阅读说明：本技术 一种超薄双金属钼酸盐纳米片包覆纳米管的异质结构材料、及其制备方法和应用 (Heterostructure material of ultrathin bimetal molybdate nanosheet coated nanotube, and preparation method and application thereof ) 是由 张小俊 顾明政 于 2021-09-17 设计创作，主要内容包括：本发明提供了一种超薄双金属钼酸盐纳米片包覆纳米管的异质结构材料、及其制备方法和应用,以泡沫铜为基底,在表面原位生成一层铜氧化物空心纳米管,随后在上面覆盖一层超薄双金属纳米片,形成异质结构。通过控制引入Ni的量调控CoNi比例形成双金属的钼酸盐,得到超薄CoMoO-(4)纳米片的最优形貌。与现有技术相比,本发明产物纯度高、分散性好,且可控制,生产成本低,重现性好,通过反应条件,形成稳定均匀的最优形貌结构。所制备出的超薄NiCo双金属钼酸盐纳米片包覆的CuO-(x)纳米管材料在电化学催化裂解水方面实现了高的电化学活性,长期稳定性,大的电化学活性面积,具有较高的双功能活性,在催化电解水方面具有潜在的应用价值。(The invention provides a heterostructure material of an ultrathin bimetallic molybdate nano-sheet coated nanotube, and a preparation method and application thereof. The CoNi proportion is regulated and controlled by controlling the amount of introduced Ni to form bimetallic molybdate, so that the ultrathin CoMoO is obtained 4 And (3) the optimal morphology of the nanosheets. Compared with the prior art, the product of the invention has high purity, good dispersibility, controllability, low production cost and good reproducibility, and forms a stable and uniform optimal morphology structure through reaction conditions. Prepared outCuO coated by ultrathin NiCo bimetallic molybdate nanosheets x The nanotube material realizes high electrochemical activity, long-term stability and large electrochemical activity area in the aspect of electrochemical catalytic water splitting, has higher bifunctional activity, and has potential application value in the aspect of catalytic water splitting.)

1. A preparation method of a heterostructure material of an ultrathin bimetallic molybdate nanosheet coated nanotube is characterized by comprising the following steps:

s1: mixing the sodium hydroxide solution and the ammonium persulfate solution under stirring until the solution is clear and transparent, then adding foamy copper for soaking, and taking out to obtain Cu (OH)₂a/CF nanowire;

s2: mixing Cu (OH)₂Soaking the/CF nano-wire in a glucose solution, taking out, and completely soaking the foamy copper in a solution containing urea, a molybdenum source, a cobalt source and a nickel source to perform hydrothermal reaction; obtaining CoNiMoO Pre/CuO_xa/CF precursor;

s3: CoNiMoO Pre/CuO_xthe/CF precursor is calcined at high temperature to obtain CoNiMoO₄/CuO_x/CF。

2. The method according to claim 1, wherein the concentration of the sodium hydroxide solution in step S1 is 2.0 to 3.0mol L^-1The concentration of the ammonium persulfate solution is 0.075-0.175mol L^-1(ii) a The volume ratio of the sodium hydroxide solution to the ammonium persulfate solution is 2:1-1: 2.

3. The method according to claim 1, wherein the concentration of the glucose solution in step S2 is 0.5 to 1.5M; the Cu (OH)₂The soaking time of the/CF in 1M glucose solution is 3-9 h.

4. The method according to claim 1, wherein in step S2, the solution containing urea, molybdenum source, cobalt source and nickel source is prepared by: dissolving molybdenum source and urea in deionized water as cobalt source and nickel source, and performing ultrasonic treatment.

5. The preparation method according to claim 4, wherein the solution containing urea, molybdenum source, cobalt source and nickel source has a molybdenum source molar concentration of 0.0125 to 0.0375 mol/L; the molar concentration of the urea is 0.125-0.375mol/L, and the total molar concentration of the cobalt source and the nickel source is 0.0125-0.0375 mol/L.

6. The method according to claim 4 or 5, wherein the molar ratio of the cobalt source to the nickel source is 3:1 to 1: 3.

7. The method according to claim 4 or 5, wherein the hydrothermal reaction in step S2 is carried out at 60-140 ℃ for 6-14 h.

8. The method according to claim 1, wherein the high-temperature calcination conditions in step S3 are: the temperature is 300-400 ℃, and the calcination time is 1.5-2.5 h.

9. The heterostructure material of ultrathin bimetallic molybdate nano-sheet coated nanotubes prepared by the preparation method of any one of claims 1 to 8, which is characterized by ultrathin CoNiMoO with the thickness of 5 to 15nm₄CuO with diameter of 100-200nm covered by nano-sheet_xOn the nanotubes.

10. Use of the ultra-thin bimetallic molybdate nanosheet-coated nanotube heterostructure material prepared by the preparation method of any one of claims 1 to 8 as an electrolytic water catalyst.

Technical Field

The invention belongs to the technical field of nano materials, and particularly relates to CuO coated by ultrathin NiCo bimetallic molybdate nanosheets_xA heterostructure material of the nanotube,And a preparation method and application thereof.

Background

Hydrogen energy (H)₂) As an alternative to traditional fossil fuels, there is a long-standing goal to be further explored, which if achieved, would have revolutionary impact on various aspects of energy utilization.

Highly efficient electrochemical splitting of water driven by renewable energy is an effective way to generate pure hydrogen energy. Generally, electrolyzed water is passed through two half-cell reactions including an anodic Oxygen Evolution Reaction (OER) and a cathodic Hydrogen Evolution Reaction (HER). However, since neither thermodynamics nor kinetics are ideal, there is a need to find stable, scalable electrocatalysts to achieve cost-effective HER or OER, which can simultaneously reduce overpotential and increase reaction speed.

Disclosure of Invention

The invention aims to provide a heterostructure material of an ultrathin bimetallic molybdate nano-sheet coated nanotube, in particular to CuO coated by an ultrathin NiCo bimetallic molybdate nano-sheet_xThe heterostructure material of the nanotube has a large amount of dislocation and defects, has a large specific surface area, and provides a larger active area and active sites, thereby improving the electrochemical catalytic performance.

The invention also aims to provide a preparation method of the heterostructure material of the ultrathin bimetallic molybdate nano-sheet coated nanotube, which synthesizes CuO coated by the ultrathin NiCo bimetallic molybdate nano-sheet by a solvothermal method in one step_xThe nano tube is characterized in that foam copper is used as a substrate, a layer of copper oxide nano tube is generated on the surface in situ, and then a layer of NiCo bimetallic molybdate nano sheet is covered on the copper oxide nano tube.

It is still another object of the present invention to provide the use of the ultra-thin bimetallic molybdate nanosheet coated nanotube heterostructure material for catalyzing electrolysis of water with high activity and long-term stability during electrocatalysis.

The specific technical scheme of the invention is as follows:

a preparation method of a heterostructure material of an ultrathin bimetallic molybdate nanosheet coated nanotube comprises the following steps:

s1: mixing the sodium hydroxide solution and the ammonium persulfate solution under stirring until the solution is clear and transparent, then adding foamy copper for soaking, and taking out to obtain Cu (OH)₂a/CF nanowire;

s2: mixing Cu (OH)₂Soaking the/CF nano-wire in a glucose solution, taking out, and completely soaking the foamy copper in a solution containing urea, a molybdenum source, a cobalt source and a nickel source to perform hydrothermal reaction; obtaining CoNiMoO Pre/CuO_xa/CF precursor;

s3: CoNiMoO Pre/CuO_xthe/CF precursor is calcined at high temperature to obtain CoNiMoO₄/CuO_x/CF。

In step S1, the copper foam is pretreated before use, and the pretreatment method is as follows: ultrasonically washing the foamy copper by dilute hydrochloric acid to remove a surface oxide layer, ultrasonically washing by acetone to remove surface organic matters, and ultrasonically washing by deionized water and absolute ethyl alcohol respectively for later use;

in the pretreatment, the foam copper is cut into 2 x 4cm²Size, the concentration of the dilute hydrochloric acid solution used is preferably 3mol L^-1。

The concentration of the sodium hydroxide solution in the step S1 is 2.0-3.0mol L^-1Preferably 2.5mol L^-1The concentration of the ammonium persulfate solution is 0.075-0.175mol L^-1Preferably 0.125mol L^-1。

The volume ratio of the sodium hydroxide solution to the ammonium persulfate solution is 2:1-1:2, and preferably 1: 1.

