CN112323138B - Twin crystal-containing nano cuprous oxide powder and preparation method thereof - Google Patents

Twin crystal-containing nano cuprous oxide powder and preparation method thereof Download PDF

Info

Publication number
CN112323138B
CN112323138B CN202010940435.XA CN202010940435A CN112323138B CN 112323138 B CN112323138 B CN 112323138B CN 202010940435 A CN202010940435 A CN 202010940435A CN 112323138 B CN112323138 B CN 112323138B
Authority
CN
China
Prior art keywords
solution
stirring
molybdenum
powder
cuprous oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010940435.XA
Other languages
Chinese (zh)
Other versions
CN112323138A (en
Inventor
孙少东
张小川
梁淑华
杨曼
崔杰
杨卿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian University of Technology
Original Assignee
Xian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian University of Technology filed Critical Xian University of Technology
Priority to CN202010940435.XA priority Critical patent/CN112323138B/en
Publication of CN112323138A publication Critical patent/CN112323138A/en
Application granted granted Critical
Publication of CN112323138B publication Critical patent/CN112323138B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides

Abstract

The invention discloses a preparation method of nano cuprous oxide powder containing twin crystals, which comprises the steps of taking molybdenum dioxide as a sacrificial template, adding a copper source, dispersing the copper source in a solvent, and adding a precipitator and a reducing agent at a certain temperature to finally prepare the nano cuprous oxide powder containing twin crystals. The invention controllably prepares the nano cuprous oxide material which is uniformly distributed and uniform in size and contains high-density twin crystals by a simple liquid-phase sacrificial template method; compared with other nano cuprous oxide, the electrochemical enzyme-free glucose sensing performance is more excellent; the invention also provides the nano cuprous oxide powder containing twin crystals prepared by the method.

