CN113235112B - Copper oxide nanoparticle catalyst with large-cavity eggshell structure and preparation method and application thereof - Google Patents
Copper oxide nanoparticle catalyst with large-cavity eggshell structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a copper oxide nanoparticle catalyst with a large-cavity eggshell structure, and a preparation method and application thereof, wherein the preparation method comprises the following steps: dropwise adding cuprous oxide solution into the selenium ion solution, stirring for reaction, centrifugally separating a reaction product, drying, grinding and sieving to obtain copper selenide coated cuprous oxide nano cubic blocks; reacting the copper selenide coated cuprous oxide nano cubic block with ammonia water, centrifugally separating, drying, grinding and sieving to obtain the copper oxide nano granular catalyst with a large-cavity eggshell structure. The invention effectively synthesizes the copper oxide nano-particle catalyst with a large-cavity eggshell structure by utilizing the Cokendall effect, and the maximum Faraday efficiency of ammonia of the catalyst is 99.5 percent under-0.15V Vs RHE potential by virtue of the eggshell structure, and reaches 864.7mmol g cat ‑1 h ‑1 The ammonia formation rate of (a) is about 4.3 times the conversion rate of ammonia of the Haber-Bosch reaction.
Description
Technical Field
The invention relates to the field of preparation of electrochemical reduction catalysts, in particular to a copper oxide nanoparticle catalyst with a large-cavity eggshell structure, and a preparation method and application thereof.
Background
Ammonia (NH) 3 ) Not only is an important industrial raw material, but also ammonia has a high energy density (4.3kWh kg) -1 ) Easy storage and transportation, and green environmental protection, and is very expected to become a next-generation green and clean energy carrier. In the current industrial production, the main ammonia production is by the Haber-Bosch process (Haber-Bosch), under high temperature and pressure, the direct reaction of nitrogen and hydrogen to form ammonia, but under reaction conditionsHarsh, high temperature and high pressure (350-. Electrocatalytic' NO 3 - -to-NH 3 The reaction energy barrier required by the reaction is low, and the reaction is easy to carry out, so that the design and preparation of the electrocatalytic material with the advantages of low energy consumption, high selectivity and the like are core scientific problems in the field of synthesizing ammonia by electrocatalytic reduction of nitrate.
In recent reports, non-noble metal copper-based catalysts have achieved NH 3 The high faradaic efficiency (over 90%), but the limitation of the competing reaction Hydrogen Evolution Reaction (HER) makes the application challenging, so it is highly desirable to design a device that can achieve high current density (greater than 100mA cm) -2 ) And simultaneously has higher ammonia selectivity and a catalyst for inhibiting hydrogen evolution reaction.
Accordingly, there is a need for improvements and developments in the art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a copper oxide nanoparticle catalyst with a large-cavity eggshell structure, and a preparation method and an application thereof, and aims to solve the problem of low ammonia conversion rate of the existing electrochemical nitrate reduction catalyst.
The technical scheme of the invention is as follows:
a preparation method of a copper oxide nanoparticle catalyst with a large-cavity eggshell structure comprises the following steps:
providing a cuprous oxide solution and a selenium ion solution;
dropwise adding the cuprous oxide solution into the selenium ion solution, stirring for reaction, centrifugally separating a reaction product, drying, grinding and sieving to obtain copper selenide coated cuprous oxide nano cubic blocks;
reacting the copper selenide coated cuprous oxide nano cubic block with ammonia water, centrifugally separating, drying, grinding and sieving to obtain the copper oxide nano granular catalyst with a large-cavity eggshell structure.
The preparation method of the copper oxide nanoparticle catalyst with the large-cavity eggshell structure comprises the following steps of:
dropwise adding the copper ion solution into the strong alkali solution, and reacting after stirring to obtain a hydroxyl copper solution;
dissolving ascorbic acid in deionized water, and stirring to obtain a colorless transparent solution;
adding the copper hydroxide solution into the colorless transparent solution under the stirring state, and reacting to obtain orange precipitate after stirring;
centrifugally washing, drying and drying the orange precipitate to obtain cuprous oxide nano cubic blocks;
and dispersing the cuprous oxide nano cubic blocks into deionized water to obtain the cuprous oxide solution.