In the step S1, the soaking time is 5-15min, preferably 10 min; the soaking is carried out at normal temperature and normal pressure.

Taking out the foam copper in the step S1, washing the foam copper with ethanol and deionized water respectively, and finally drying the foam copper in vacuum to obtain Cu (OH)₂a/CF nanowire; the vacuum drying condition is vacuum drying for 4 hours at 60 ℃.

In step S1, the foamy copper, sodium hydroxide and ammonium persulfate undergo an in-situ redox reaction to generate a layer of copper hydroxide nanowires, wherein the ammonium persulfate is an oxidant: cu +4NaOH + (NH)₄)₂S₂O₈＝Cu(OH)₂↓+2Na₂SO₄+2NH₃↑+2H₂O。

The concentration of the glucose solution in step S2 is 0.5 to 1.5M, preferably 1M; the Cu (OH)₂The soaking time of the/CF in the glucose solution is 3-9h, and the preferred soaking time is 6 h. The reaction is carried out at normal temperature and normal pressure.

In step S2, the method for preparing the solution containing urea, molybdenum source, cobalt source, and nickel source comprises: dissolving a molybdenum source, urea, a cobalt source and a nickel source in deionized water, and carrying out ultrasonic treatment to obtain the product. The ultrasonic treatment time is 5-15min, preferably 10 min.

The urea is added to act as a precipitant and is decomposed with the rise of temperature in the hydrothermal reaction to generate weak alkalinity. Followed by dehydration of the hydroxide to the oxide under hydrothermal conditions at elevated temperature and pressure.

The molybdenum source is selected from Na₂MoO₄·2H₂O; the cobalt source is selected from Co (NO)₃)₂ 6H₂O; the nickel source is selected from Ni (NO)₃)₂6H₂O; if the nano-sheet is replaced by other materials, the structure of the nano-sheet coated nano-tube cannot be obtained, but the nano-sheet on the surface is thicker and rougher and the nano-tube becomes thicker.

In step S2, the molar concentration of the molybdenum source in the solution containing urea, the molybdenum source, the cobalt source and the nickel source is 0.0125-0.0375 mol/L; preferably 0.025 mol/L; the molar concentration of the urea is 0.125-0.375mol/L, preferably 0.25 mol/L; the total molar concentration of the cobalt source and the nickel source is 0.0125-0.0375mol/L, preferably 0.025 mol/L. CoNiMoO Pre/CuO with different CoNi proportions is prepared by adjusting different dosage ratios of a cobalt source and a nickel source in a solution_xa/CF precursor.

The molar ratio of the cobalt source to the nickel source is 3:1-1: 3; preferably 2: 1. The material obtained in the preferred proportion has the best electrochemical activity, long-term stability, electrochemical active area and the like.

The hydrothermal reaction in step S2 is carried out at 60-140 deg.C for 6-14h, preferably at 100 deg.C for 10 h.

And after the hydrothermal reaction in the step S2 is finished, naturally cooling to room temperature, taking out the copper foam, washing with absolute ethyl alcohol and deionized water, and finally drying in vacuum for later use. The vacuum drying condition is vacuum drying for 4 hours at 60 ℃.

Step S3 specifically includes: CoNiMoO Pre/CuO_xputting/CF in a tube furnace, calcining at high temperature, and naturally cooling to obtain black final target product CoNiMoO with different CoNi proportions₄/CuO_x/CF。

The high-temperature calcination conditions in step S3 are: the temperature is 300 ℃ to 400 ℃, and the temperature is N₂Under the protection of atmosphere, the high-temperature calcination time is 1.5 to 2.5 hours, and the heating rate is 2 to 10 ℃ for min^-1. Preferably 350 ℃ under N₂Calcining at high temperature for 2h under atmosphere protection, and heating rate of 5 deg.C for min^-1。

The preparation method of the heterostructure material of the ultrathin bimetallic molybdate nano-sheet coated nanotube provided by the invention is to obtain the CuO coated by the ultrathin NiCo bimetallic molybdate nano-sheet_xNanotube heterostructure material, in which ultrathin CoNiMoO with thickness of 5-15nm is used₄CuO with diameter of 100-200nm covered by nano-sheet_xOn the nanotubes.

CuO coated by ultrathin NiCo bimetallic molybdate nanosheet prepared by the invention_xHeterostructure material of nanotubes, said CuO_xThe value of x of the nanotube ranges from 0.5 to 1.

CuO_xCalcining the dehydrated product after reducing copper hydroxide with glucose solution, and controlling CuO by controlling the time of soaking reduction of glucose solution_xFor the values of x, the invention has performed three experiments: reducing the copper hydroxide into Cu by glucose for 12 hours₂O; reducing the solution by glucose solution for 6 hours, calcining and dehydrating to obtain CuO_x(ii) a The CuO is directly obtained by calcination and dehydration without being reduced by glucose solution. The ratio of CuOx is between Cu₂The value range of x between O and CuO is 0.5-1.

The invention also provides application of the heterostructure material of the ultrathin bimetallic molybdate nano-sheet coated nanotube as an electrolytic water catalyst.

CuO coated by the ultrathin NiCo bimetallic molybdate nano-sheet prepared by the invention_xThe foamy copper of the nanotube material is directly used as a working electrode material for water electrolysis, so that high electrochemical activity and long-term stability are realized, a large specific surface area is provided, a larger active area is provided, more active sites are carried, and efficient water electrolysis is realized.

In the technical scheme provided by the invention, foamy copper is taken as a substrate, the foamy copper, sodium hydroxide and ammonium persulfate are subjected to in-situ redox reaction to generate a layer of copper hydroxide nanowires, and the ammonium persulfate is taken as an oxidant; and generating a layer of copper oxide hollow nanotube on the surface in situ, and then covering a layer of ultrathin bimetallic nanosheet on the copper oxide hollow nanotube to form a heterostructure. The CoNi proportion is regulated and controlled by controlling the amount of introduced Ni to form bimetallic molybdate, so that the ultrathin CoMoO is obtained₄And (3) the optimal morphology of the nanosheets. The urea is added in the hydrothermal reaction to play a role of a precipitator, and the urea is decomposed to generate weak alkalinity along with the increase of temperature in the hydrothermal reaction. Subsequently dehydrating the hydroxide to an oxide at high temperature and high pressure under hydrothermal conditions; CoMoO, a single metal molybdate, is formed when Ni is not introduced₄/CuO_xThe surface lamellar structure formed in the/CF process is compact, and thicker nanosheets cover the copper oxide nanotubes. When a small amount of Ni is gradually introduced, the flaky structure on the surface becomes thinner, and the ultrathin nanosheets and the hollow nanotubes form a more obvious hierarchical structure. However, when the Ni content is higher than that of Co, a sheet structure is more difficult to form, and the surface of the hollow nanotube is smoother. Therefore, the invention introduces Ni to form bimetallic molybdate, and can regulate and control the surface ultrathin CoMoO₄Electrocatalytic performance of the optimum morphology of the nanoplatelets. It is noted that the structure of the hierarchical structure can significantly enlarge the surface area of the catalyst, provide rich channels, allow the electrolyte to fully contact the catalyst inside, and allow the generated gas to properly diffuse. According to the invention, due to the difference of atomic radii of the bimetallic molybdate nanosheets formed by introducing Ni, crystal lattices are changed to generate defects, and meanwhile, the formation of a heterostructure can also adjust an interface electronic structure and crystal lattice strain to create a new catalytic site, so that the interface charge transfer dynamics is enhanced.Prepared CuO coated by ultrathin NiCo bimetallic molybdate nanosheets_xNanotube materials have a large number of dislocations and defects, thus having more active sites and thus increasing their electrocatalytic activity.