Description

Twin crystal-containing nano cuprous oxide powder and preparation method thereof
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to nano cuprous oxide powder containing twin crystals and a preparation method of the nano cuprous oxide powder containing twin crystals.
Background
At present, a number of literature studies have shown that: the nanometer material has a certain number of defects, which can damage periodically arranged atoms in the crystal, generate lattice distortion internal stress and improve the internal energy of the crystal, thereby being beneficial to regulating and controlling the crystal structure and the electronic structure of the material. The crystal defects are mainly divided into: point defects (vacancies, interstitial and heteroatoms), line defects (edge, screw and disclinations), face defects (surface, grain boundary, phase boundary, twin and stacking faults) and bulk defects (pores and cracks). The crystal defects have great influence on the crystal growth, the mechanical property, the electrical property, the magnetic property and the optical property of the crystal, are very important in the aspects of engineering and basic research, and are important basic contents in the field of material science. Therefore, reasonable design and construction of crystal defects can provide new opportunities for improving material properties.
Twin crystals are a typical surface defect with a symmetrical and highly ordered arrangement of atoms along the twin boundary. Therefore, the twin crystal is constructed in the single crystal metal or alloy, which is not only beneficial to promoting the electron transfer, but also can improve the mechanical property of the single crystal metal or alloy. The formation of twins within a single crystal semiconductor results in a fermi level between the conduction and valence bands of the semiconductor, which induces band bending and thus a "back-to-back" schottky barrier around the twin boundaries. Such schottky barriers can control the migration of free charges, generally repelling majority carriers and attracting minority carriers. Therefore, the twin boundary is not a recombination center of carriers, but accelerates the separation of charges by forming an electrostatic field for positive and negative charge separation. This allows carriers to pass through the twin boundaries of the monoatomic layer without being trapped or scattered. In short, the introduction of twin crystals into a semiconductor material not only optimizes the migration path of electrons or photogenerated carriers, but also promotes efficient separation of electrons or photogenerated carriers, as compared to ordinary grain boundaries. Therefore, the semiconductor functional material containing the nano twin crystal is constructed, which is beneficial to obtaining excellent photo-catalytic performance and electro-catalytic performance.
Cuprous oxide is a promising semiconductor due to its unique physicochemical properties, abundant raw material sources and low cost. The cuprous oxide has various microscopic appearances and is easy to be controllably synthesized, so the cuprous oxide is an ideal material for researching the correlation between the appearances and the performances. The preparation method of the cuprous oxide mainly comprises the following steps: solid phase method, liquid phase reduction method, hydrothermal method, electrochemical method, chemical precipitation method, etc. At present, various cuprous oxide micro-nano crystals such as thin films, low-dimensional nanostructures and various three-dimensional polyhedral solid structures, hollow and porous structures have been reported. However, nano cuprous oxide powder containing twins has not been reported yet.
Disclosure of Invention
The invention aims to provide a method for preparing nano cuprous oxide powder containing twin crystals, which can prepare the nano cuprous oxide powder containing twin crystals with uniform distribution, uniform size and high purity.
A second object of the present invention is to provide a nano cuprous oxide powder containing twin crystals.
The invention adopts the technical scheme that the preparation method of the nano cuprous oxide powder containing twin crystals is implemented according to the following steps:
step 1, adding molybdenum powder and hydrogen peroxide into deionized water, mixing, stirring for a certain time to obtain a molybdenum ion precursor solution, filtering the molybdenum ion precursor solution, putting filtrate into a reaction kettle, putting the filtrate into an oven, carrying out solvothermal reaction for a certain time to obtain a reaction solution of molybdenum dioxide, and carrying out centrifugal separation, washing and drying on the reaction solution of molybdenum dioxide to obtain molybdenum dioxide powder;
step 2, adding the molybdenum dioxide powder obtained in the step 1 into a solvent A for ultrasonic dispersion to obtain a molybdenum dioxide dispersion solution; dropwise adding the copper salt solution into the molybdenum dioxide dispersion solution, and stirring for a certain time to obtain the copper salt/molybdenum dioxide dispersion solution;
and 3, transferring the copper salt/molybdenum dioxide dispersion solution obtained in the step 2 to an oil bath stirrer, heating to a certain temperature, then dropwise adding a precipitator solution, stirring, continuing to add a reducing agent after stirring for a certain time, continuing to stir for a certain time, centrifugally washing the reacted solution while the solution is hot, and then centrifugally separating, washing and drying to obtain the cuprous oxide nano powder containing twin crystals.
