WO2017107999A1

WO2017107999A1 - Method for preparing copper oxide nanowire

Info

Publication number: WO2017107999A1
Application number: PCT/CN2016/111953
Authority: WO
Inventors: 李�浩
Original assignee: 李�浩
Priority date: 2015-12-25
Filing date: 2016-12-24
Publication date: 2017-06-29
Also published as: CN105712741A

Abstract

A method for preparing a copper oxide nanowire comprises: preparing a Cu(II) salt solution and a complexing agent solution; adding a complexing agent to the Cu(II) salt solution, and stirring the mixture evenly to form a mixed Cu(II) salt solution; slowly adding a sodium hydroxide solution to the mixed Cu(II) salt solution under intense stirring, and stirring the mixture evenly to form a mixture solution; and transferring the mixture solution to a reactor having an inner wall attached with a graphite paper substrate to perform reaction to obtain a two-dimensional material loaded with a nanostructured copper oxide. This method has a short reaction period and a high efficiency.

Description

Method for preparing copper oxide nanowire

Technical field

The invention relates to the technical field of nano new material processing and manufacturing, and in particular to a method for preparing copper oxide nanowires.

Background technique

At present, common methods for preparing supported copper oxide nanowires (that is, loading copper oxide nanowires onto a planar substrate) are template method-chemical precipitation method (such as patent CN201510061151.2) and template-thermal oxidation method (such as CN200910038947.0). The thermal oxidation method (such as the patent CN200610034006.6, CN201110094054.5) and the plasma bombardment method (such as the patent CN201210264695.5), the preparation process of the above method is complicated or requires high process conditions. For example, in the above thermal oxidation method (CN201110094054.5), it is necessary to first deposit a metallic copper film on a substrate by magnetron sputtering in a high vacuum, and then anneal the prepared film in an atmospheric atmosphere. Copper oxide nanowire array film; for example, in the above plasma bombardment method (such as patent CN201210264695.5), the copper film is first subjected to thermal oxidation to form a copper oxide film, and then oxidized by a physical method-plasma bombardment method. The copper film is engraved into a nanowire array. Another example is the template-thermal oxidation method reported in the patent CN200910038947.0, which firstly prepares a plurality of transition layers, a metal film and a protective layer on a substrate, and then selectively exposes the surface of the metal film by photolithography. Finally, the surface is placed in an atmosphere containing oxygen to heat the growth of the oxide nanowires. In general, most of these methods involve physical processing processes (such as photolithography, sputtering, plasma bombardment, etc.) in the preparation process, so the preparation process is complicated and the process cost is high, and the solution chemistry method is currently easy to implement. The deposition of copper oxide nanoparticles on a planar substrate to obtain supported copper oxide nanomaterials, but the use of solution chemistry to deposit copper oxide nanowires on a planar substrate to obtain supported copper oxide nanowires is difficult because of nanowires. Longer, its steric hindrance is much larger than spherical nanoparticles, and it is not easy to deposit on the substrate. Therefore, the existing methods mostly adopt (or partially adopt) physical methods to realize the deposition of copper oxide nanowires on the substrate.

Summary of the invention

The technical problem to be solved by the present invention is to provide a two-dimensional planar substrate supporting copper oxide nanowire preparation method with low production cost, short reaction period and high efficiency against the above-mentioned deficiencies of the prior art.

The technical solution adopted by the present invention to solve the above problems is as follows:

The invention provides a preparation method of copper oxide nanowires, comprising the following steps:

(1) take 2 ~ 200mmol of divalent copper salt dissolved in 40mL of water and stir to form a divalent copper salt solution, take a certain amount of complexing agent dissolved in water and stir to form a complexing agent solution, to the divalent copper salt solution Adding a complexing agent to form a mixed solution of a divalent copper salt, the molar ratio of the complexing agent to the divalent copper salt is 1:1 to 4:1;

(2) taking 25-300 mmol of sodium hydroxide dissolved in 40 mL of water to form a sodium hydroxide solution;

(3) slowly adding the sodium hydroxide solution to the divalent copper salt mixed solution under vigorous stirring to form a mixture solution;

(4) transferring the mixture solution into a reaction vessel having an inner wall and a reaction substrate, and uniformly depositing nanostructured copper oxide on the graphite paper substrate and forming on the graphite paper substrate. A nanostructured copper oxide film is obtained to obtain a two-dimensional material loaded with a nanostructured copper oxide film.