Compared with the prior art, the product obtained by the preparation method has high purity, good dispersibility, controllability, low production cost and good reproducibility, and a stable and uniform optimal morphology structure is formed by controlling the use amount and concentration of raw materials and the temperature and time of reaction. CuO coated by prepared ultrathin NiCo bimetallic molybdate nanosheet_xThe nanotube material realizes high electrochemical activity, long-term stability and large electrochemical activity area in the aspect of electrochemical catalytic water splitting, has higher bifunctional activity, and has potential application value in the aspect of catalytic water splitting.

Drawings

FIG. 1 is a Scanning Electron Microscope (SEM) photograph at low resolution (a) and high resolution (b) of bare CF pretreated at step S1 in example 1;

FIG. 2 is CuO coated with ultrathin NiCo bimetallic molybdate nanosheets as in example 3_xHeterostructure material of nanotubes (CoNiMoO)₄-21/CuO_xScanning Electron Micrographs (SEM) at low resolution (a) and high resolution (b) of/CF);

FIG. 3 is CuO coated with ultrathin NiCo bimetallic molybdate nanosheets as in example 3_xHeterostructure material of nanotubes (CoNiMoO)₄-21/CuO_xTransmission Electron Micrographs (TEM) at low resolution (a) and high resolution (b) of/CF);

FIG. 4 is CuO coated with ultrathin NiCo bimetallic molybdate nanosheets as in example 3_xHeterostructure material of nanotubes (CoNiMoO)₄-21/CuO_x/CF) EDX element map;

wherein a is CoNiMoO in example 3₄-21/CuO_xSTEM map of/CF;

b is an EDX element map of Cu element in example 3;

c is an EDX element map of Co element in example 3;

d is an EDX element map of the Ni element in example 3;

e is an EDX element map of the Mo element in example 3;

f is the EDX element map of the O element in example 3;

FIG. 5 is CuO coated with ultrathin NiCo bimetallic molybdate nanosheets as in example 3_xHeterostructure material of nanotubes (CoNiMoO)₄-21/CuO_x/CF) X-ray spectrometer (EDX) diagram;

FIG. 6 is CuO coated with ultrathin NiCo bimetallic molybdate nanosheets as in example 3_xHeterostructure material of nanotubes (CoNiMoO)₄-21/CuO_x/CF) X-ray diffraction pattern (XRD);

FIG. 7 is CuO coated with ultrathin NiCo bimetallic molybdate nanosheets prepared in example 3_xHeterostructure material of nanotubes (CoNiMoO)₄-21/CuO_x/CF) X-ray photoelectron spectroscopy (XPS) contrast;

FIG. 8 is CuO coated with bimetallic molybdate nanosheets of different CoNi ratios prepared in examples 1-2 and 4-7_xHeterostructure material of nanotubes (CoNiMoO)₄/CuO_x/CF) Scanning Electron Micrograph (SEM);

wherein a is example 1CoMoO₄/CuO_xa/CF low resolution SEM image; b is example 1CoMoO₄/CuO_xa/CF high resolution SEM image;

c is CoNiMoO in example 2₄-31/CuO_xa/CF low resolution SEM image; d is CoNiMoO in example 2₄-31/CuO_xa/CF high resolution SEM image;

e is CoNiMoO in example 4₄-11/CuO_xa/CF low resolution SEM image; f is CoNiMoO in example 4₄-11/CuO_xa/CF high resolution SEM image;

g is CoNiMoO in example 5₄-12/CuO_xa/CF low resolution SEM image; h is CoNiMoO in example 5₄-12/CuO_xa/CF high resolution SEM image;

i is CoNiMoO in example 6₄-13/CuO_xa/CF low resolution SEM image; j is CoNiMoO in example 6₄-13/CuO_xa/CF high resolution SEM image;

k is NiMoO in example 7₄/CuO_xa/CF low resolution SEM image; l is NiMoO in example 7₄/CuO_xa/CF high resolution SEM image;

FIG. 9 is CuO coated with bimetallic molybdate nanosheets of different CoNi ratios prepared in examples 1-2 and 4-7_xHeterostructure material of nanotubes (CoNiMoO)₄/CuO_x/CF) X-ray spectrometer (EDX) diagram;

wherein a is example 1CoMoO₄/CuO_xX-ray spectrometer (EDX) diagram for/CF;

b is CoNiMoO in example 2₄-31/CuO_xX-ray spectrometer (EDX) diagram for/CF;

c is CoNiMoO in example 4₄-11/CuO_xX-ray spectrometer (EDX) diagram for/CF;

d is CoNiMoO in example 5₄-12/CuO_xX-ray spectrometer (EDX) diagram for/CF;

e is CoNiMoO in example 6₄-13/CuO_xX-ray spectrometer (EDX) diagram for/CF;

f is NiMoO in example 7₄/CuO_xX-ray spectrometer (EDX) diagram for/CF;

FIG. 10 shows copper hydroxide nanowires (Cu (OH) in comparative example 1₂Scanning Electron Micrographs (SEM) at low resolution (a) and high resolution (b) of/CF);

FIG. 11 is a copper oxide nanotube (CuO) in comparative example 2_xScanning Electron Micrographs (SEM) at low resolution (a) and high resolution (b) of/CF);

FIG. 12 shows cuprous oxide nanotubes (Cu) in comparative example 3₂O/CF) low resolution (a) and high resolution (b);

FIG. 13 is a Scanning Electron Micrograph (SEM) of copper oxide nanowires (CuO/CF) at low resolution (a) and high resolution (b) of comparative example 4;

FIG. 14 is a graph of CoNiMoO in comparative examples 5-7₄Scanning electron microscope for low resolution (a) and high resolution (b) of/CF materialsPhotograph (SEM);

wherein a is CoMoO₄Low resolution Scanning Electron Micrograph (SEM) of/CF, b is CoMoO₄Low resolution Scanning Electron Micrograph (SEM) of/CF;

c is CoNiMoO₄Low resolution Scanning Electron Micrograph (SEM) of-21/CF, d is CoNiMoO₄-low resolution Scanning Electron Micrograph (SEM) of 21/CF;

e is NiMoO₄Low resolution Scanning Electron Micrograph (SEM) of/CF, f is NiMoO₄Low resolution Scanning Electron Micrograph (SEM) of/CF;

FIG. 15 is CoNi-proportioned bimetallic molybdate nanosheet coated CuO prepared in examples 1, 3 and 7_xComparative curves (LSV) for linear sweep voltammetry testing of heterostructure materials of nanotubes and copper hydroxide nanowires and copper oxide nanotubes of comparative examples 1, 2 and bare Copper Foam (CF) hydrogen evolution reaction;

FIG. 16 is a CoNi ratio bimetallic molybdate nanosheet coated CuO prepared in examples 2-6_xA comparison curve (LSV) of a linear sweep voltammetry test of hydrogen evolution reaction of a heterostructure material of nanotubes;

FIG. 17 is a comparison curve (LSV) of the linear sweep voltammetry tests of hydrogen evolution reactions for different copper oxides prepared in comparative examples 2-4;

FIG. 18 is a graph of different CoNiMoOs prepared in comparative examples 5-7₄A comparison curve (LSV) for linear sweep voltammetry testing of hydrogen evolution reaction of/CF;

