CN110002416B - Preparation method of niobium oxygen acid phosphate monoatomic layer sheet - Google Patents
Preparation method of niobium oxygen acid phosphate monoatomic layer sheet Download PDFInfo
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- CN110002416B CN110002416B CN201910200487.0A CN201910200487A CN110002416B CN 110002416 B CN110002416 B CN 110002416B CN 201910200487 A CN201910200487 A CN 201910200487A CN 110002416 B CN110002416 B CN 110002416B
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
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Abstract
The invention belongs to the technical field of chemical material synthesis, and particularly relates to a preparation method of a niobium oxy acid phosphate monoatomic layer sheet. The method comprises the following steps: preparing an acid niobium phosphate oxygen precursor block by adopting a chemical liquid phase synthesis method, and washing and drying the block to obtain powder; an ultrasonic solvent auxiliary stripping method is adopted to prepare the niobium oxy hydrogen phosphate monoatomic layer slice which is a uniform and stable ultrathin nanosheet colloid. The transverse size of the prepared niobium oxyphosphate monoatomic layer slice is dozens of nanometers to hundreds of nanometers, the thickness is about 1nm, and the high-concentration stable dispersion of 10mg/mL in a water phase or an ethanol solvent can be realized. The synthesis and stripping yield achieved by the method can be stably maintained above 98%. The method is simple, convenient, safe and efficient, and has potential value for application research of layered acid phosphorus niobium oxygen in the fields of electrochemical energy storage, photoelectric conversion devices, chemical catalysis, electrocatalysis and the like.
Description
Technical Field
The invention belongs to the technical field of chemical material synthesis, and particularly relates to a preparation method of an acid niobium phosphate oxygen monoatomic layer sheet.
Background
Since 2004 british scientists stripped graphene with single carbon atom thickness from pyrolytic graphite, the two-dimensional material with the ultrathin structure has wide application prospect in lithium ion batteries, super capacitors, solar batteries, heat conducting films and the like due to the structural characteristics of single or multiple carbon atom thickness, extremely high electron mobility, good mechanical flexibility, chemical stability and optical transparency, and excellent electric conduction and heat conducting properties. Taking graphene as a trigger and a breakthrough, a series of two-dimensional layered materials such as hexagonal boron nitride (h-BN), Transition Metal Sulfides (TMDs), layered transition metal Oxides (Oxides), Hydroxides (Hydroxides) and double Hydroxides (LDHs) and a plurality of two-dimensional systems are gradually concerned by the scientific research community and the industrial community; the research on the preparation method, the stripping process and the self-assembly technology of the novel and unique two-dimensional layered material enables the excellent physical and chemical properties of the material to be better served for the application of functional materials, and is a great research field which is significant and rapidly developed in recent years.
Niobium oxy acid phosphate (2 NbOPO)4· H3PO4· H2O) is used as a mature niobium compound applied in the field of catalysis, and is applied to certain extent in the aspects of solid acid catalyst, mesoporous catalytic system design and the like by virtue of the advantages of greenness, no toxicity, high catalytic activity and the like. According to the literature, niobium oxygen acid phosphate has been used in the preparation of beta-enaminones (Wodtke F., Lerhepeng. NbOPO) by catalytic condensation4Simple preparation of catalytic beta-enaminoketones [ J]China journal of the pharmaceutical industry 2017: 1174), catalytic hydrolysis/alcoholysis of cellulose to produce levulinic acid and methyl levulinate (Royal celery, Daqian, Xiajeng, Liu Xiao Hui, mesoporous NbOPO4Acid property control and action research in cellulose hydrolysis and alcoholysis [ C]The 18 th national molecular sieves academy, shanghai, china 2015), etc. It should be noted that most of the niobium phosphate oxygen materials reported in the existing literature are three-dimensional mesoporous systems, and no literature is available focusing on lamellar phase acid niobium phosphate oxygen synthesis regulation and monatomic thin-layer structure exfoliation. Meanwhile, based on the open layer space characteristics of the two-dimensional structure, the extremely large specific surface area and the abundant active reaction sites, the layered niobium phosphate oxygen and the corresponding ultrathin nanosheets have huge application prospects in the fields of electrochemical energy storage, photoelectric conversion devices, chemical catalysis, electrocatalysis and the like. Therefore, the development of a safe, environment-friendly and high-yield preparation method of lamellar-phase niobium oxygen acid phosphate and the preparation of high-yield single-atomic-layer niobium oxygen acid phosphate slice have important significance for the further application of the system in the field of functional materials.
Disclosure of Invention
The invention provides a preparation method of a niobium oxy-hydrogen phosphate monoatomic layer sheet with safety, environmental protection and high yield aiming at the blank of the existing two-dimensional layered material synthesis and stripping technology.