The present invention is also characterized in that,
in the step 1, the particle size of the molybdenum powder is 100 nm-800 nm, and the molar volume ratio of the molybdenum powder to the deionized water is 5 mol/L-25 mol/L.
In the step 1, the mass fraction of the hydrogen peroxide solution is 20-40%; the stirring speed is 200 r/min-600 r/min, and the stirring time is 2 h-6 h; the volume ratio of the hydrogen peroxide solution to the deionized water is 1: 1-1: 10, and the volume ratio of the solvent selected by the solvothermal method to the hydrogen peroxide is 10: 1-100: 1; the solvent is any one of methanol, ethanol and glycol.
In the step 1, mixing the hydrogen peroxide solution and the molybdenum powder solution for 2-6 hours; the solvothermal reaction temperature is 120-200 ℃, and the time is 12-24 h; the drying method is vacuum drying, the temperature is 40-60 ℃, and the time is 12-24 hours.
In the step 2, the time for ultrasonically dispersing the molybdenum dioxide in the solvent A is 20-60 min.
In the step 2, the solvent A is any one of methanol, ethanol, ethylene glycol, glycerol and isopropanol, and the mass-volume ratio of the molybdenum dioxide powder to the solvent A is 0.1-5 mg/mL.
In the step 2, the selected copper salt solution is any one of copper nitrate, copper chloride, copper sulfate and copper acetate; the molar concentration of the copper salt solution is 0.01-2 mol/L, and the volume ratio of the copper salt solution to the solvent A is 1: 20-1: 100; the stirring speed is 100 r/min-500 r/min, and the stirring time is 4 h-24 h.
In step 3, heating the copper salt/molybdenum dioxide dispersion solution to 60-95 ℃; the stirring speed is 100 r/min-500 r/min, and the first stirring time is 5 min-20 min; adding a reducing agent and continuously stirring for 5-30 min;
the precipitant solution is any one of a sodium hydroxide solution, a potassium hydroxide solution, a sodium bicarbonate solution and an ammonium bicarbonate solution, the molar concentration of the precipitant solution is 0.01-2 mol/L, and the volume ratio of the precipitant solution to the solvent A is 1: 5-1: 30; the reducing agent is any one of glucose, ascorbic acid and sodium ascorbate, and the molar ratio of the copper salt to the reducing agent is 1: 2-1: 15.
In the step 3, the drying is vacuum drying, the vacuum drying temperature is 40-60 ℃, and the vacuum drying time is 12-24 hours.
The second technical scheme adopted by the invention is that the nano cuprous oxide powder containing twin crystals is prepared by the method.
The invention has the beneficial effects that:
1. the preparation method can prepare the twin crystal-containing nano cuprous oxide powder with uniform distribution, uniform size and high purity by a simple liquid phase sacrificial template method. The preparation method has the characteristics of simple and controllable reaction process, low cost, good repeatability and the like.
2. The nano cuprous oxide containing the twin crystal prepared by the invention has better electrochemical glucose sensing performance than the common nano cuprous oxide, and the twin crystal in the cuprous oxide containing the twin crystal has symmetrical and highly ordered atomic arrangement along the twin crystal boundary, so that the electron transfer capability of the cuprous oxide containing the twin crystal is promoted. In addition, the method has a great application prospect in the fields of solar batteries, lithium ion batteries, electrochemical sensing, optoelectronic devices and the like.
3. The preparation method provides a new synthesis strategy for the research of the growth mechanism of the cuprous oxide nanopowder containing twin crystals, and provides a new idea for preparing other nano materials containing twin crystals.
Drawings
FIG. 1 is a low power transmission electron micrograph of a twin crystal containing nano cuprous oxide powder prepared in example 1;
FIG. 2 is a high transmission electron micrograph of a twin crystal containing nano cuprous oxide powder prepared in example 1;
FIG. 3 is a graph showing the current response results of continuous addition of glucose to a sodium hydroxide solution every 60 seconds for an electrode prepared using a nano-cuprous oxide powder containing twins prepared in example 1 as a raw material and an electrode prepared using a nano-cuprous oxide powder of a general structure as a raw material;
FIG. 4 is a graph of the glucose concentration-current calibration of FIG. 3;
fig. 5 is a histogram comparing glucose sensing sensitivity of an electrode prepared using the nano cuprous oxide powder containing twin crystals prepared in example 1 as a raw material with that of an electrode prepared using a nano cuprous oxide powder having a general structure as a raw material.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of nano cuprous oxide powder containing twin crystals, which is implemented according to the following steps:
step 1, adding molybdenum powder and hydrogen peroxide into deionized water, mixing, stirring for a certain time to obtain a molybdenum ion precursor solution, filtering the molybdenum ion precursor solution, putting filtrate into a reaction kettle, putting the filtrate into an oven, carrying out solvothermal reaction for a certain time to obtain a reaction solution of molybdenum dioxide, and carrying out centrifugal separation, washing and drying on the reaction solution of molybdenum dioxide to obtain molybdenum dioxide powder;