FIG. 19 is CoNiMoO₄-21/CuO_xComparative Curve (CP) of chronopotentiometric method for/CF material; the insets are CoNiMoO₄-comparison LSV after recycling of 21/CF material;

FIG. 20 is CoNi ratio bimetallic molybdate nanosheet coated CuO prepared in examples 1, 3 and 7_xHeterostructure material of nanotubes and comparative curves (LSV) of linear sweep voltammetry tests of copper hydroxide nanowires and copper oxide nanotubes and bare Copper Foam (CF) oxygen evolution reaction of comparative examples 1, 2;

FIG. 21 shows the CoNi ratios prepared in examples 2-6The CuO coated by the bimetallic molybdate nano-sheet_xA contrast curve (LSV) for linear sweep voltammetry testing of oxygen evolution reactions of the heterostructure material of nanotubes;

FIG. 22 is a comparison curve (LSV) of the linear sweep voltammetry tests of the oxygen evolution reaction for different copper oxides prepared in comparative examples 2-4;

FIG. 23 is a graph of different CoNiMoOs prepared in comparative examples 5-7₄A comparison curve (LSV) of the linear sweep voltammetry test of the oxygen evolution reaction of/CF;

FIG. 24 is CoNiMoO₄-21/CuO_xComparative Curve (CP) of chronopotentiometric method for/CF material; the insets are CoNiMoO₄-comparison LSV after recycling of 21/CF material;

FIG. 25 is a Cyclic Voltammogram (CV) for different materials prepared in examples 1, 3, 7 and comparative examples 1, 2 and bare Copper Foam (CF);

wherein a is the Cyclic Voltammogram (CV) of bare Copper Foam (CF);

b is copper hydroxide nanowire (Cu (OH) of comparative example 1₂/CF) Cyclic Voltammogram (CV);

c is copper oxide nanotube (CuO) in comparative example 2_x/CF) Cyclic Voltammogram (CV);

d is NiMoO in example 7₄/CuO_xCyclic Voltammogram (CV) of/CF;

e is CoMoO in example 1₄/CuO_xCyclic Voltammogram (CV) of/CF;

f is CoNiMoO in example 3₄-21/CuO_xCyclic Voltammogram (CV) of/CF;

FIG. 26 is a plot of the electrocatalytic active surface area (ECSA) from cyclic voltammetry for different materials prepared in examples 1, 3, 7 and comparative examples 1, 2 and bare Copper Foam (CF);

FIG. 27 is an electrochemical impedance plot (EIS) of different materials prepared in examples 1, 3, 7 and comparative examples 1, 2 and bare Copper Foam (CF);

fig. 28 is a Scanning Electron Microscope (SEM) of the nanomaterial obtained in comparative example 8.

Detailed Description

The present invention will be described in detail with reference to the following examples and drawings.

Example 1(Co Metal alone, for comparison)

CuO coated by ultrathin Co metal molybdate nanosheets_xThe preparation method of the nanotube material comprises the following steps:

s1: cutting foamy Copper (CF) into 2X 4cm²Size, in each case 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to remove a surface oxide layer, ultrasonic washing with acetone to remove surface organic matters, and ultrasonic washing with deionized water and absolute ethyl alcohol for 5 times respectively for later use;

the CF Scanning Electron Micrograph (SEM) after the processing of step S1 is shown in fig. 1.

S2: 10ml of a 2.5M sodium hydroxide solution and 10ml of a 0.125M ammonium persulfate solution were mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foam copper for 10 minutes, taking out the foam copper, respectively washing the foam copper for 10 times by using ethanol and deionized water, and finally drying the foam copper for 4 hours in vacuum at the temperature of 60 ℃ to obtain Cu (OH)₂The product obtained is Cu (OH)₂/CF；

S3: firstly, the prepared Cu (OH)₂the/CF was first soaked in 1M glucose solution for 6 hours and partially reduced. Then 1mmol of Na₂MoO₄·2H₂O, 10mmol of urea and Co (NO)₃)₂·6H₂O and Ni (NO)₃)₂·6H₂Dissolving the mixture with the molar ratio of O being 1:0 (wherein the total molar number of Co ions and Ni ions is 1mmol, Co ions is 1mmol and Ni ions is 0mmol) in 40ml of deionized water, carrying out ultrasonic treatment for 10 minutes, transferring the solution to a stainless steel high-temperature high-pressure reaction kettle with a 100ml polytetrafluoroethylene lining, and adding the synthesized Cu (OH)₂the/CF was immersed in it completely and heated at 100 ℃ for 10 hours. After the reaction is finished, the copper foam is naturally cooled to room temperature, and the copper foam is taken out and washed with absolute ethyl alcohol and deionized water for several times. Finally, vacuum drying is carried out for 4h at the temperature of 60 ℃ for standby. The product obtained is noted as CoMoO₄ Pre/CuO_x/CF；

S4: mixing CoMoO₄ Pre/CuO_x/CF placed in a tube furnace at 350At a temperature of N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1And obtaining the CuO coated by the ultrathin Co metal molybdate nanosheet after the CuO is naturally cooled_xNanotube material, the resulting product being noted as CoMoO₄/CuO_x/CF。

Example 2

CuO coated by ultrathin NiCo bimetallic molybdate nanosheets_xThe preparation method of the nanotube material comprises the following steps:

s1: cutting the foam copper into 2 × 4cm²Size, in each case 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to remove surface oxide layer, ultrasonic washing with acetone to remove surface organic matter, and ultrasonic washing with deionized water and anhydrous ethanol for 5 times respectively;

s2: 10ml of a 2.5M sodium hydroxide solution and 10ml of a 0.125M ammonium persulfate solution were mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foam copper for 10 minutes, taking out the foam copper, respectively washing the foam copper for 10 times by using ethanol and deionized water, and finally drying the foam copper for 4 hours in vacuum at the temperature of 60 ℃ to obtain Cu (OH)₂a/CF nanowire; the product obtained is designated Cu (OH)₂/CF；

S3: firstly, the prepared Cu (OH)₂the/CF was first soaked in 1M glucose solution for 6 hours and partially reduced. Then 1mmol of Na₂MoO₄·2H₂O, 10mmol of urea and Co (NO)₃)₂·6H₂O and Ni (NO)₃)₂·6H₂Dissolving the O molar ratio of 3:1 (wherein the total molar number of Co ions and Ni ions is 1mmol) in 40ml of deionized water, performing ultrasonic treatment for 10 minutes, transferring the solution into a 100ml stainless steel high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and adding synthesized Cu (OH)₂the/CF was immersed in it completely and heated at 100 ℃ for 10 hours. After the reaction is finished, the copper foam is naturally cooled to room temperature, and the copper foam is taken out and washed with absolute ethyl alcohol and deionized water for several times. Finally, vacuum drying is carried out for 4h at the temperature of 60 ℃ for standby. The product obtained is designated CoNiMoO according to the proportion of CoNi added₄-31 Pre/CuO_x/CF；

S4: mixing CoMoO₄ Pre/CuO_xthe/CF is placed in a tube furnace at 350 ℃ under N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1And obtaining the CuO coated by the ultrathin NiCo bimetal molybdate nano-sheets after the CuO is naturally cooled_xNanotube material, the resulting product being designated CoNiMoO₄-31/CuO_x/CF。

Example 3

CuO coated by ultrathin NiCo bimetallic molybdate nanosheets_xThe preparation method of the nanotube material comprises the following steps:

s1: cutting the foam copper into 2 × 4cm²Size, in each case 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to remove a surface oxide layer, ultrasonic washing with acetone to remove surface organic matters, and ultrasonic washing with deionized water and absolute ethyl alcohol for 5 times respectively for later use;

s2: 10ml of a 2.5M sodium hydroxide solution and 10ml of a 0.125M ammonium persulfate solution were mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foam copper for 10 minutes, taking out the foam copper, respectively washing the foam copper for 10 times by using ethanol and deionized water, and finally drying the foam copper for 4 hours in vacuum at the temperature of 60 ℃ to obtain Cu (OH)₂The product obtained is Cu (OH)₂/CF；