Further, the divalent copper salt in the step (1) is one or more of CuSO ₄ ·5H ₂ O, CuCl ₂ and Cu(NO ₃ ) ₂ , and the complexing agent is EDTA, sodium citrate, One or more of sodium tartrate, ethylenediamine, salicylic acid, 8-hydroxyquinoline-5-sulfonic acid, and triethylenetetramine.

Further, the substrate in the step (4) is graphite paper, and the substrate is a substrate having a length of 12 cm and a width of 5 cm.

Further, the reaction time of the mixture solution in the step (4) in the reaction vessel is 1 to 6 hours, and the temperature is 100 to 180 °C.

The beneficial effects of the invention are:

The preparation method of a copper oxide nanowire provided by the invention is a one-step method, the reagents used are all cheap reagents, the reaction period is short, and the fastest one hour, and further, since the method uses a suitable complexing agent, these The complexing agent can be complexed with the divalent copper salt to control the rate of formation of copper oxide, so that the formed copper oxide nanocrystals have preferential growth orientation to form some non-spherical nanocrystals with specific morphology, Therefore, the basic constituent unit of the copper oxide prepared by the method is not a spherical or spheroidal particle, but a nanowire having a special shape. In addition, the graphite paper has high conductivity, and when the copper oxide nano material is loaded on the graphite paper as a catalyst, It is beneficial to the charge separation of the catalyst, thereby achieving higher catalytic efficiency.

DRAWINGS

1 is an XRD spectrum of a graphite paper-supported copper oxide nanowire prepared in Example 1;

2 is a low-power SEM image of a graphite paper-supported copper oxide nanowire prepared in Example 1;

3 is a high-SEM image of a graphite paper-supported copper oxide nanowire prepared in Example 1;

4 is a diagram showing the effect of catalytic hydrogen peroxide degradation of Congo red by graphite paper supported copper oxide nanowires prepared in Example 1;

Fig. 5 is a graph showing the effect of catalytic hydrogen peroxide degradation of Congo red on total organic carbon (TOC) removal rate of graphite paper supported copper oxide nanowires prepared in Example 1.

detailed description

The embodiments of the present invention are specifically described below with reference to the accompanying drawings, which are for the purpose of illustration only, and are not to be construed as limiting. The scope of the invention is limited, and many modifications may be made to the invention without departing from the spirit and scope of the invention.

Example 1

Take 2mmol CuSO ₄ ·5H ₂ O dissolved in 20mL water to form CuSO ₄ ·5H ₂ O solution, take 4mmol of complexing agent such as triethylenetetramine dissolved in 20mL water to form a complexing agent solution, CuSO ₄ ·5H ₂ O solution The complexing agent solution is mixed and stirred to form a mixed solution, and then 40 mL of a sodium hydroxide solution having a concentration of 5 mol/L is added dropwise to the above mixed solution, and stirred, and finally the reaction liquid is transferred into the reaction vessel, and the cutting is performed. a good, 12 cm long and 5 cm wide graphite paper is rolled into a cylindrical shape against the inner wall of the reaction vessel, and reacted at 180 ° C for 3 hours to uniformly deposit nanostructured copper oxide on the graphite paper substrate, and A nanostructured copper oxide film is formed on the graphite paper substrate to obtain a two-dimensional material loaded with a nanostructured copper oxide film.