in the step 1, the particle size of molybdenum powder is 100 nm-800 nm, and the molar volume ratio of the molybdenum powder to deionized water is 5 mol/L-25 mol/L;
in the step 1, the mass fraction of the hydrogen peroxide solution is 20-40%; the stirring speed is 200 r/min-600 r/min, and the stirring time is 2 h-6 h; the volume ratio of the hydrogen peroxide solution to the deionized water is 1: 1-1: 10, and the volume ratio of the solvent selected by the solvothermal method to the hydrogen peroxide is 10: 1-100: 1; the selected solvent is any one of methanol, ethanol and glycol;
in the step 1, mixing the hydrogen peroxide solution and the molybdenum powder solution for 2-6 hours; the solvothermal reaction temperature is 120-200 ℃, and the time is 12-24 h; the drying method is vacuum drying, the temperature is 40-60 ℃, and the time is 12-24 hours;
in the step 2, the ultrasonic dispersion time of the molybdenum dioxide in the solvent A is 20-60 min;
step 2, adding the molybdenum dioxide powder obtained in the step 1 into a solvent A for ultrasonic dispersion to obtain a molybdenum dioxide dispersion solution; dropwise adding the copper salt solution into the molybdenum dioxide dispersion solution, and stirring for a certain time to obtain the copper salt/molybdenum dioxide dispersion solution;
in the step 2, the solvent A is any one of methanol, ethanol, ethylene glycol, glycerol and isopropanol, and the mass-volume ratio of the molybdenum dioxide powder to the solvent A is 0.1-5 mg/mL;
in the step 2, the selected copper salt solution is any one of copper nitrate, copper chloride, copper sulfate and copper acetate; the molar concentration of the copper salt solution is 0.01-2 mol/L, and the volume ratio of the copper salt solution to the solvent A is 1: 20-1: 100; the stirring speed is 100 r/min-500 r/min, and the stirring time is 4 h-24 h.
Step 3, transferring the copper salt/molybdenum dioxide dispersion solution obtained in the step 2 to an oil bath stirrer, heating, dropwise adding a precipitator solution after heating to a certain temperature, stirring, continuously adding a reducing agent after stirring for a certain time, continuously stirring for a certain time, centrifugally washing the solution after reaction while the solution is hot, and then centrifugally separating, washing and drying to obtain cuprous oxide nano powder containing twin crystals;
in step 3, heating the copper salt/molybdenum dioxide dispersion solution to 60-95 ℃; the stirring speed is 100 r/min-500 r/min, and the first stirring time is 5 min-20 min; adding a reducing agent and continuously stirring for 5-30 min;
the precipitant solution is any one of a sodium hydroxide solution, a potassium hydroxide solution, a sodium bicarbonate solution and an ammonium bicarbonate solution, the molar concentration of the precipitant solution is 0.01-2 mol/L, and the volume ratio of the precipitant solution to the solvent A is 1: 5-1: 30; the reducing agent is any one of glucose, ascorbic acid and sodium ascorbate, and the molar ratio of the copper salt to the reducing agent is 1: 2-1: 15;
in the step 3, the drying is vacuum drying, the vacuum drying temperature is 40-60 ℃, and the vacuum drying time is 12-24 hours.
The invention also provides the nanometer cuprous oxide powder containing twin crystals, which is prepared by the method.
Example 1
Adding molybdenum powder with the molar concentration of 15mol/L and the particle size of 550nm into deionized water, placing the mixture on a stirrer at the rotating speed of 500r/min, then adding a hydrogen peroxide solution with the mass fraction of 30%, wherein the volume ratio of the hydrogen peroxide solution to the deionized water is 1:3, and stirring for 4 hours to fully react; filtering with anhydrous ethanol, wherein the volume ratio of the hydrogen peroxide solution to the anhydrous ethanol is 1:35, putting the filtrate into a reaction kettle, and placing the reaction kettle in an oven for solvothermal reaction, wherein the reaction time is 8 hours and the temperature is 180 ℃; carrying out centrifugal separation on the reaction solution, washing and centrifuging the reaction solution for 4 times by using absolute ethyl alcohol, and then placing the reaction solution in a 40 ℃ drying oven for vacuum drying for 24 hours to obtain molybdenum dioxide powder; adding molybdenum dioxide powder into ethylene glycol according to the mass-to-volume ratio of 0.5mg/mL, and performing ultrasonic dispersion for 20 min; dropwise adding a copper nitrate solution with the molar concentration of 0.6mol/L, wherein the volume ratio of the copper nitrate solution to the ethylene glycol is 1:50, and then placing the mixture on a stirrer with the rotating speed of 300r/min for stirring for 24 hours to fully and uniformly mix the mixture; transferring the solution to an oil bath stirrer, heating to 90 ℃, stirring at the rotating speed of 300r/min, dropwise adding a sodium hydroxide solution with the molar concentration of 0.5mol/L, wherein the volume ratio of the sodium hydroxide solution to the glycol solution of molybdenum dioxide is 1:8, and continuously stirring for 10 min; adding glucose powder with a molar ratio of copper nitrate to glucose powder of 1:3, and continuously stirring for 20 min; centrifuging while hot, washing with deionized water and absolute ethyl alcohol, centrifuging for 4 times, and then vacuum drying in an oven at 40 ℃ for 24 hours to obtain the cuprous oxide nanopowder containing twin crystals.