The preparation method of the copper oxide nanoparticle catalyst with the large-cavity eggshell structure is characterized in that the copper ion solution is one of a copper nitrate solution, a copper chloride solution or a copper bromide solution; the strong alkali solution is one of sodium hydroxide solution or potassium hydroxide solution.
The preparation method of the copper oxide nanoparticle catalyst with the large-cavity eggshell structure comprises the step of stirring at the speed of 400-600 rpm.
The preparation method of the copper oxide nanoparticle catalyst with the large-cavity eggshell structure comprises the step of centrifuging at 8000-10000 rpm.
The preparation method of the copper oxide nanoparticle catalyst with the large-cavity eggshell structure comprises the following steps of:
dissolving sodium borohydride into deionized water to obtain a sodium borohydride solution;
and dispersing selenium powder in ethanol, adding the sodium borohydride solution, and stirring to obtain the selenium ion solution.
The invention relates to a copper oxide nanoparticle catalyst with a large-cavity eggshell structure, which is prepared by the preparation method of the copper oxide nanoparticle catalyst with the large-cavity eggshell structure.
The invention relates to application of a copper oxide nanoparticle catalyst with a large-cavity eggshell structure, wherein the copper oxide nanoparticle catalyst with the large-cavity eggshell structure is used for nitrate electrochemical reduction.
Has the advantages that: the invention effectively synthesizes a copper oxide nano-particle catalyst with a large-cavity eggshell structure by utilizing the Kerkinjel effect, and the catalyst shows remarkable performance on electrocatalytic reduction of nitrate by virtue of a special eggshell structure, and the maximum Faraday efficiency of ammonia is 99.5 percent under the potential of-0.15V Vs RHE, and reaches 864.7mmol g cat -1 h -1 The ammonia formation rate of (a) is about 4.3 times the conversion rate of ammonia of the Haber-Bosch reaction. The catalyst has the advantages of cheap and easily-obtained raw materials, simple and convenient synthesis method, mild conditions, and far higher ammonia generation rate than that of an industrial method, and has guiding significance for the industrial use of electrocatalytic reduction of nitrate.
Drawings
Fig. 1 is a flow chart of a preferred embodiment of a method for preparing a copper oxide nanoparticle catalyst with a large-cavity eggshell structure according to the present invention.
FIG. 2 shows nitrate reduction catalysts of examples 1 to 3 in the presence of 0.1M KNO 3 Linear Sweep Voltammetry (LSV) profile in 1M KOH.
FIG. 3 is a graph of the Linear Sweep Voltammetry (LSV) in 1M KOH for the nitrate reduction catalysts of examples 1-3 of the present invention.
FIG. 4 shows nitrate reduction catalysts of examples 1 to 3 in 0.1M KNO 3 The first efficiency diagram of ammonia production when electrolyzing for 1h in 1M KOH under different potentials.
FIG. 5 is a TEM image of nitrate reduction catalysts of examples 2 to 3 in the present invention.
FIG. 6 is a TEM-EDS picture of the nitrate-reducing catalyst of example 3 in the present invention. .
Detailed Description
The invention provides a copper oxide nanoparticle catalyst with a large-cavity eggshell structure, and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flow chart illustrating a method for preparing a copper oxide nanoparticle catalyst with a large-cavity eggshell structure according to a preferred embodiment of the present invention, which includes the following steps:
s10, providing a cuprous oxide solution and a selenium ion solution;
s20, dropwise adding the cuprous oxide solution into the selenium ion solution, stirring for reaction, centrifugally separating a reaction product, drying, grinding and sieving to obtain copper selenide coated cuprous oxide nano cuboids;
s30, reacting the copper selenide coated cuprous oxide nano cubic block with ammonia water, centrifugally separating, drying, grinding and sieving to obtain the copper oxide nano granular catalyst with a large-cavity eggshell structure.
In the embodiment, a cuprous oxide solution and a selenium ion solution react to form a core-shell structure of cuprous oxide nano cubic blocks coated by a copper selenide shell by utilizing a kirkendall effect; and etching cuprous oxide by ammonia water to form an eggshell structure in which a cuprous oxide nano cubic block is coated by a copper selenide shell, thus obtaining the copper oxide nanoparticle catalyst with the large-cavity eggshell structure, and the catalyst shows remarkable performance for electrocatalytic reduction of nitrate by virtue of the special eggshell structure of the catalyst, wherein the maximum Faraday efficiency of ammonia is 99.5% under the potential of-0.15V Vs RHE, and the maximum Faraday efficiency reaches 864.7mmol g cat -1 h -1 The ammonia formation rate of (a) is about 4.3 times the conversion rate of ammonia of the Haber-Bosch reaction. The catalyst has the advantages of cheap and easily-obtained raw materials, simple and convenient synthesis method, mild conditions, and far higher ammonia generation rate than that of an industrial method, and has guiding significance for the industrial use of electrocatalytic reduction of nitrate.