S3: firstly, the prepared Cu (OH)₂the/CF was first soaked in 1M glucose solution for 6 hours and partially reduced. Then 1mmol of Na₂MoO₄·2H₂O, 10mmol of urea and Co (NO)₃)₂·6H₂O and Ni (NO)₃)₂·6H₂Dissolving O molar ratio of 2:1 (total molar number of Co ions and Ni ions is 1mmol) in 40ml of deionized water, performing ultrasonic treatment for 10min, transferring the solution into a 100ml stainless steel high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and adding synthesized Cu (OH)₂the/CF was immersed in it completely and heated at 100 ℃ for 10 hours. After the reaction is finished, the copper foam is naturally cooled to room temperature, and the copper foam is taken out and washed with absolute ethyl alcohol and deionized water for several times. Finally, vacuum drying is carried out for 4h at the temperature of 60 ℃ for standby. The product obtained is noted as CoNiMoO₄-21/CuO_x/CF；

S4: mixing CoMoO₄ Pre/CuO_xthe/CF is placed in a tube furnace at 350 ℃ under N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1And obtaining the CuO coated by the ultrathin NiCo bimetal molybdate nano-sheets after the CuO is naturally cooled_xNanotube material, the resulting product being designated CoNiMoO₄-21/CuO_xand/CF. Their SEM at low resolution are shown in fig. 2 as a, respectively, and their SEM at high resolution are shown in fig. 2 as b, respectively; their TEMs at low resolution are respectively shown as a in fig. 3, and their TEMs at high resolution are respectively shown as b in fig. 3; the SEM and TEM images show that the material is a material with a hierarchical structure assembled by nano sheets and nano tubes. Meanwhile, the corresponding element mapping shows that CoNiMoO₄-21/CuO_xThe Cu, Co, Ni, Mo and O elements in the/CF (figure 4) are uniformly distributed, and the outer layer of bimetallic molybdate is obviously covered on the hollow CuO_xOn nanotubes, this further supports CoNiMoO₄-21/CuO_xSuccessful preparation of/CF. The x-ray spectrometer (EDX) diagram is shown in FIG. 5, signals of Co, Ni, Mo, Cu and O are detected, which indicates that the CoNi bimetallic molybdate coated CuO is successfully synthesized_xA material of nanotubes. FIG. 6 is CuO coated with ultra-thin NiCo bimetallic molybdate nanosheets_xHeterostructure material of nanotubes (CoNiMoO)₄-21/CuO_xX-ray diffraction pattern (XRD) of/CF), Cu was detected₂O、CuO、CoMoO₄、NiMoO₄The corresponding PDF standard card shows that CoNiMoO is successfully synthesized₄-21/CuO_xHeterostructure material of/CF. FIG. 7 is CoNiMoO₄-21/CuO_xThe X-ray photoelectron spectroscopy (XPS) pattern of/CF also successfully detected signals of Co, Ni, Mo, Cu and O.

Example 4

CuO coated by ultrathin NiCo bimetallic molybdate nanosheets_xThe preparation method of the nanotube material comprises the following steps:

s1: cutting the foam copper into 2 × 4cm²Size, in each case 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to eliminate surface oxide layer, ultrasonic washing with acetone to eliminate surface organic matter,Respectively ultrasonically washing the mixture for 5 times by using deionized water and absolute ethyl alcohol for later use;

s2: 10ml of a 2.5M sodium hydroxide solution and 10ml of a 0.125M ammonium persulfate solution were mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foam copper for 10 minutes, taking out the foam copper, respectively washing the foam copper for 10 times by using ethanol and deionized water, and finally drying the foam copper for 4 hours in vacuum at the temperature of 60 ℃ to obtain Cu (OH)₂The product obtained is Cu (OH)₂/CF；

S3: firstly, the prepared Cu (OH)₂the/CF was first soaked in 1M glucose solution for 6 hours and partially reduced. Then 1mmol of Na₂MoO₄·2H₂O, 10mmol of urea and Co (NO)₃)₂·6H₂O and Ni (NO)₃)₂·6H₂Dissolving O molar ratio of 1:1 (total molar number of Co ions and Ni ions is 1mmol) in 40ml of deionized water, performing ultrasonic treatment for 10min, transferring the solution into a 100ml stainless steel high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and adding synthesized Cu (OH)₂the/CF was immersed in it completely and heated at 100 ℃ for 10 hours. After the reaction is finished, the copper foam is naturally cooled to room temperature, and the copper foam is taken out and washed with absolute ethyl alcohol and deionized water for several times. Finally, vacuum drying is carried out for 4h at the temperature of 60 ℃ for standby. The product obtained is noted as CoNiMoO₄-11 Pre/CuO_x/CF；

S4: mixing CoMoO₄ Pre/CuO_xthe/CF is placed in a tube furnace at 350 ℃ under N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1And obtaining the CuO coated by the ultrathin NiCo bimetal molybdate nano-sheets after the CuO is naturally cooled_xNanotube material, the resulting product being designated CoNiMoO₄-11/CuO_x/CF。

Example 5

CuO coated by ultrathin NiCo bimetallic molybdate nanosheets_xThe preparation method of the nanotube material comprises the following steps:

s1: cutting the foam copper into 2 × 4cm²Size, in each case 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to remove surface oxide layer, and ultrasonic washing with acetoneWashing to remove organic matters on the surface, and respectively ultrasonically washing for 5 times by using deionized water and absolute ethyl alcohol for later use;

s2: 10ml of a 2.5M sodium hydroxide solution and 10ml of a 0.125M ammonium persulfate solution were mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foam copper for 10 minutes, taking out the foam copper, respectively washing the foam copper for 10 times by using ethanol and deionized water, and finally drying the foam copper for 4 hours in vacuum at the temperature of 60 ℃ to obtain Cu (OH)₂The product obtained is Cu (OH)₂/CF；

S3: firstly, the prepared Cu (OH)₂the/CF was first soaked in 1M glucose solution for 6 hours and partially reduced. Then 1mmol of Na₂MoO₄·2H₂O, 10mmol of urea and Co (NO)₃)₂·6H₂O and Ni (NO)₃)₂·6H₂Dissolving O molar ratio of 1:2 (total molar number of Co ions and Ni ions is 1mmol) in 40ml of deionized water, performing ultrasonic treatment for 10min, transferring the solution into a 100ml stainless steel high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and adding synthesized Cu (OH)₂the/CF was immersed in it completely and heated at 100 ℃ for 10 hours. After the reaction is finished, the copper foam is naturally cooled to room temperature, and the copper foam is taken out and washed with absolute ethyl alcohol and deionized water for several times. Finally, vacuum drying is carried out for 4h at the temperature of 60 ℃ for standby. The product obtained is noted as CoNiMoO₄-12/CuO_x/CF；

S4: mixing CoMoO₄ Pre/CuO_xthe/CF is placed in a tube furnace at 350 ℃ under N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1And obtaining the CuO coated by the ultrathin NiCo bimetal molybdate nano-sheets after the CuO is naturally cooled_xNanotube material, the resulting product being designated CoNiMoO₄-12/CuO_x/CF。

Example 6

CuO coated by ultrathin NiCo bimetallic molybdate nanosheets_xThe preparation method of the nanotube material comprises the following steps:

s1: cutting the foam copper into 2 × 4cm²Size, in each case 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to remove surface oxygenUltrasonically washing a layer and acetone to remove organic matters on the surface, and then ultrasonically washing the layer and the acetone respectively for 5 times for later use by using deionized water and absolute ethyl alcohol;

s2: 10ml of a 2.5M sodium hydroxide solution and 10ml of a 0.125M ammonium persulfate solution were mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foam copper for 10 minutes, taking out the foam copper, respectively washing the foam copper for 10 times by using ethanol and deionized water, and finally drying the foam copper for 4 hours in vacuum at the temperature of 60 ℃ to obtain Cu (OH)₂The product obtained is Cu (OH)₂/CF；