Example 2
Adding molybdenum powder with the molar concentration of 5mol/L and the particle size of 100nm into deionized water, placing the mixture on a stirrer at the rotating speed of 200r/min, then adding a hydrogen peroxide solution with the mass fraction of 25%, wherein the volume ratio of the hydrogen peroxide solution to the deionized water is 1:1, and stirring for 6 hours to fully react; filtering with anhydrous ethanol, wherein the volume ratio of the hydrogen peroxide solution to the anhydrous ethanol is 1:10, putting the filtrate into a reaction kettle, and placing the reaction kettle in an oven for solvothermal reaction, wherein the reaction time is 24 hours and the temperature is 140 ℃; carrying out centrifugal separation on the reaction solution, washing and centrifuging the reaction solution for 5 times by using absolute ethyl alcohol, and then drying the reaction solution in a vacuum drying oven at the temperature of 45 ℃ for 20 hours to obtain molybdenum dioxide powder; adding molybdenum dioxide powder into methanol according to the mass-to-volume ratio of 0.1mg/mL, and performing ultrasonic dispersion for 30 min; dropwise adding a copper chloride solution with the molar concentration of 0.1mol/L, wherein the volume ratio of the copper chloride solution to the methanol is 1:35, and then placing the mixture on a stirrer with the rotating speed of 200r/min for stirring for 8 hours to fully and uniformly mix the mixture; transferring the solution to an oil bath stirrer, heating to 80 ℃, stirring at the rotating speed of 200r/min, dropwise adding a potassium hydroxide solution with the molar concentration of 0.1mol/L, wherein the volume ratio of the potassium hydroxide solution to the methanol solution of molybdenum dioxide is 1:10, and continuously stirring for 8 min; adding ascorbic acid powder with a molar ratio of copper chloride to ascorbic acid powder of 1:2, and continuously stirring for 10 min; and (3) centrifuging and washing while hot, washing and centrifuging for 5 times by using deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at the temperature of 45 ℃ for 20 hours to obtain the cuprous oxide nano powder containing twin crystals.
Example 3
Adding molybdenum powder with the molar concentration of 15mol/L and the particle size of 300nm into deionized water, placing the mixture on a stirrer at the rotating speed of 400r/min, then adding a hydrogen peroxide solution with the mass fraction of 35%, wherein the volume ratio of the hydrogen peroxide solution to the deionized water is 1:6, and stirring for 4 hours to fully react; filtering with methanol at a volume ratio of 1:50, placing the filtrate in a reaction kettle, and heating in an oven at 180 deg.C for 18 h; carrying out centrifugal separation on the reaction solution, washing and centrifuging the reaction solution for 5 times by using absolute ethyl alcohol, and then drying the reaction solution in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to obtain molybdenum dioxide powder; adding molybdenum dioxide powder into ethanol according to the mass-to-volume ratio of 2mg/mL, and performing ultrasonic dispersion for 40 min; dropwise adding a copper sulfate solution with the molar concentration of 0.5mol/L, wherein the volume ratio of the copper sulfate solution to the ethanol is 1:50, and then placing the mixture on a stirrer with the rotating speed of 300r/min for stirring for 12 hours to fully and uniformly mix the mixture; transferring the solution to an oil bath stirrer, heating to 70 ℃, stirring at the rotating speed of 300r/min, dropwise adding a sodium bicarbonate solution with the molar concentration of 0.5mol/L, wherein the volume ratio of the sodium bicarbonate solution to the ethanol solution of the molybdenum dioxide is 1:15, and continuously stirring for 12 min; adding ascorbic acid powder with a molar ratio of copper sulfate to ascorbic acid powder of 1:6, and continuously stirring for 20 min; and (3) centrifuging and washing while hot, washing and centrifuging for 5 times by using deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the cuprous oxide nano powder containing twin crystals.
Example 4
Adding molybdenum powder with the molar concentration of 20mol/L and the particle size of 700nm into deionized water, placing the mixture on a stirrer at the rotating speed of 500r/min, then adding a hydrogen peroxide solution with the mass fraction of 40%, wherein the volume ratio of the hydrogen peroxide solution to the deionized water is 1:4, and stirring for 3 hours to fully react; filtering with methanol, wherein the volume ratio of the hydrogen peroxide solution to the methanol is 1:70, putting the filtrate into a reaction kettle, and placing the reaction kettle in an oven for solvothermal reaction, wherein the reaction time is 14 hours and the temperature is 190 ℃; carrying out centrifugal separation on the reaction solution, wherein the centrifugal rotation speed is 9000r/min, the centrifugal time is 4min, washing and centrifuging for 6 times by using absolute ethyl alcohol, and then carrying out vacuum drying for 4h to obtain molybdenum dioxide powder; adding molybdenum dioxide powder into isopropanol according to the mass-to-volume ratio of 3mg/mL, and performing ultrasonic dispersion for 50 min; dropwise adding a copper acetate solution with the molar concentration of 1mol/L, wherein the volume ratio of the copper acetate solution to the isopropanol is 1:80, and then placing the mixture on a stirrer with the rotating speed of 400r/min for 18 hours to fully and uniformly mix the mixture; transferring the solution to an oil bath stirrer, heating to 60 ℃, stirring at the rotating speed of 400r/min, dropwise adding an ammonium bicarbonate solution with the molar concentration of 1mol/L, wherein the volume ratio of the ammonium bicarbonate solution to the isopropanol solution of molybdenum dioxide is 1:20, and continuously stirring for 15 min; adding sodium ascorbate powder with a molar ratio of copper acetate to sodium ascorbate powder of 1:8, and continuously stirring for 25 min; and (3) centrifuging and washing while hot, washing and centrifuging for 6 times by using deionized water and absolute ethyl alcohol, and then drying for 4 hours in vacuum to obtain the cuprous oxide nano powder containing twin crystals.