In some embodiments, the preparation of the cuprous oxide solution comprises the steps of: dropwise adding the copper ion solution into the strong alkali solution, and reacting after stirring to obtain a hydroxyl copper solution; dissolving ascorbic acid in deionized water, and stirring to obtain a colorless transparent solution; adding the copper hydroxide solution into the colorless transparent solution under the stirring state, and reacting to obtain orange precipitate after stirring; centrifugally washing, drying and drying the orange precipitate to obtain cuprous oxide nano cubic blocks; and dispersing the cuprous oxide nano cubic blocks into deionized water to obtain the cuprous oxide solution.
In the embodiment, copper ions form hydroxyl copper complexes with tetragonal structures in a strong alkaline solution, and cuprous oxide nano-cubic blocks are formed under the reduction of ascorbic acid.
In the embodiment, a magnetic stirrer is used for each stirring, the stirring speed is preferably 400-600rpm, and the preferred rotating speed is 500 rpm; a centrifuge is used for each centrifugation, the centrifugation speed is 8000-10000rpm, and the preferred rotation speed is 10000 rpm.
In some specific embodiments, the copper ion solution is one of a copper nitrate solution, a copper chloride solution, or a copper bromide solution, but is not limited thereto; the alkali solution is one of a sodium hydroxide solution or a potassium hydroxide solution, but is not limited thereto.
In some embodiments, the preparation of the selenium ion solution comprises the steps of: dissolving sodium borohydride into deionized water to obtain a sodium borohydride solution; and dispersing selenium powder in ethanol, adding the sodium borohydride solution, and stirring to obtain the selenium ion solution.
In some embodiments, the method for preparing the copper oxide nanoparticle catalyst with a large-cavity eggshell structure comprises the following steps: dropwise adding an ethanol solution of copper nitrate into a concentrated sodium hydroxide solution, and stirring at room temperature for 5-10 minutes to obtain a dark blue solution A; dissolving ascorbic acid into deionized water, and stirring at room temperature for 5-10 minutes to obtain a colorless transparent solution B; pouring the solution A into the solution B under the stirring condition, and continuously stirring for 15-20 minutes at room temperature to obtain orange precipitate; centrifugally washing the obtained orange precipitate, washing with ethanol and water respectively, and then putting the orange precipitate into a vacuum drying oven at 60 ℃ for 24 hours for drying to obtain orange solid powder Cu 2 O; dissolving sodium borohydride to remove sodium borohydrideObtaining colorless transparent solution C in the sub-water; dispersing selenium powder in trace ethanol, adding the solution C, and continuously stirring for 15-20 minutes at room temperature to obtain a colorless transparent solution D; the above orange solid Cu 2 Grinding and sieving the O powder, and dispersing the O powder into deionized water to obtain an orange solution E; dropwise adding the solution D into the solution E, and continuously stirring for 15-20 minutes at room temperature to obtain a black precipitate; centrifugally washing the black precipitate, washing with ethanol and water respectively, and drying in a vacuum drying oven at 60 deg.C for 24 hr to obtain black solid powder Cu 2-x Se@Cu 2 O; and grinding and sieving the black solid powder, dispersing the powder into ammonia water for treatment for 1h, performing centrifugal washing on the treated black solid, washing the black solid with ethanol and water respectively, and drying the black solid in a vacuum drying oven at 60 ℃ for 24 h to obtain the copper oxide nanoparticle catalyst with a large-cavity eggshell structure. In this embodiment, a magnetic stirrer is used for each stirring, and the stirring speed is 400-; a centrifuge is used for each centrifugation, and the centrifugation speed is 8000-10000 rpm.
In some embodiments, a copper oxide nanoparticle catalyst with a large-cavity eggshell structure is also provided, wherein the copper oxide nanoparticle catalyst with a large-cavity eggshell structure is prepared by the preparation method of the copper oxide nanoparticle catalyst with a large-cavity eggshell structure.