S3: firstly, the prepared Cu (OH)₂the/CF was first soaked in 1M glucose solution for 6 hours and partially reduced. Then 1mmol of Na₂MoO₄·2H₂O, 10mmol of urea and Co (NO)₃)₂·6H₂O and Ni (NO)₃)₂·6H₂Dissolving O molar ratio of 1:3 (total molar number of Co ions and Ni ions is 1mmol) in 40ml of deionized water, performing ultrasonic treatment for 10min, transferring the solution into a 100ml stainless steel high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and adding synthesized Cu (OH)₂the/CF was immersed in it completely and heated at 100 ℃ for 10 hours. After the reaction is finished, the copper foam is naturally cooled to room temperature, and the copper foam is taken out and washed with absolute ethyl alcohol and deionized water for several times. Finally, vacuum drying is carried out for 4h at the temperature of 60 ℃ for standby. The product obtained is noted as CoNiMoO₄-13 Pre/CuO_x/CF；

S4: mixing CoMoO₄ Pre/CuO_xthe/CF is placed in a tube furnace at 350 ℃ under N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1And obtaining the CuO coated by the ultrathin NiCo bimetal molybdate nano-sheets after the CuO is naturally cooled_xNanotube material, the resulting product being designated CoNiMoO₄-13/CuO_x/CF。

Example 7 (Ni Metal only, for comparison)

CuO coated by ultrathin NiCo bimetallic molybdate nanosheets_xThe preparation method of the nanotube material comprises the following steps:

s1: cutting the foam copper into 2 × 4cm²Size, respectivelyWith 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to remove a surface oxide layer, ultrasonic washing with acetone to remove surface organic matters, and ultrasonic washing with deionized water and absolute ethyl alcohol for 5 times respectively for later use;

s2: 10ml of a 2.5M sodium hydroxide solution and 10ml of a 0.125M ammonium persulfate solution were mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foam copper for 10 minutes, taking out the foam copper, respectively washing the foam copper for 10 times by using ethanol and deionized water, and finally drying the foam copper for 4 hours in vacuum at the temperature of 60 ℃ to obtain Cu (OH)₂The product obtained is Cu (OH)₂/CF；

S3: firstly, the prepared Cu (OH)₂the/CF was first soaked in 1M glucose solution for 6 hours and partially reduced. Then 1mmol of Na₂MoO₄·2H₂O, 10mmol of urea and Co (NO)₃)₂·6H₂O and Ni (NO)₃)₂·6H₂Dissolving O molar ratio of 0:1 (total molar number of Co ions and Ni ions is 1mmol) in 40ml of deionized water, performing ultrasonic treatment for 10min, transferring the solution into a 100ml stainless steel high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and adding synthesized Cu (OH)₂the/CF was immersed in it completely and heated at 100 ℃ for 10 hours. After the reaction is finished, the copper foam is naturally cooled to room temperature, and the copper foam is taken out and washed with absolute ethyl alcohol and deionized water for several times. Finally, vacuum drying is carried out for 4h at the temperature of 60 ℃ for standby. The product obtained is noted as NiMoO₄/CuO_x/CF；

S4: mixing CoMoO₄ Pre/CuO_xthe/CF is placed in a tube furnace at 350 ℃ under N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1And obtaining the CuO coated by the ultrathin Ni metal molybdate nanosheet after the CuO is naturally cooled_xNanotube material, the product obtained is noted as NiMoO₄/CuO_x/CF。

FIG. 8 shows the scanning electron microscope of the nanomaterials obtained in examples 1-2 and 4-7, and it can be seen from the figure that the CuO coated with CoNi bimetallic molybdate nanosheets can be obtained by properly controlling the ratio of CoNi by controlling the amount of Ni added_xMorphology of nanotubesThe retention is good.

Wherein a is example 1CoMoO₄/CuO_xa/CF low resolution SEM image; b is example 1CoMoO₄/CuO_xa/CF high resolution SEM image; c is CoNiMoO in example 2₄-31/CuO_xa/CF low resolution SEM image; d is CoNiMoO in example 2₄-31/CuO_xa/CF high resolution SEM image; e is CoNiMoO in example 4₄-11/CuO_xa/CF low resolution SEM image; f is CoNiMoO in example 4₄-11/CuO_xa/CF high resolution SEM image; g is CoNiMoO in example 5₄-12/CuO_xa/CF low resolution SEM image; h is CoNiMoO in example 5₄-12/CuO_xa/CF high resolution SEM image; i is CoNiMoO in example 6₄-13/CuO_xa/CF low resolution SEM image; j is CoNiMoO in example 6₄-13/CuO_xa/CF high resolution SEM image; k is NiMoO in example 7₄/CuO_xa/CF low resolution SEM image; l is NiMoO in example 7₄/CuO_xa/CF high resolution SEM image;

FIG. 9 shows the X-ray spectrographs (EDX) of the nanomaterials obtained in examples 1-2 and 4-7, and it can be seen that CuO coated with CoNi bimetallic molybdate nanosheets at different ratios_xThe ratio and the charge ratio of the CoNi in the nanotubes are basically consistent. Wherein a is example 1CoMoO₄/CuO_xX-ray spectrometer (EDX) diagram for/CF; b is CoNiMoO in example 2₄-31/CuO_xX-ray spectrometer (EDX) diagram for/CF; c is CoNiMoO in example 4₄-11/CuO_xX-ray spectrometer (EDX) diagram for/CF; d is CoNiMoO in example 5₄-12/CuO_xX-ray spectrometer (EDX) diagram for/CF; e is CoNiMoO in example 6₄-13/CuO_xX-ray spectrometer (EDX) diagram for/CF; f is NiMoO in example 7₄/CuO_xX-ray spectrometer (EDX) diagram for/CF;

the invention reduces the copper hydroxide nano-wire into a multivalent copper oxide nano-tube. The invention carries out the following comparative experiment and researches the influence of the design of bimetallic molybdate and the formation of the heterostructure of molybdate and the copper oxide nanotube on the electro-catalytic performance.

Comparative example 1

Cu (OH)₂The preparation method of the/CF nanowire material comprises the following steps:

s1: cutting the foam copper into 2 × 4cm²Size, in each case 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to remove a surface oxide layer, ultrasonic washing with acetone to remove surface organic matters, and ultrasonic washing with deionized water and absolute ethyl alcohol for 5 times respectively for later use;

s2: 10ml of a 2.5M sodium hydroxide solution and 10ml of a 0.125M ammonium persulfate solution were mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foam copper for 10 minutes, taking out the foam copper, washing the foam copper respectively with ethanol and deionized water for 10 times, and finally drying the foam copper for 4 hours in vacuum at 60 ℃ to obtain a product which is recorded as Cu (OH)₂a/CF nanowire. The SEM at low resolution is shown as a in fig. 10, and the SEM at high resolution is shown as b in fig. 10.

It can be seen from the subsequent experiments that the reduction of copper hydroxide to copper oxide is beneficial to the improvement of the performance.