Analysis of the substance on the substrate revealed that the material nanostructured copper oxide film supported on the substrate was copper oxide, and the copper oxide nanowire prepared in the first embodiment was analyzed, as shown in Fig. 1, Fig. 1 (a) ) is an XRD spectrum of the graphite paper-supported copper oxide nanowire prepared in Example 1; (b) is a graphite paper base The XRD spectrum of the material, the curve (b) in the figure shows peaks at 2θ=26.8°, 54.6° and 87.4°, corresponding to rhombohedral phase graphite (PDF#75-2078), and curve (a) except the above three The peaks are also at peaks of 2θ=36.8°, 42.7°, 61.8° and 74.1°, which correspond to (111), (200), (220) and (face-to-face cubic) copper oxide, respectively. 311) crystal face, (PDF#78-0428), it can be seen from Fig. 2 and Fig. 3 that the copper oxide nanowire deposited on the graphite paper has a diameter of 50-150 nm, a length of 2-3 micrometers, and a crystal growth shape. Very regular, the degree of crystallinity is high. It can be seen from Figure 4 that when the reaction time is 36 min, the degradation rate of Congo red can reach 97.5%.

It can be seen from Fig. 5 that when the reaction time is 80 min, the total organic carbon (TOC) removal rate of Congo red can reach 77%. The graphite paper supported copper oxide nanowire prepared by comprehensive analysis has good physical and chemical properties.

The preparation method of a copper oxide nanowire provided by the invention is a one-step method, and the reagents used are all cheap reagents, the preparation cost is low, the reaction period is short, and the fastest one hour, which greatly improves the preparation efficiency, and further, Since the method uses a suitable complexing agent, these complexing agents can be complexed with a divalent copper salt to control the rate of formation of copper oxide, so that the formed copper oxide nanocrystals have preferential growth orientation to form some specific morphology. The non-spherical nanocrystals, therefore, the basic constituent units of the copper oxide film prepared by the method are not spherical or spheroidal particles, but nanocrystals having a special shape, such as nanowires.

Example 2

Take 0.4mol of Cu(NO ₃ ) ₂ dissolved in 40mL of water to form Cu(NO ₃ ) ₂ solution, add 0.8mol of salicylic acid, stir and dissolve in 40mL of water to form salicylic acid solution, Cu(NO ₃ ) ₂ solution, water The salicylic acid solution is stirred and mixed, and then 200 mL of a 20 mol/L sodium hydroxide solution is added dropwise to the above mixed solution, and stirred, and finally the reaction liquid is transferred into the reaction vessel, and the cut, 6 cm long and 1 cm wide graphite is cut. The paper roll is placed in a cylindrical shape against the inner wall of the reaction vessel, and reacted at 120 ° C for 8 hours. Nanostructured copper oxide is uniformly deposited on the graphite paper substrate, and nanostructured copper oxide is formed on the graphite paper substrate. Thereby, a two-dimensional material loaded with a nanostructured copper oxide film is obtained.

Example 3

10 mol of CuCl _{2 was} dissolved in 40 mL of water to form a CuCl ₂ solution, and 10 mol of sodium tartrate was added thereto and stirred and dissolved in 40 mL of water to form a sodium tartrate solution. The CuCl ₂ solution and the sodium tartrate solution were stirred and mixed, and then 200 mL of a sodium hydroxide solution having a concentration of 20 mol/L was added dropwise to the above mixed solution, followed by stirring. Finally, the reaction solution was transferred to the reaction vessel, and the cut, 6 cm long and 2 cm wide graphite paper was rolled into a cylindrical shape and pressed against the inner wall of the reaction vessel, and reacted at 160 ° C for 6 hours to uniformly deposit on the graphite paper substrate. There is a nanostructured copper oxide, and nanostructured copper oxide is formed on the graphite paper substrate to obtain a two-dimensional material loaded with a nanostructured copper oxide film.