In some embodiments, there is also provided a use of a copper oxide nanoparticle catalyst having a large hollow eggshell structure, wherein the copper oxide nanoparticle catalyst having a large hollow eggshell structure according to the present invention is used for electrochemical reduction of nitrate.
Specifically, the copper oxide nanoparticle catalyst with a large-cavity eggshell structure provided by the embodiment is mainly used for nitrate reduction, has high catalytic activity and selectivity for nitrate reduction, has high current density and low required overpotential, and improves the generation rate of ammonia. In addition, the preparation method of the catalyst is simple and flexible, the conditions of the whole process are mild, the yield of each step is considerable, and the catalyst is easy to put into industrial production.
The following is a further explanation of the copper oxide nanoparticle catalyst with a large-cavity eggshell structure, and the preparation method and application thereof, by specific examples:
example 1
0.3624g of copper nitrate trihydrate is dissolved in 3ml of absolute ethyl alcohol and then is dripped into 60ml of 5M sodium hydroxide solution drop by drop, and the mixture is continuously stirred for 10 to 15 minutes at room temperature to obtain a dark blue solution; dissolving 0.585g of ascorbic acid into 400ml of deionized water, pouring the dark blue solution into the deionized water, continuously stirring for 10-15 minutes at room temperature, standing and aging for 6 hours, pouring out supernatant, centrifugally washing orange precipitate with ethanol and water respectively, putting the orange precipitate into a vacuum drying oven at 60 ℃ for 24 hours for drying, grinding and sieving to obtain Cu 2 O nano cubic catalyst.
Ammonia was prepared by electrochemical reduction of nitrate using the catalyst material produced in example 1.
Ethanol and 5 wt.% of Nafion 117 membrane solution were mixed in a volume ratio of 980: 20 to prepare Nafion diluent, and then 0.5mg of Cu is added 2 Adding O nano cube block into 50 μ l Nafion diluent, ultrasonic dispersing, and applying the dispersion solution on 0.5 × 0.5cm washed with hydrochloric acid, ethanol and deionized water 2 The carbon paper is baked and dried by an infrared lamp to obtain the working electrode. An Hg/HgO electrode as a reference electrode, and a Pt electrode as an auxiliary electrode; the working electrode and the reference electrode are arranged in a cathode chamber of an H tank, argon is introduced to remove oxygen, the auxiliary electrode is arranged in an anode chamber, and the two chambers are separated by an anion exchange membrane FAB-PK-130. Respectively with 0.1M KNO 3 The 1M KOH aqueous solution and the 1M KOH aqueous solution were used as electrolytes, and the test was performed at room temperature under normal pressure.
Example 2
0.3624g of copper nitrate trihydrate is dissolved in 3ml of absolute ethyl alcohol and then is dripped into 60ml of 5M sodium hydroxide solution drop by drop, and the mixture is continuously stirred for 10 to 15 minutes at room temperature to obtain a dark blue solution; dissolving 0.585g ascorbic acid into 400ml deionized water, pouring the dark blue solution into the mixture, continuously stirring for 10-15 minutes at room temperature, standing and aging for 6 hours, pouring out supernate, and centrifuging by using ethanol and water respectivelyWashing the orange precipitate, drying in a vacuum drying oven at 60 deg.c for 24 hr, grinding, sieving and dispersing in 30ml deionized water; dissolving 0.24g of sodium borohydride into 50ml of deionized water, pouring the solution into 0.036g of selenium powder in ethanol dispersion (trace ethanol), continuously stirring the solution for 10 to 15 minutes at room temperature to obtain colorless solution, slowly dripping 5ml of the colorless solution into cuprous oxide dispersion, continuously stirring the solution for 10 to 15 minutes at room temperature, performing centrifugal separation, pouring out supernatant, centrifugally washing the obtained black solid with ethanol and water respectively, then placing the black solid into a vacuum drying oven at 60 ℃ for 24 hours for drying, grinding and sieving the black solid to obtain Cu 2-x Se@Cu 2 O nano cubic catalyst.