Comparative example 2

CuO (copper oxide)_xThe preparation method of the/CF nanowire material comprises the following steps:

s1: cutting the foam copper into 2 × 4cm²Size, in each case 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to remove a surface oxide layer, ultrasonic washing with acetone to remove surface organic matters, and ultrasonic washing with deionized water and absolute ethyl alcohol for 5 times respectively for later use;

s2: 10ml of a 2.5M sodium hydroxide solution and 10ml of a 0.125M ammonium persulfate solution were mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foam copper for 10 minutes, taking out the foam copper, washing the foam copper respectively with ethanol and deionized water for 10 times, and finally drying the foam copper for 4 hours in vacuum at 60 ℃ to obtain a product which is recorded as Cu (OH)₂/CF。

S3: mixing Cu (OH) already prepared₂the/CF was first soaked in 1M glucose solution for 6 hours and partially reduced. Then placed in a tube furnace at 350 ℃ under N₂Calcining at high temperature for 2h under the protection of atmosphere and at the rate of temperature riseAt 5 deg.C for min^-1After it is naturally cooled, CuO is obtained_xand/CF. The SEM at low resolution is shown as a in fig. 11, and the SEM at high resolution is shown as b in fig. 11.

Comparative example 3

Cu₂The preparation method of the O/CF nanowire material comprises the following steps:

s1: cutting the foam copper into 2 × 4cm²Size, in each case 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to remove a surface oxide layer, ultrasonic washing with acetone to remove surface organic matters, and ultrasonic washing with deionized water and absolute ethyl alcohol respectively for 6 times for later use;

s2: 10ml of a 2.5M sodium hydroxide solution and 10ml of a 0.125M ammonium persulfate solution were mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foam copper for 10 minutes, taking out the foam copper, respectively washing the foam copper for multiple times by using ethanol and deionized water, and finally drying the foam copper for 4 hours in vacuum at the temperature of 60 ℃, wherein the obtained product is marked as Cu (OH)₂/CF。

S3: mixing Cu (OH) already prepared₂the/CF was first soaked in 1M glucose solution for 12 hours and completely reduced. Then placed in a tube furnace at 350 ℃ under N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1After it is naturally cooled, Cu is obtained₂O/CF. The SEM at low resolution is shown as a in fig. 12, and the SEM at high resolution is shown as b in fig. 12.

Comparative example 4

A preparation method of a CuO/CF nanowire material comprises the following steps:

s1: cutting the foam copper into 2 × 4cm²Size, in each case 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to remove a surface oxide layer, ultrasonic washing with acetone to remove surface organic matters, and ultrasonic washing with deionized water and absolute ethyl alcohol for 5 times respectively for later use;

s2: 10ml of a 2.5M sodium hydroxide solution and 10ml of a 0.125M ammonium persulfate solution were mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foamy copper for 10 minutes, taking out the foamy copper, respectively washing the foamy copper for 10 times by using ethanol and deionized water, finally drying the foamy copper for 4 hours in vacuum at the temperature of 60 ℃,the product obtained is designated Cu (OH)₂/CF。

S3: mixing Cu (OH) already prepared₂the/CF is placed directly in a tube furnace at 350 ℃ in N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1And obtaining CuO/CF after natural cooling. The SEM at low resolution is shown as a in fig. 13, and the SEM at high resolution is shown as b in fig. 13.

Comparative examples 2, 3, and 4 are the results of calcining the copper hydroxide nanowires after being soaked in the glucose solution for different periods of time, respectively, wherein comparative example 2 is calcining after being soaked for 6 hours, in which only a part of the copper hydroxide is reduced to cuprous oxide, and the multivalent copper oxide CuOx is obtained after calcining and dehydrating, comparative example 3 is calcining after being soaked for 12 hours, in which the copper hydroxide is completely reduced to cuprous oxide, and comparative example 4 is directly calcining without being reduced in the glucose solution, in which the cupric oxide is obtained. CuOx and Cu reduced with glucose can be clearly seen₂O has more pores and rougher surface than CuO surface, which is more favorable for gas adsorption and desorption, and adsorption of reaction intermediates and electron transfer. With Cu₂O is more hollow and weaker than CuOx in structure. It is difficult to function as a skeleton. It is difficult to maintain stable and efficient catalytic performance during the catalytic process. Therefore, the CuOx synthesized by the control method has the best supporting framework effect and electrocatalytic performance.

Comparative example 5

CoMoO₄The preparation method of the/CF network array material comprises the following steps:

s1: adding 1mmol of Na₂MoO₄·2H₂O, 10mmol of urea and 1mmol of Co (NO)₃)₂6H₂O was dissolved in 40ml of deionized water, sonicated for 10 minutes, then transferred to a 100ml teflon lined autoclave, and the pre-treated bare CF was directly immersed in it completely. Reacting at 100 ℃ for 10h, naturally cooling to room temperature after the reaction is finished, taking out the copper foam, and washing with absolute ethyl alcohol and deionized water for several times. Finally drying for 4h under vacuum at 60 ℃. Finally at 350 deg.CN₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1After the mixture is naturally cooled, the product CoMoO is obtained₄/CF。

Comparative example 6

NiMoO₄The preparation method of the/CF network array material comprises the following steps:

s1: adding 1mmol of Na₂MoO₄·2H₂O, 10mmol of urea and 1mmol of Ni (NO)₃)₂·6H₂O was dissolved in 40ml of deionized water, sonicated for 10 minutes, then transferred to a 100ml teflon lined autoclave, and the pre-treated bare CF was directly immersed in it completely. Reacting at 100 ℃ for 10h, naturally cooling to room temperature after the reaction is finished, taking out the copper foam, and washing with absolute ethyl alcohol and deionized water for several times. Finally drying for 4h under vacuum at 60 ℃. Finally at 350 ℃ under N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1After the mixture is naturally cooled, the product NiMoO is obtained₄/CF。

Comparative example 7

CoNiMoO₄The preparation method of the-21/CF network array material comprises the following steps:

s1: adding 1mmol of Na₂MoO₄·2H₂O, 10mmol of urea and Co (NO)₃)₂·6H₂O and Ni (NO)₃)₂·6H₂The O ratio was 2:1 (total moles of CoNi 1mmol) was dissolved in 40ml of deionized water, sonicated for 10 minutes, then transferred to a 100ml teflon lined autoclave, and the pre-treated bare CF was directly immersed in it completely. Reacting at 100 ℃ for 10h, naturally cooling to room temperature after the reaction is finished, taking out the copper foam, and washing with absolute ethyl alcohol and deionized water for several times. Finally drying for 4h under vacuum at 60 ℃. Finally at 350 ℃ under N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1After the mixture is naturally cooled, the product CoNiMoO is obtained₄-21/CF。

Scanning of the nanomaterials obtained in comparative examples 5 to 7 as described aboveThe electron microscope is shown in FIG. 14, in which a is CoMoO₄Low resolution Scanning Electron Micrograph (SEM) of/CF, b is CoMoO₄Low resolution Scanning Electron Micrograph (SEM) of/CF; c is CoNiMoO₄Low resolution Scanning Electron Micrograph (SEM) of-21/CF, d is CoNiMoO₄-low resolution Scanning Electron Micrograph (SEM) of 21/CF; e is NiMoO₄Low resolution Scanning Electron Micrograph (SEM) of/CF, f is NiMoO₄Low resolution Scanning Electron Micrograph (SEM) of/CF;

as can be seen from the figure, CoNiMoO₄-21/CF (c-d in FIG. 14) vs. CoMoO₄(a-b in FIG. 14) and NiMoO₄the/CF (e-f in figure 14) has a denser sheet array structure, and the nano-sheets are thinner and smaller. As can be seen from the scale, this is the same as the 200nm scale. Compared with single-metal molybdate, the double-metal molybdate has a more compact three-dimensional network structure and a thinner thickness. Meaning that it has a larger specific surface area and more active sites to enhance its electrocatalytic properties.

The invention improves the electrocatalytic performance by the combined synergistic effect of the heterostructure and the bimetal. From subsequent performance tests, it can be seen that comparative examples 5, 6, 7 demonstrate low catalytic activity when no heterostructure with copper oxide is formed, and low electrocatalytic activity of the monometallic molybdate compared to the bimetallic molybdate in optimal proportions.

Example 8

CuO coated by ultrathin NiCo bimetallic molybdate nanosheet_xThe application of the nanotube material in the aspect of water electrolysis comprises the following specific application methods:

HER catalytic activity assay: electrolyte is 1M KOH solution, and CuO coated by the materials prepared in comparative examples 1-7 and the bimetallic molybdate nano-sheets prepared in examples 1-7 with different NiCo ratios is respectively added_xThe nano tube material and the pretreated foamy copper are directly used as working electrodes and respectively used as catalysts, a Pt wire electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the sweep rate is 5mV^-1Until a steady state is reached, and then at a sweep rate of 5mVs^-1When the voltage interval is 0-1.0VMeasuring the linear sweep voltammetry curves, as shown in FIGS. 15-18, it can be seen that CoNiMoO is compared to other materials₄/CuO_xThe smaller overpotential is needed when the/CF material is used as the HER catalyst, which shows that NiCo bimetallic molybdate nanosheet coated CuO_xThe nanotube heterostructure material is a highly efficient HER catalyst. Meanwhile, CoNiMoO can be seen from the figure₄-21/CuO_xthe/CF material exhibited the best catalytic performance.

CoNiMoO prepared in example 3 was used as an electrolyte in the presence of 1M KOH solution₄-21/CuO_xthe/CF material is directly used as a working electrode, a Pt wire electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the current density is 10mA^-2A chronopotentiometric curve was obtained, and as shown in FIG. 19, CoNiMoO was observed from the chronopotentiometric curve₄-21/CuO_xthe/CF material has better stability. The insert in FIG. 19 is CoNiMoO₄-21/CuO_xComparison of LSV after recycle of/CF Material, it can be seen that CoNiMoO prepared in example 3 was prepared after recycle₄-21/CuO_xThe LSV of the/CF material does not vary much.

OER catalytic activity test: electrolyte is 1M KOH solution, and the CuO coated by the materials prepared in comparative examples 1 to 7 and the bimetallic molybdate nano-sheets prepared in examples 1 to 7 with different NiCo ratios_xThe heterostructure material of the nanotube and the pretreated bare foam copper are directly used as working electrodes and respectively used as catalysts, a Pt wire electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the sweep rate is 5mV^-1Until a steady state is reached, and then at a sweep rate of 5mVs^-1And the voltage interval is 0-1.0V, as shown in FIGS. 20-23, it can be seen that CoNiMoO is compared with other materials₄/CuO_xThe smaller overpotential is needed when the/CF material is used as an OER catalyst, which shows that NiCo bimetallic molybdate nanosheet-coated CuO_xThe nanotube material is an efficient OER catalyst. Meanwhile, CoNiMoO can be seen from the figure₄-21/CuO_xthe/CF material exhibited the best catalytic performance.

By 1MKOH solution as electrolyte, CoNiMoO prepared in example 3₄-21/CuO_xthe/CF material is directly used as a working electrode, a Pt wire electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the current density is 100mA^-2A chronopotentiometric curve was obtained, and as shown in FIG. 24, CoNiMoO was observed from the chronopotentiometric curve₄-21/CuO_xthe/CF material has better stability. The insert in FIG. 24 is CoNiMoO₄-21/CuO_xComparison of LSV after recycle of/CF Material, it can be seen that CoNiMoO prepared in example 3 was prepared after recycle₄-21/CuO_xThe LSV of the/CF material does not vary much.

The electrochemically active surface area of the catalyst was evaluated by Cyclic Voltammetry (CV), FIG. 25 being CoNiMoO₄-21/CuO_xCV plot for different sweep rates of/CF and other materials, the electrochemically active surface area (ECSA) of the catalyst by CV 26, it can be seen that CoNiMoO is compared to other materials₄-21/CuO_xthe/CF has higher activity, namely larger electrochemical active surface area, wherein CoNiMoO₄-21/CuO_xthe/CF has the largest electrochemically active surface area and corresponds to LSV.

FIG. 27 is CoNiMoO₄Electrochemical impedance plots (EIS) of 21/CuOx/CF and other materials, AC impedance spectra in the frequency range 0.01Hz-10000Hz, and EIS measured at a potential of 1.58V in 1M KOH. As can be seen from the figure, CoNiMoO is compared to other materials₄the-21/CuOx/CF has the smallest electrochemical impedance value, which indicates that CoNiMoO4-21/CuOx/CF has the highest electron transport efficiency compared with other materials.

Comparative example 8

CuO coated by NiCo bimetallic molybdate nanosheets_xThe preparation method of the nanotube material comprises the following steps:

s1: cutting the foam copper into 2 × 4cm²Size, in each case 3mol L^-1Ultrasonic washing with dilute hydrochloric acid to remove a surface oxide layer, ultrasonic washing with acetone to remove surface organic matters, and ultrasonic washing with deionized water and absolute ethyl alcohol for 5 times respectively for later use;

s2: 10ml of 2.5M sodium hydroxide solution and 10Ml 0.125M ammonium persulfate solution was mixed with stirring until the solution was clear and transparent. Then soaking the pretreated foam copper for 10 minutes, taking out the foam copper, respectively washing the foam copper for 10 times by using ethanol and deionized water, and finally drying the foam copper for 4 hours in vacuum at the temperature of 60 ℃ to obtain Cu (OH)₂The product obtained is Cu (OH)₂/CF；

S3: firstly, the prepared Cu (OH)₂the/CF was first soaked in 1M glucose solution for 6 hours and partially reduced. Then 1mmol of Na₂MoO₄·2H₂O, 10mmol of urea and CoCl₂·6H₂O and NiCl₂·6H₂Dissolving O molar ratio of 2:1 (total molar number of Co ions and Ni ions is 1mmol) in 40ml of deionized water, performing ultrasonic treatment for 10min, transferring the solution into a 100ml stainless steel high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and adding synthesized Cu (OH)₂the/CF was immersed in it completely and heated at 100 ℃ for 10 hours. After the reaction is finished, the copper foam is naturally cooled to room temperature, and the copper foam is taken out and washed with absolute ethyl alcohol and deionized water for several times. Finally, vacuum drying is carried out for 4h at the temperature of 60 ℃ for standby. The product obtained is noted as CoNiMoO₄-21-Cl Pre/CuO_x/CF；

S4: mixing CoMoO₄ Pre/CuO_xthe/CF is placed in a tube furnace at 350 ℃ under N₂Calcining at high temperature for 2h under the protection of atmosphere, with the heating rate of 5 ℃ for min^-1And obtaining the CuO coated by the ultrathin NiCo bimetal molybdate nano-sheets after the CuO is naturally cooled_xNanotube material, the resulting product being designated CoNiMoO₄-21-Cl/CuO_x/CF。

Scanning Electron Microscope (SEM) of the nanomaterial obtained in comparative example 8 is shown in FIG. 28, from which it can be seen that CoCl was used in place of the Co source and Ni source₂·6H₂O and NiCl₂·6H₂When O is subjected to hydrothermal reaction, the CuO coated by ultrathin NiCo bimetallic molybdate nanosheets cannot be formed_xHeterostructure materials for nanotubes. The surface agglomeration of the nano-particles is covered by a layer of reticular nano-sheets. And the array structures of the nanotubes are clustered together, which can greatly reduce the specific surface area of the material and reduce the active sites of the reaction. And do notThe adsorption and desorption of the reaction intermediate and the transmission of electrons are facilitated, so that the electrocatalysis performance of the reaction intermediate is greatly influenced.

CuO coated with ultra-thin NiCo bimetallic molybdate nanosheets as described above with reference to the examples_xThe detailed description of the preparation method of the heterostructure material of nanotubes and its application in the electrolysis of water are illustrative and not restrictive, and several examples are cited within the limits of the invention, so that variations and modifications thereof are within the scope of the invention as claimed.