Example 4

0.4 mol of Cu(NO ₃ ) _{2 was} dissolved in 40 mL of water to form a Cu(NO ₃ ) ₂ solution, and 0.8 mol of ethanolamine was added thereto and stirred and dissolved in 40 mL of water to form an ethanolamine solution. The Cu(NO ₃ ) ₂ solution and the ethanolamine solution are stirred and mixed, and then 200 mL of a 20 mol/L sodium hydroxide solution is added dropwise to the above mixed solution, and stirred, and finally the reaction liquid is transferred to the reaction vessel, which is cut. The graphite paper having a length of 12 cm and a width of 8 cm is rolled into a cylindrical shape and closely attached to the inner wall of the reaction vessel, and reacted at 120 ° C for 8 hours to uniformly deposit nanostructured copper oxide on the graphite paper substrate, and on the graphite paper base. Nanostructured copper oxide is formed on the material to obtain a two-dimensional material loaded with a nanostructured copper oxide film.

Example 5

0.1 mol of CuCl _{2 was} dissolved in 40 mL of water to form a CuCl ₂ solution, and 0.2 mol of 8-hydroxyquinoline-5-sulfonic acid was added and stirred to dissolve in 40 mL of water to form an 8-hydroxyquinoline-5-sulfonic acid solution, and the CuCl ₂ solution was added. The 8-hydroxyquinoline-5-sulfonic acid solution is stirred and mixed, and then 10 mL of a 20 mol/L sodium hydroxide solution is added dropwise to the above mixed solution, and the mixture is stirred, and finally the reaction liquid is transferred into the reaction vessel, which is cut. The graphite paper having a length of 6 cm and a width of 6 cm was rolled into a cylindrical shape to abut against the inner wall of the reaction vessel. After reacting at 140 ° C for 6 hours, nanostructured copper oxide was uniformly deposited on the graphite paper substrate, and nanostructured copper oxide was formed on the graphite paper substrate to obtain a two-dimensional nanostructured copper oxide film. material

The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and combinations thereof may be made without departing from the spirit and scope of the invention. Simplifications should all be equivalent replacements and are included in the scope of the present invention.

Claims

A method for preparing a copper oxide nanowire, comprising the steps of:

(1) take 2 ~ 200mmol of divalent copper salt dissolved in 40mL of water and stir to form a divalent copper salt solution, take a certain amount of complexing agent dissolved in water and stir to form a complexing agent solution, to the divalent copper salt solution Adding a complexing agent solution and stirring uniformly to form a mixed solution of a divalent copper salt, the molar ratio of the complexing agent to the divalent copper salt is 1:1 to 4:1;

(2) taking 25-300 mmol of sodium hydroxide dissolved in 40 mL of water to form a sodium hydroxide solution;

(3) slowly adding the sodium hydroxide solution to the divalent copper salt mixed solution under vigorous stirring to form a mixture solution;

(4) transferring the mixture solution into a reaction vessel having an inner wall and a graphite paper substrate, and uniformly depositing nanostructured copper oxide on the graphite paper substrate, and on the graphite paper substrate A nanostructured copper oxide film is formed to obtain a two-dimensional material loaded with a nanostructured copper oxide film.
The method for preparing a copper oxide nanowire according to claim 1, wherein the divalent copper salt in the step (1) is CuSO 4 · 5H 2 O, CuCl 2 and Cu(NO 3 ) 2 One or more, the complexing agent is one or more of EDTA, sodium citrate, sodium tartrate, ethylenediamine, salicylic acid, 8-hydroxyquinoline-5-sulfonic acid and triethylenetetramine Kind.
The method for preparing a copper oxide nanowire according to claim 1, wherein the substrate in the step (4) is graphite paper, and the substrate is a substrate having a length of 12 cm and a width of 5 cm.
The method for preparing a copper oxide nanowire according to claim 1, wherein the reaction solution in the step (4) is in the reaction vessel for a reaction time of 1 to 6 hours and a temperature of 100 to 180 °C.