Preparation of Ammonia by electrochemical reduction of nitrate Using the catalyst Material produced in example 2
Ethanol and 5 wt.% of Nafion 117 membrane solution were mixed in a volume ratio of 980: 20 to prepare Nafion diluent, and then 0.5mg of Cu is added 2 Adding O nano cubic block into 50 μ l Nafion diluent, ultrasonically dispersing, and uniformly dripping the dispersion with a pipette to 0.5 × 0.5cm washed with hydrochloric acid, ethanol and deionized water 2 And baking and drying the carbon paper by using an infrared lamp to obtain the working electrode. An Hg/HgO electrode as a reference electrode, a Pt electrode as an auxiliary electrode; the working electrode and the reference electrode are arranged in a cathode chamber of an H tank, argon is introduced to remove oxygen, the auxiliary electrode is arranged in an anode chamber, and the two chambers are separated by an anion exchange membrane FAB-PK-130. Respectively with 0.1M KNO 3 The 1M KOH aqueous solution and the 1M KOH aqueous solution were used as electrolytes, and the test was performed at room temperature under normal pressure.
Example 3
0.3624g of copper nitrate trihydrate is dissolved in 3ml of absolute ethyl alcohol and then is dripped into 60ml of 5M sodium hydroxide solution drop by drop, and the mixture is continuously stirred for 10 to 15 minutes at room temperature to obtain a dark blue solution; dissolving 0.585g of ascorbic acid into 400ml of deionized water, pouring the dark blue solution into the solution, continuously stirring for 10-15 minutes at room temperature, standing and aging for 6 hours, pouring out supernate, centrifugally washing orange precipitate by using ethanol and water respectively, then putting the orange precipitate into a vacuum drying oven at 60 ℃ for 24 hours for drying, grinding and sieving the dried orange precipitate, and then dispersing the ground orange precipitate into 30ml of deionized water; dissolving 0.24g of sodium borohydride into 50ml of deionized water, pouring the solution into 0.036g of selenium powder in ethanol dispersion (trace ethanol), continuously stirring for 10-15 minutes at room temperature to obtain a colorless solution, slowly dripping 5ml of the colorless solution into cuprous oxide dispersion, continuously stirring for 10-15 minutes at room temperature, performing centrifugal separation, pouring out supernatant, centrifugally washing the obtained black solid with ethanol and water respectively, then placing the black solid into a 60 ℃ vacuum drying oven for 24 hours to perform drying, then grinding and sieving, dispersing the black solid into 6-7% ammonia water, placing the obtained black solid for 1 hour, performing centrifugal separation, pouring out supernatant, centrifugally washing the obtained black solid with ethanol and water respectively, then placing the obtained black solid into a 60 ℃ vacuum drying oven for 24 hours to perform drying, and grinding and sieving to obtain the copper oxide nanoparticle catalyst with the large-cavity eggshell structure.
Preparation of Ammonia by electrochemical reduction of nitrate Using the catalyst Material produced in example 3
Ethanol and 5 wt.% of Nafion 117 membrane solution were mixed in a volume ratio of 980: 20 to prepare Nafion diluent, and then 0.5mg of Cu is added 2 Adding O nano cubic block into 50 μ l Nafion diluent, ultrasonically dispersing, and uniformly dripping the dispersion with a pipette to 0.5 × 0.5cm washed with hydrochloric acid, ethanol and deionized water 2 And baking and drying the carbon paper by using an infrared lamp to obtain the working electrode. An Hg/HgO electrode as a reference electrode, and a Pt electrode as an auxiliary electrode; the working electrode and the reference electrode are arranged in a cathode chamber of an H tank, argon is introduced to remove oxygen, the auxiliary electrode is arranged in an anode chamber, and the two chambers are separated by an anion exchange membrane FAB-PK-130. Respectively with 0.1M KNO 3 The 1M KOH aqueous solution and the 1M KOH aqueous solution were used as electrolytes, and the test was performed at room temperature under normal pressure.
FIG. 2 shows the nitrate radical reduction catalysts of examples 1 to 3 in the presence of 0.1M KNO 3 The electrochemical test was carried out in an electrochemical test system (CHI 760E, CH Instrument Inc) using an H cell, carbon paper carrying a catalyst as a working electrode, a platinum electrode as an auxiliary electrode, and Hg/HgO as a reference electrodeAs shown in fig. 2, of the 3 catalysts, the catalyst activity in example 3 was the best, and both the peak potential and the current density were superior to those of the two catalysts in example 1 and example 2.
