hydrochloric acid volumetric ratio is 1/50.Last deionized water centrifugation
Cleaning, is then freeze-dried.Compared to ball milling and evaporation, this method energy consumption reduces for 70%, sustainable, time by contracting in tens hours
Be as short as 60 minutes, it is at low cost；Compared to other two wet chemistry method, this method yield is increased to 90%, easy scale.
Claims (3)
1. the preparation method of a kind of nanometer of red phosphorus, which is characterized in that specific steps are as follows:
(1) it prepares the amine aqueous solution of phosphorus: red phosphorus is added in amine, 2 ~ 36 h are then stirred at a temperature of 25 ~ 150 DEG C；It is described red
Concentration of the phosphorus in amine aqueous solution is 0.001g/ml ~ 10g/ml；
(2) it prepares nanometer red phosphorus: measuring the amine aqueous solution of the phosphorus of certain volume, it is the dilute of 0 ~ 1.0 mol/L that concentration is added dropwise thereto
Hydrochloric acid, rate of addition are 0.5 ~ 1000 ml/h, and the amine aqueous solution and dilute hydrochloric acid volume ratio of phosphorus are 1 ~ 1/50；Finally use deionized water
Eccentric cleaning, then be freeze-dried.
2. the preparation method of nanometer red phosphorus according to claim 1, which is characterized in that by adjusting the concentration of dilute hydrochloric acid,
Control the grain diameter of nanometer red phosphorus: dilute hydrochloric acid concentration is 0 ~ 1.0 mol/L, and the grain diameter of nanometer red phosphorus is 20 ~ 50 nm.
3. the preparation method of according to claim 1 nanometer of red phosphorus, which is characterized in that solvent uses second two in step (1)
Amine, butylamine or triethylamine.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112295679A (en) * | 2020-09-30 | 2021-02-02 | 西南科技大学 | Red phosphorus grinding method |
| CN112679258A (en) * | 2020-12-24 | 2021-04-20 | 广东金正大生态工程有限公司 | Composite microbial fertilizer and preparation method thereof |
| CN112919438A (en) * | 2021-04-13 | 2021-06-08 | 北京理工大学 | Controllable preparation method of nano red phosphorus hollow sphere |
| CN113307239A (en) * | 2021-06-09 | 2021-08-27 | 东华理工大学 | Method for preparing phosphorus oxynitride |
| CN113620265A (en) * | 2021-08-20 | 2021-11-09 | 清华大学 | Liquid phase preparation method of crystalline red phosphorus |
| CN113957524A (en) * | 2021-11-02 | 2022-01-21 | 陕西科技大学 | Crystal red phosphorus fiber and efficient preparation method thereof |
| CN114314535A (en) * | 2021-12-06 | 2022-04-12 | 上海大学 | Porous nano red phosphorus ball and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112295679A (en) * | 2020-09-30 | 2021-02-02 | 西南科技大学 | Red phosphorus grinding method |
| CN112679258A (en) * | 2020-12-24 | 2021-04-20 | 广东金正大生态工程有限公司 | Composite microbial fertilizer and preparation method thereof |
| CN112919438A (en) * | 2021-04-13 | 2021-06-08 | 北京理工大学 | Controllable preparation method of nano red phosphorus hollow sphere |
| CN112919438B (en) * | 2021-04-13 | 2022-04-05 | 北京理工大学 | Controllable preparation method of nano red phosphorus hollow sphere |
| CN113307239A (en) * | 2021-06-09 | 2021-08-27 | 东华理工大学 | Method for preparing phosphorus oxynitride |
| CN113307239B (en) * | 2021-06-09 | 2023-06-23 | 东华理工大学 | Method for preparing phosphorus oxynitride |
| CN113620265A (en) * | 2021-08-20 | 2021-11-09 | 清华大学 | Liquid phase preparation method of crystalline red phosphorus |
| CN113620265B (en) * | 2021-08-20 | 2022-10-25 | 清华大学 | Liquid phase preparation method of crystalline red phosphorus |
| CN113957524A (en) * | 2021-11-02 | 2022-01-21 | 陕西科技大学 | Crystal red phosphorus fiber and efficient preparation method thereof |
| CN114314535A (en) * | 2021-12-06 | 2022-04-12 | 上海大学 | Porous nano red phosphorus ball and preparation method thereof |
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Application publication date: 20191015 |