Example 5
Adding molybdenum powder with the molar concentration of 25mol/L and the particle size of 800nm into deionized water, placing the mixture on a stirrer at the rotating speed of 600r/min, then adding a hydrogen peroxide solution with the mass fraction of 30%, wherein the volume ratio of the hydrogen peroxide solution to the deionized water is 1:1, and stirring for 2 hours to fully react; filtering with ethylene glycol, wherein the volume ratio of the hydrogen peroxide solution to the ethylene glycol is 1:100, putting the filtrate into a reaction kettle, and placing the reaction kettle in an oven for solvothermal reaction, wherein the reaction time is 12 hours and the temperature is 200 ℃; carrying out centrifugal separation on the reaction solution, washing and centrifuging for 4 times by using absolute ethyl alcohol, and then carrying out vacuum drying for 8 hours to obtain molybdenum dioxide powder; adding molybdenum dioxide powder into glycerol according to the mass-to-volume ratio of 5mg/mL, and performing ultrasonic dispersion for 60 min; dropwise adding a copper nitrate solution with the molar concentration of 2mol/L, wherein the volume ratio of the copper nitrate solution to the glycerol is 1:100, and then placing the mixture on a stirrer with the rotating speed of 500r/min for 24 hours to fully and uniformly mix the mixture; transferring the solution to an oil bath stirrer, heating to 95 ℃, stirring at the rotating speed of 500r/min, dropwise adding a sodium hydroxide solution with the molar concentration of 5mol/L, wherein the volume ratio of the sodium hydroxide solution to the glycerol solution of molybdenum dioxide is 1:30, and continuously stirring for 20 min; adding glucose powder with a molar ratio of copper nitrate to glucose powder of 1:10, and continuously stirring for 30 min; and (3) centrifuging and washing while hot, washing and centrifuging for 5 times by using deionized water and absolute ethyl alcohol, and then drying for 8 hours in vacuum to obtain the cuprous oxide nano powder containing twin crystals.
The invention controllably prepares the cuprous oxide nanopowder containing the high-density twin crystals by a simple liquid-phase sacrificial template method. The preparation method has the advantages of simple and controllable reaction process, wide raw material source, low cost, no pollution, good repeatability and the like. The low power TEM results of the cuprous oxide powder prepared in example 1 are shown in fig. 1, and it can be seen from fig. 1 that the cuprous oxide powder prepared has a large amount of twin crystals, and the size thereof can be effectively controlled to about 27 nm. The high-power TEM result of the cuprous oxide powder is shown in fig. 2, and it can be seen that twin crystals in the prepared powder exhibit a symmetrical and ordered atomic arrangement along twin boundaries.
The nano cuprous oxide material containing the twin crystal prepared by the method of the invention has more excellent electrochemical glucose sensing performance than other nano cuprous oxide, because the twin crystal in the cuprous oxide containing the twin crystal has symmetrical and highly ordered atomic arrangement along the twin boundary, which promotes the electron transfer capability. Therefore, the material has a wide application prospect in the fields of solar cells, lithium ion batteries, electrochemical sensing, optoelectronic devices and the like. FIGS. 3 to 5 are the results of measuring the current response characteristics of the enzyme-free glucose sensor containing nano cuprous oxide powder comprising twin crystals prepared in example 1, wherein FIG. 3 is twin crystal-Cu2O electrode and ordinary-Cu2The results of the current response of the O-electrode to the continuous addition of glucose to the sodium hydroxide solution every 60 seconds are shown schematically, and fig. 4 is a graph of the glucose concentration-current calibration of fig. 3, it can be seen that the electrode prepared according to the present invention exhibits a higher current response to glucose. FIG. 5 is a twin crystal-Cu2O electrode and ordinary-Cu2The glucose sensing sensitivity of the O electrode is compared with a histogram, and the oxidation containing twin crystals prepared by the method can be seenGlucose sensing sensitivity of cuprous Material (2180.3 muA. mM)-1·cm-2) Glucose sensing sensitivity (1300 muA. mM) over cuprous oxide material prepared without sacrificial template-1·cm-2) Is more excellent.
The preparation method provides a new synthesis strategy for the research on the growth mechanism of the nano cuprous oxide powder containing twin crystals and provides a new idea for preparing other materials containing twin crystals.