Fig. 3 is an LSV diagram of nitrate radical reduction catalysts of examples 1 to 3 in a 1M KOH aqueous solution, and an electrochemical test was performed in an electrochemical test system (CHI 760E, CH Instrument Inc), the test apparatus was an H tank, carbon paper supporting a catalyst was used as a working electrode, a platinum electrode was used as an auxiliary electrode, and Hg/HgO was used as a reference electrode, as shown in fig. 3, among the 3 catalysts, the activity of example 3 with respect to a hydrogen evolution reaction was the smallest, and it was possible to effectively suppress a competitive reaction and improve the selectivity of ammonia.
FIG. 4 shows the results of the nitrate radical reduction catalysts of examples 1 to 3 in the presence of 0.1M KNO 3 The faradaic efficiency of the catalyst in example 3 is kept above 90% at the potential interval of 0-0.25V Vs RHE in 3 catalysts, and the faradaic efficiency can reach 99.5% at the potential of-0.15V Vs RHE, which is better than the two catalysts in example 1 and example 2.
FIG. 5 is a TEM image of nitrate radical reduction catalysts of examples 2 to 3 in the present invention, and as shown in FIG. 5, the average size of the cavity in the catalyst of example 2 is about 30 nm; the catalyst of example 3 has a cavity which is obviously enlarged under the etching of ammonia water, and the average size is about 80 nm.
FIG. 6 is a TEM-EDS pattern of the nitrate-reduced catalyst of example 3 of the present invention, in which the outer shell is mainly composed of elemental selenium and elemental copper and the core contains almost no elemental selenium, as shown in FIG. 6. In conclusion, the invention utilizes the Cokendall effect to effectively synthesize the copper oxide nanoparticle catalyst with the large-cavity eggshell structure, and the catalyst shows remarkable performance on electrocatalytic reduction of nitrate by virtue of the special eggshell structure, and the maximum Faraday efficiency of ammonia is 99.5 percent under-0.15V Vs RHE potential, and reaches 864.7mmol g cat -1 h -1 The ammonia formation rate of (a) is about 4.3 of the ammonia conversion rate of the Haber-Bosch reactionAnd (4) doubling. The catalyst has the advantages of cheap and easily-obtained raw materials, simple and convenient synthesis method, mild conditions, and far higher ammonia generation rate than that of an industrial method, and has guiding significance for the industrial use of electrocatalytic reduction of nitrate.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (6)
1. The application of the cuprous oxide nano cuboidal catalyst coated by the copper selenide shell with a large-cavity eggshell structure is characterized by being used for nitrate electrochemical reduction;
the preparation method of the cuprous oxide nano cubed catalyst coated by the copper selenide shell with the large-cavity eggshell structure comprises the following steps:
providing a cuprous oxide solution and a selenium ion solution;
dropwise adding the cuprous oxide solution into the selenium ion solution, stirring for reaction, centrifugally separating a reaction product, drying, grinding and sieving to obtain copper selenide coated cuprous oxide nano cubic blocks;
and reacting the copper selenide coated cuprous oxide nano cubic block with ammonia water, centrifugally separating, drying, grinding and sieving to obtain the copper selenide shell coated cuprous oxide nano cubic catalyst with a large-cavity eggshell structure.
2. Use according to claim 1, characterized in that the preparation of the cuprous oxide solution comprises the steps of:
dropwise adding the copper ion solution into the strong alkali solution, and reacting after stirring to obtain a hydroxyl copper solution;
dissolving ascorbic acid in deionized water, and stirring to obtain a colorless transparent solution;
adding the copper hydroxide solution into the colorless transparent solution under the stirring state, and reacting to obtain orange precipitate after stirring;
centrifugally washing, drying and drying the orange precipitate to obtain cuprous oxide nano cubic blocks;
and dispersing the cuprous oxide nano cubic blocks into deionized water to obtain the cuprous oxide solution.
3. The use of claim 2, wherein the copper ion solution is one of a copper nitrate solution, a copper chloride solution, or a copper bromide solution; the strong alkali solution is one of sodium hydroxide solution or potassium hydroxide solution.
4. Use according to claim 2, wherein the stirring rate is 400-600 rpm.
5. Use according to claim 2, wherein the centrifugation rate is 8000-.
6. The use according to claim 1, wherein the preparation of the selenium ion solution comprises the steps of:
dissolving sodium borohydride into deionized water to obtain a sodium borohydride solution;
and dispersing selenium powder in ethanol, adding the sodium borohydride solution, and stirring to obtain the selenium ion solution.
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