The invention provides a preparation method of an acid niobium phosphate oxygen monoatomic layer sheet, which comprises the following specific steps:
(1) preparing a niobium-oxygen acid phosphate precursor block by adopting a chemical liquid phase synthesis method, and washing and drying the block to obtain a split body;
(2) an ultrasonic solvent auxiliary stripping method is adopted to prepare the niobium oxy hydrogen phosphate monoatomic layer slice which is a uniform and stable ultrathin nanosheet colloid.
In the invention, the molecular formula of the acid niobium phosphate oxygen precursor block is 2NbOPO4· H3PO4· H2O is a two-dimensional structure lamellar phase with the side length of 1-2 mu m and the thickness of 10-100 nm; the element ratio of Nb to O to P =2 (12-16) to (2-4) in the block body is preferably Nb to O to P ≈ 2 to 15: 3.
In the invention, the side length of the niobium oxygen acid phosphate monoatomic layer sheet is 50-1000nm, and the thickness is about 1nm (the thickness error is less than 0.1 nm). The element ratio of the sheet is Nb: O: P =1, (4-6) to (0.8-1.2), and Nb: O: P is preferably approximately equal to 1:5: 1.
In the invention, the yield of both bulk synthesis and sheet structure peeling exceeds 98%.
In the chemical liquid phase synthesis method, a niobium source and phosphoric acid in a certain proportion are used as original reactants, deionized water is used as a synthesis solvent environment, the reactants are fully mixed in a three-neck flask, a reaction system is heated in a hot oil bath at the temperature of 100-200 ℃ for 5-20 h to complete a synthesis reaction, the reaction system is naturally cooled to room temperature, and a product is washed and dried.
The fully mixed reactants are stirred on a magnetic stirring system by taking a magnetic stirrer as a stirring medium until a transparent clear solution is formed.
The washing treatment is to transfer the product obtained by chemical liquid phase synthesis to a Buchner funnel covered with two layers of filter paper and tightly fixed on a filter flask, wash the product with deionized water and fill the inner volume of the funnel, then pump out the washing liquid with an external vacuum pump, and repeatedly carry out the operation flow for 3-6 times.
And the drying treatment is to place the washed product on a filter paper support, and transfer the product into a forced air drying oven to dry the product for 12 to 24 hours at the temperature of between 60 and 80 ℃.
In the invention, the niobium source is commercial grade niobium oxalate powder (mass fraction is more than or equal to 98 percent), and the using amount is 0.5-1.0 g; the phosphoric acid is aqueous solution (mass fraction is more than or equal to 85%) of commercial grade phosphoric acid, and the using amount is 3-8 mL; the deionized water is high-purity commercial grade deionized water, and the usage amount is 80-150 mL.
In the invention, the ultrasonic solvent auxiliary stripping method is to disperse the powder product obtained by chemical liquid phase synthesis in a water phase or an organic phase equivalent, wherein the dispersion concentration is 1 g/L-10 g/L; the dispersion was then placed in an ultrasonic cleaner filled with an appropriate amount of water and the dispersion was subjected to moderate sonication for 30-60 min.
In the invention, the water phase is high-purity deionized water; the organic phase is commercial grade absolute ethyl alcohol (mass fraction is more than or equal to 99.8 percent), commercial grade methanol (more than or equal to 99.9 percent) or commercial grade acetone (more than or equal to 99.7 percent).
Compared with the prior art, the invention has the technical effects that:
(1) in the invention, the adopted raw materials of niobium oxalate (niobium source) and phosphoric acid are green, environment-friendly, safe, nontoxic and low in cost; the selected liquid phase synthesis method and the nano-sheet stripping method are simple and easy to implement and have higher efficiency;
(2) the acid niobium phosphate oxygen lamellar phase obtained by the invention has a stable two-dimensional layer structure, and is easier to strip and realize ultrathin nanosheets compared with the niobium phosphate oxygen block reported in the literature;
(3) the niobium phosphate oxygen colloidal solution obtained by the invention has the stripping yield of over 98 percent, the thickness is uniformly distributed about 1nm, and the niobium phosphate oxygen colloidal solution has the characteristics of high stripping yield, high single-layer proportion, high concentration of the prepared nanosheet colloidal solution and the like.
The method has potential value for the application research of the layered acid phosphorus niobium oxygen in the fields of electrochemical energy storage, photoelectric conversion devices, chemical catalysis, electrocatalysis and the like, and has reference significance for the preparation of other two-dimensional layered nano materials and the high-efficiency stripping method of a single-layer structure.
Drawings
FIG. 1 shows a synthesized layered niobium oxy acid phosphate 2NbOPO4· H3PO4· H2An X-ray powder diffraction pattern of O and a corresponding scanning electron micrograph.