Claims (1)

1. A preparation method of nanometer cuprous oxide powder containing twin crystals is characterized by comprising the following steps:
step 1, adding molybdenum powder and hydrogen peroxide into deionized water, mixing, stirring for a certain time to obtain a molybdenum ion precursor solution, filtering the molybdenum ion precursor solution, putting filtrate into a reaction kettle, putting the filtrate into an oven, carrying out solvothermal reaction for a certain time to obtain a reaction solution of molybdenum dioxide, and carrying out centrifugal separation, washing and drying on the reaction solution of molybdenum dioxide to obtain molybdenum dioxide powder;
step 2, adding the molybdenum dioxide powder obtained in the step 1 into a solvent A for ultrasonic dispersion to obtain a molybdenum dioxide dispersion solution; dropwise adding the copper salt solution into the molybdenum dioxide dispersion solution, and stirring for a certain time to obtain the copper salt/molybdenum dioxide dispersion solution;
step 3, transferring the copper salt/molybdenum dioxide dispersion solution obtained in the step 2 to an oil bath stirrer, heating, dropwise adding a precipitator solution after heating to a certain temperature, stirring, continuously adding a reducing agent after stirring for a certain time, continuously stirring for a certain time, centrifugally washing the solution after reaction while the solution is hot, and then centrifugally separating, washing and drying to obtain cuprous oxide nano powder containing twin crystals;
in the step 1, the particle size of molybdenum powder is 100 nm-800 nm, and the molar volume ratio of the molybdenum powder to deionized water is 5 mol/L-25 mol/L;
in the step 1, the mass fraction of the hydrogen peroxide solution is 20-40%; the stirring speed is 200 r/min-600 r/min, and the stirring time is 2 h-6 h; the volume ratio of the hydrogen peroxide solution to the deionized water is 1: 1-1: 10, and the volume ratio of the solvent selected by the solvothermal method to the hydrogen peroxide is 10: 1-100: 1; the selected solvent is any one of methanol, ethanol and glycol;
in the step 1, mixing the hydrogen peroxide solution and the molybdenum powder solution for 2-6 hours; the solvothermal reaction temperature is 120-200 ℃, and the time is 12-24 h; the drying method is vacuum drying, the temperature is 40-60 ℃, and the time is 12-24 hours;
in the step 2, the ultrasonic dispersion time of the molybdenum dioxide in the solvent A is 20-60 min;
in the step 2, the solvent A is any one of methanol, ethanol, ethylene glycol, glycerol and isopropanol, and the mass-volume ratio of the molybdenum dioxide powder to the solvent A is 0.1-5 mg/mL;
in the step 2, the selected copper salt solution is any one of copper nitrate, copper chloride, copper sulfate and copper acetate; the molar concentration of the copper salt solution is 0.01-2 mol/L, and the volume ratio of the copper salt solution to the solvent A is 1: 20-1: 100; the stirring speed is 100 r/min-500 r/min, and the stirring time is 4 h-24 h;
in step 3, heating the copper salt/molybdenum dioxide dispersion solution to 60-95 ℃; the stirring speed is 100 r/min-500 r/min, and the first stirring time is 5 min-20 min; adding a reducing agent and continuously stirring for 5-30 min;
the precipitator solution is sodium hydroxide solution or potassium hydroxide solution, the molar concentration of the precipitator solution is 0.01-2 mol/L, and the volume ratio of the precipitator solution to the solvent A is 1: 5-1: 30; the reducing agent is any one of glucose, ascorbic acid and sodium ascorbate, and the molar ratio of the copper salt to the reducing agent is 1: 2-1: 15;
in the step 3, the drying is vacuum drying, the vacuum drying temperature is 40-60 ℃, and the vacuum drying time is 12-24 hours.
CN202010940435.XA 2020-09-09 2020-09-09 Twin crystal-containing nano cuprous oxide powder and preparation method thereof Active CN112323138B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010940435.XA CN112323138B (en) 2020-09-09 2020-09-09 Twin crystal-containing nano cuprous oxide powder and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010940435.XA CN112323138B (en) 2020-09-09 2020-09-09 Twin crystal-containing nano cuprous oxide powder and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112323138A CN112323138A (en) 2021-02-05
CN112323138B true CN112323138B (en) 2021-10-22