FIG. 2 is a photomicrograph of a monoatomic layer of niobium oxy acid phosphate flake colloidal solution prepared by the present invention.
FIG. 3 is a Tyndall phenomenon photograph of the niobium oxy acid phosphate monoatomic layer flake colloidal solution prepared by the present invention and an atomic force microscope photograph of the corresponding nanosheets.
Detailed Description
The invention is further illustrated by the following specific examples. The present invention is not limited to these examples.
Example 1:
weighing 0.5g of commercial grade niobium oxalate powder, transferring the powder into a 250mL three-neck flask which is pre-cleaned and dried, and sequentially adding 80mL of deionized water and 5mL of commercial grade phosphoric acid; after a magnetic stirrer is added into the three-necked bottle, the three-necked bottle is transferred and fixed on an oil bath pot reaction system provided with a condensation reflux device, the reaction liquid is continuously stirred until a transparent clear solution is formed, and the reaction temperature is adjusted to 120 ℃ for 15 hours of reaction. After the reaction is finished, cooling the system to room temperature, taking a white precipitate product at the bottom of the bottle, transferring the white precipitate product into a Buchner funnel which is covered with two layers of filter paper and is completely sealed on a filter flask, performing suction filtration washing operation on the white product for five times by using deionized water, and transferring the fully washed product into a forced air drying oven to dry for 8 hours at the temperature of 60 ℃ to obtain an acid niobium phosphate oxygen lamellar phase; and (3) transferring 0.01g of dried powder into a beaker filled with 10mL of deionized water, placing the beaker into an ultrasonic cleaner, and continuously acting for 30min by moderate ultrasound to obtain niobium phosphate oxygen nano-flake colloid stripped into a monoatomic layer, wherein the concentration of the colloid solution is 1 g/L.
Example 2:
weighing 0.5g of commercial grade niobium oxalate powder, transferring the powder into a 250mL three-neck flask which is pre-cleaned and dried, and sequentially adding 80mL of deionized water and 5mL of commercial grade phosphoric acid; after a magnetic stirrer is added into the three-necked bottle, the three-necked bottle is transferred and fixed on an oil bath reaction system provided with a condensing reflux device, reaction liquid is continuously stirred until a transparent clear solution is formed, and the reaction temperature is adjusted to 120 ℃ for 15h reaction. After the reaction is finished, cooling the system to room temperature, taking a white precipitate product at the bottom of the bottle, transferring the white precipitate product into a Buchner funnel which is covered with two layers of filter paper and is completely sealed on a filter flask, performing suction filtration washing operation on the white product for five times by using deionized water, and transferring the fully washed product into a forced air drying oven to dry for 8 hours at the temperature of 60 ℃ to obtain an acid niobium phosphate oxygen lamellar phase; and (3) transferring 0.1g of dried powder into a beaker filled with 10mL of deionized water, placing the beaker into an ultrasonic cleaner, and continuously acting for 30min by moderate ultrasound to obtain the niobium phosphate oxygen nano-flake colloid stripped into a monoatomic layer, wherein the concentration of the colloid solution is 10 g/L.
Example 3:
weighing 0.5g of commercial grade niobium oxalate powder, transferring the powder into a 250mL three-neck flask which is pre-cleaned and dried, and sequentially adding 80mL of deionized water and 5mL of commercial grade phosphoric acid; after a magnetic stirrer is added into the three-necked bottle, the three-necked bottle is transferred and fixed on an oil bath pot reaction system provided with a condensation reflux device, the reaction liquid is continuously stirred until a transparent clear solution is formed, and the reaction temperature is adjusted to 120 ℃ for 15 hours of reaction. After the reaction is finished, cooling the system to room temperature, taking a white precipitate product at the bottom of the bottle, transferring the white precipitate product into a Buchner funnel which is covered with two layers of filter paper and is completely sealed on a filter flask, performing suction filtration washing operation on the white product for five times by using deionized water, and transferring the fully washed product into a forced air drying oven to dry for 8 hours at the temperature of 60 ℃ to obtain an acid niobium phosphate oxygen lamellar phase; and (3) transferring 0.01g of dried powder into a beaker filled with 10mL of commercial grade absolute ethyl alcohol, placing the beaker into an ultrasonic cleaner, and continuously acting for 30min by moderate ultrasound to obtain the niobium phosphate oxygen nano-sheet colloid stripped into a monoatomic layer, wherein the concentration of the colloid solution is 1 g/L.
Example 4:
weighing 0.5g of commercial grade niobium oxalate powder, transferring the powder into a 250mL three-neck flask which is pre-cleaned and dried, and sequentially adding 80mL of deionized water and 5mL of commercial grade phosphoric acid; after a magnetic stirrer is added into the three-necked bottle, the three-necked bottle is transferred and fixed on an oil bath pot reaction system provided with a condensation reflux device, the reaction liquid is continuously stirred until a transparent clear solution is formed, and the reaction temperature is adjusted to 120 ℃ for 15 hours of reaction. After the reaction is finished, cooling the system to room temperature, taking a white precipitate product at the bottom of the bottle, transferring the white precipitate product into a Buchner funnel which is covered with two layers of filter paper and is completely sealed on a filter flask, performing suction filtration washing operation on the white product for five times by using deionized water, and transferring the fully washed product into a forced air drying oven to dry for 8 hours at the temperature of 60 ℃ to obtain an acid niobium phosphate oxygen lamellar phase; and (3) transferring 0.1g of dried powder into a beaker filled with 10mL of commercial grade absolute ethyl alcohol, placing the beaker into an ultrasonic cleaner, and continuously acting for 30min by moderate ultrasound to obtain the niobium phosphate oxygen nano-sheet colloid stripped into a monoatomic layer, wherein the concentration of the colloid solution is 10 g/L.
Claims (3)
1. A preparation method of niobium oxygen acid phosphate monoatomic layer sheets comprises the following specific steps:
(1) preparing a niobium-oxygen acid phosphate precursor block by adopting a chemical liquid phase synthesis method, and washing and drying the block to obtain a split body; the molecular formula of the niobium oxygen hydrogen phosphate precursor block is 2NbOPO4· H3PO4· H2O is a two-dimensional structure lamellar phase with the side length of 1-2 mu m and the thickness of 10-100 nm; the element ratio of Nb to O to P =2, (12-16) to (2-4) in the block body;
(2) preparing an acid niobium phosphate oxygen monoatomic layer slice which is a uniform and stable ultrathin nanosheet colloid by adopting an ultrasonic solvent assisted stripping method; the side length of the niobium oxy hydrogen phosphate monoatomic layer sheet is 50-1000nm, the thickness of the sheet is 1nm, the thickness error is less than 0.1nm, and the element ratio of Nb to O to P =1, (4-6) to (0.8-1.2) in the sheet;
the chemical liquid phase synthesis method in the step (1) is characterized in that a niobium source and phosphoric acid in a certain proportion are used as original reactants, deionized water is used as a synthesis solvent environment, the reactants are fully mixed in a three-neck flask, a reaction system is heated in a hot oil bath at the temperature of 100 ℃ and 200 ℃ for 5-20 h to complete a synthesis reaction, the reaction system is naturally cooled to room temperature, and products are washed and dried;
the fully mixed reactant is obtained by taking a magnetic stirrer as a stirring medium and stirring the mixed reactant system on a magnetic stirring system until a transparent clear solution is formed;
the washing treatment is to transfer a product obtained by chemical liquid phase synthesis into a Buchner funnel which is covered with two layers of filter paper and is tightly fixed on a filter flask, wash the product with deionized water and fill the inner volume of the funnel, then pump out the washing liquid with an external vacuum pump, and repeatedly carry out the operation flow for 3-6 times;
putting the washed product in a filter paper support, and transferring the product into a forced air drying oven to dry for 12-24h at the temperature of 60-80 ℃;
the niobium source is commercial grade niobium oxalate powder, and the using amount is 0.5-1.0 g; the phosphoric acid is aqueous solution of commercial grade phosphoric acid, and the using amount is 3-8 mL; the deionized water is commercial grade deionized water, and the using amount is 80-150 mL.
2. The preparation method according to claim 1, wherein the ultrasonic solvent-assisted stripping method comprises dispersing a powder product obtained by chemical liquid phase synthesis in an aqueous phase or an organic phase at a dispersion concentration of 1g/L to 10 g/L; the dispersion was then placed in an ultrasonic cleaner filled with an appropriate amount of water and the dispersion was subjected to moderate sonication for 30-60 min.
3. The method of claim 2, wherein the aqueous phase is high purity deionized water; the organic phase is commercial grade absolute ethyl alcohol, commercial grade methanol or commercial grade acetone.
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| CN113851633B (en) * | 2021-11-29 | 2022-04-08 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
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| CN106732701A (en) * | 2017-01-11 | 2017-05-31 | 贵州大学 | A kind of Fe2O3 doping niobium phosphate solid acid catalyst |
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| CN102962085A (en) * | 2011-09-01 | 2013-03-13 | 华东理工大学 | Preparation method of niobium phosphate solid acid catalyst and application in sugar dehydration |
| CN106732701A (en) * | 2017-01-11 | 2017-05-31 | 贵州大学 | A kind of Fe2O3 doping niobium phosphate solid acid catalyst |
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