Family

ID=74303781

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010940435.XA Active CN112323138B (en) 2020-09-09 2020-09-09 Twin crystal-containing nano cuprous oxide powder and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112323138B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805011A (en) * 2010-04-06 2010-08-18 厦门大学 Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof
CN102351238A (en) * 2011-07-18 2012-02-15 西安交通大学 Method for preparing hollow copper sulphide crystal with nano-twin structure
CN103435089A (en) * 2013-07-16 2013-12-11 上海应用技术学院 Spherical cuprous oxide micro-nano particles with roughness surface and preparation method thereof
CN108585018A (en) * 2018-02-26 2018-09-28 西安理工大学 A kind of size is less than the Cu of 100nm2The preparation method of O nanospheres

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805011A (en) * 2010-04-06 2010-08-18 厦门大学 Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof
CN102351238A (en) * 2011-07-18 2012-02-15 西安交通大学 Method for preparing hollow copper sulphide crystal with nano-twin structure
CN103435089A (en) * 2013-07-16 2013-12-11 上海应用技术学院 Spherical cuprous oxide micro-nano particles with roughness surface and preparation method thereof
CN108585018A (en) * 2018-02-26 2018-09-28 西安理工大学 A kind of size is less than the Cu of 100nm2The preparation method of O nanospheres

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
不同结构Cu2O多晶的合成及其对高氯酸铵热分解的催化作用;罗小林等;《物理化学学报》;20140331;第30卷;第520-526页 *

Also Published As

Publication number Publication date
CN112323138A (en) 2021-02-05

Similar Documents

Publication Publication Date Title
CN110021757B (en) Preparation method of nanorod material wrapped by nickel selenide sulfide film growing on surface of foamed nickel
CN109037617B (en) Cobalt selenide/nitrogen-doped carbon composite material and preparation method and application thereof
Wei et al. Three kinds of Cu 2 O/ZnO heterostructure solar cells fabricated with electrochemical deposition and their structure-related photovoltaic properties
CN102569508B (en) Thin-film solar photovoltaic cell with nano wire array structure and preparation method for thin-film solar photovoltaic cell
CN110124706B (en) Preparation method of titanium carbide/indium zinc sulfide composite visible-light-driven photocatalyst
CN101429680A (en) Production method for direct growth of one-dimensional nano cuprous oxide array on metallic copper substrate
CN1884090A (en) ZnIn2S4 nano materials and their synthesis method and application
CN110707311B (en) High-nickel ternary material and nano zinc oxide composite cathode material and preparation method thereof
CN113000054B (en) Bi 2 O 2 Preparation method of Se material
CN113087016A (en) Preparation method of rod-shaped bismuth sulfide/reduced graphene oxide composite material
JP2017511784A (en) Method for doping Cu (In, Ga) (S, Se) 2 nanoparticles with sodium or antimony
CN114188434A (en) TiO2/BiFeO3/BiOI ternary nano heterojunction photoelectrode and preparation method and application thereof
CN104701138A (en) Preparation method for CZTS (Se) nano-crystalline thin film
Wang et al. Self-assembled CuO nanoarchitectures and their catalytic activity in the thermal decomposition of ammonium perchlorate
CN102345162B (en) One-dimensional axial type nano zinc oxide / zinc sulfide heterojunction and preparation method thereof
CN106920932B (en) A kind of leaf of bamboo shape Co (OH)2/ graphene combination electrode material and preparation method thereof
Patwary et al. Copper oxide nanostructured thin films processed by SILAR for optoelectronic applications
CN111217537A (en) Preparation method of core-shell molybdenum trioxide @ tungsten oxide nanocrystalline electrochromic film
CN105236472A (en) Preparation method of SnO2 nano-wire array
CN112323138B (en) Twin crystal-containing nano cuprous oxide powder and preparation method thereof
CN108031481B (en) Ultrathin bismuth oxyhalide nanosheet photocatalyst stripped by silver intercalation and preparation method thereof
CN111196610A (en) Zn2GeO4Molten salt method for synthesizing nano rod
CN114156593B (en) Diaphragm functional material for improving performance of lithium metal battery, preparation and application
CN102912333B (en) Method for preparing thermoelectric film by using layer by layer self-assembly
CN114408976A (en) High-performance alpha-MnO2Al nanorod and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant