CN110331414B - MOF (Metal organic framework) composite copper-based nanorod array @ foam copper-based composite electrode material as well as preparation method and application thereof - Google Patents

MOF (Metal organic framework) composite copper-based nanorod array @ foam copper-based composite electrode material as well as preparation method and application thereof Download PDF

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CN110331414B
CN110331414B CN201910267713.7A CN201910267713A CN110331414B CN 110331414 B CN110331414 B CN 110331414B CN 201910267713 A CN201910267713 A CN 201910267713A CN 110331414 B CN110331414 B CN 110331414B
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electrode material
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喻发全
李攀
王建芝
谌伟民
蔡宁
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Wuhan Institute of Technology
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Abstract

The invention discloses an MOF (metal organic framework) composite copper-based nanorod array @ foam copper-based composite electrode material and a preparation method and application thereof. The MOF composite copper-based nanorod array @ foam copper-based composite electrode material is characterized in that foam copper is used as a substrate, and an MOF composite copper hydroxide nanorod array grows on the surface of the foam copper; the MOF is ZIF-67. The preparation method adopts an in-situ synthesis method to directly grow Cu (OH) on a foam copper substrate2The nanorod array of (1), further comprising Cu (OH)2The nano-rod array is used as a substrate, MOF particles grow on the surface of the substrate through directional growth of a template, and finally, the electrode material with the electrocatalytic performance is obtained through dehydration treatment. The composite material has stable performance under alkaline conditions, higher repeated utilization degree and larger electrochemical active area, and greatly improves the catalytic activity of the material; the preparation method has the advantages of simple preparation process, low sintering temperature, low energy consumption in the preparation process and convenience for industrial production.

Description

MOF (Metal organic framework) composite copper-based nanorod array @ foam copper-based composite electrode material as well as preparation method and application thereof
Technical Field
The invention relates to an MOF (metal organic framework) composite copper-based nanorod array @ foam copper-based composite electrode material and a preparation method and application thereof, belonging to the technical field of catalytic oxygen evolution of electrolyzed water.
Background
Energy is the fundamental driving force for the development of human productivity as a cornerstone for various production activities in the human society. From ancient times to the present, fossil energy, which is a main energy source utilized by human, is consumed at a rate that becomes faster and faster as human develops, and particularly, since the fossil energy enters an industrial society, the existing storage is about to be depleted over centuries. The consumption of fossil energy also brings environmental pollution problems, and therefore, the development of sustainable and clean alternative energy is urgent. Hydrogen is considered to be a sustainable source of heat because the combustion process releases enormous amounts of energy and the product is waterClean energy. From the aspect of environmental friendliness, hydrogen production by electrochemically catalyzing and decomposing water is one of ideal ways for preparing hydrogen. The electrolytic water comprises an anodic oxygen generation reaction (OER) and a cathodic Hydrogen Evolution Reaction (HER), wherein the OER reaction is a kinetic slow process of four electron transfer and tends to consume higher energy. At present, noble metal based catalysts (RuO)2/IrO2) Is a high-efficiency oxygen-producing catalyst, however, the noble metal-based catalysts are expensive and have limited reserves, which limits the large-scale industrial application of the noble metal-based catalysts. Therefore, in order to meet the requirement of developing sustainable energy, it is important to develop and apply an efficient and cheap oxygen evolution catalyst to replace an expensive noble metal catalyst.
In recent years, some non-noble metals have been used as oxygen evolution catalysts, but the catalytic stability and catalytic performance cannot meet the requirements of industrial production. Therefore, the development of a non-noble metal catalyst which is low in cost, easy to prepare and high in performance has important significance for promoting the industrial development of the oxygen evolution reaction. Researches find that the oxygen evolution reaction under the alkaline condition has the advantages of no pollution, convenient operation, mature technology, easy large-scale production and the like, and becomes one of the research hotspots. However, the catalyst for oxygen evolution reaction under alkaline conditions has problems of poor catalytic activity and stability, and further research is required.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a MOF composite copper-based nanorod array @ foam copper-based composite electrode material (ZIF-67@ Cu (OH))2@ foamy copper) and methods of making and using the same. The composite electrode material has high catalytic activity, high stability, high oxygen evolution performance and high repeated utilization rate. The preparation process is simple, the sintering temperature is low, the energy consumption in the preparation process is low, and the industrial production is facilitated.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
MOF composite copper-based nanorod array @ foam copper-based composite electrode material (ZIF-67@ Cu (OH))2@ foamy copper), characterized in that the composite electrode material is based on foamy copper, the foamGrowing a copper hydroxide nanorod array with MOF (metal organic framework) composition on the surface of the copper foam; the MOF is ZIF-67.
The invention also provides a preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material, which is characterized by comprising the following steps of:
1) preparing a precursor solution from an ammonium persulfate aqueous solution and a potassium hydroxide aqueous solution, immersing the foamy copper into the precursor solution for reaction, and after the reaction is finished, washing and drying to obtain the foamy copper (Cu (OH)) with the surface growing with a metal copper hydroxide nanorod array2@ copper foam);
2) putting the foamy copper with the copper hydroxide nanorod array growing on the surface obtained in the step 1) into a precursor solution of ZIF-67, reacting for a period of time, loading ZIF-67 particles on the surfaces of the nanorods through crystallization and aging, washing with water and drying to obtain a non-dehydrated MOF-compounded copper-based nanorod array @ foamy copper-based composite electrode material;
3) annealing the non-dehydrated MOF-compounded copper-based nanorod array @ foam copper-based composite electrode material obtained in the step 2) to obtain a final product MOF-compounded copper-based nanorod array @ foam copper-based composite electrode material (ZIF-67@ Cu (OH)2@ copper foam).
According to the scheme, preferably, the molar ratio of the ammonium persulfate to the potassium hydroxide in the step 1) is 0.5-4: 20 to 50. More preferably, the molar ratio of the ammonium persulfate to the potassium hydroxide is 1: 25.
according to the scheme, preferably, the concentration of the ammonium persulfate aqueous solution in the step 1) is 0.1-1 mol/L; the concentration of the potassium hydroxide aqueous solution is 6-15 mol/L.
According to the scheme, preferably, the foam copper in the step 1) is subjected to pretreatment of removing surface oil stains and an oxidation layer, and the pretreatment specifically comprises the following steps: and removing oil stains and an oxide layer on the surface of the foamy copper by adopting an organic solvent and acid soaking.
According to the scheme, preferably, the reaction temperature in the step 1) is normal temperature, and the reaction time is 10-60 min.
According to the scheme, preferably, in the step 2), the precursor solution of the ZIF-67 is prepared by the following method:
respectively dissolving cobalt salt and dimethyl imidazole in methanol to prepare A, B solution, and mixing the AB solution to obtain the precursor solution of the ZIF-67. More preferably, the molar ratio of the cobalt salt to the dimethyl imidazole is 1-2: 4 to 8. More preferably, the concentration range of the solute in the solution A is 0.01-0.1 mol/L, and the concentration range of the solute in the solution B is 0.1-0.4 mol/L. More preferably, the cobalt salt is one or more of cobalt nitrate, cobalt chloride and cobalt sulfate.
According to the scheme, preferably, in the step 2), the reaction is specifically as follows: stirring for 1-10min at normal temperature, stopping stirring, and standing in the dark for 10-24 h.
According to the above scheme, preferably, in the step 3), the annealing treatment specifically comprises the following steps: and (3) under the condition of introducing Ar gas, heating to 280-320 ℃ at the speed of 5 ℃/min, preserving the heat for 1-3 h, and cooling to room temperature at the speed of 5 ℃/min.
The invention also provides application of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material, which is characterized in that the composite electrode material can be used as an electrode or a catalyst for electrolyzing water to separate oxygen.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the electrolyzed water oxygen evolution electrode material is a composite material generated by a method of compounding a novel inorganic functional material of a metal copper hydroxide nanorod array and a metal organic framework, can effectively improve the stability of a catalyst, can remarkably improve the catalytic oxygen evolution performance of the electrolyzed water oxygen evolution electrode material under an alkaline condition after further annealing treatment, and makes up the defects of the existing non-noble metal catalyst.
(2) The MOF composite copper-based nanorod array @ foam copper-based composite electrode material directly grows on the surface of a foam copper framework structure in situ, is used as a self-supported catalyst, and is directly used as an electrode without any auxiliary means.
(3) The MOF composite copper-based nanorod array @ foam copper-based composite electrode material prepared by the invention has the advantage of large surface area, provides more active sites, and has better catalytic oxygen evolution performance.
(4) The composite electrode material has good stability and high repeated utilization degree, can be widely used as an alkaline electrolyzed water oxygen evolution electrode material, and has wide application prospect.
(5) The composite electrode material disclosed by the invention is simple in preparation process, low in sintering temperature, low in energy consumption in the preparation process and convenient for industrial production.
Drawings
FIG. 1 is an SEM image of an array of metallic copper hydroxides grown on copper foam as an intermediate product prepared in step b of example 1 of the present invention.
FIG. 2 is an SEM image of an intermediate product prepared in step c of example 1, namely a copper-based nanorod array @ foam copper-based composite electrode composited by MOF without dehydration.
FIG. 3 is an SEM image of the final product MOF composited copper-based nanorod array @ foam copper-based composite electrode material prepared in step d of example 1 of the invention.
FIG. 4 is ZIF-67@ Cu (OH) prepared in application example 1 of the present invention2@ foamy copper is used as a working electrode for oxygen evolution experiment polarization curve chart under alkaline condition. Wherein curve 1 is ZIF-67@ Cu (OH)2@ foamy copper, curve 2 RuO2@ copper foam.
Detailed Description
Example 1
The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material comprises the following steps:
a. pretreatment of the copper foam: cutting the foam copper into the size of 1cm multiplied by 2cm, placing the foam copper in a beaker, adding absolute ethyl alcohol until the foam copper is immersed, performing ultrasonic treatment for 15min, pouring the absolute ethyl alcohol out, adding 1mol/L diluted hydrochloric acid until the foam copper is immersed, and performing ultrasonic treatment for 15min, and then washing the foam copper with water for later use.
b. Firstly, preparing a precursor solution: measuring 30mL of deionized water, placing the deionized water in a beaker, adding 1.64g (7.2mmol) of ammonium persulfate, stirring and ultrasonically treating for 15min until the ammonium persulfate is completely dissolved for later use; 30mL of deionized water was measured and placed in a beaker, followed by the addition of potassium hydroxide10.1g (180mmol), stirring and ultrasonic treating for 15min, adding ammonium persulfate solution after complete dissolution, and stirring uniformly to obtain the precursor solution. Then, adding the foam copper treated in the step a into the precursor solution, reacting for 20min at normal temperature, separating, washing and drying to obtain the copper (OH) with Cu (OH) growing on the surface2Foam copper of nanorods (Cu (OH)2@ copper foam).
c. Measuring 25mL of methanol, placing the methanol in a beaker, adding 0.29g (1mmol) of cobalt nitrate, and carrying out ultrasonic treatment until the cobalt nitrate is completely dissolved for later use; 25mL of methanol was weighed into a beaker, 0.33g (4mmol) of dimethylimidazole was added, after sonication to complete dissolution, a solution of cobalt nitrate in methanol was added, followed by addition of the Cu (OH) from step b2@ foam copper, stirring at normal temperature for 5min, standing in the dark for reaction for 24h, separating after reaction, washing with water, and drying to obtain the non-dehydrated MOF composite copper-based nanorod array @ foam copper-based composite electrode material (ZIF-67@ Cu (OH))2@ copper foam).
d. Putting the non-dehydrated MOF composite copper-based nanorod array @ foamy copper prepared in the step c into a tube furnace, introducing argon for 15min, heating to 300 ℃ at the speed of 5 ℃/min, preserving heat for 3h, and cooling to room temperature at the speed of 5 ℃/min to obtain dehydrated ZIF-67@ Cu (OH)2@ foamed copper composite.
FIG. 1 is an SEM image of an array of metal copper hydroxide grown on copper foam prepared in step b of this example, FIG. 2 is an SEM image of an undehydrated MOF-composited copper-based nanorod array @ copper foam composite electrode prepared in step c of this example, and FIG. 3 is an SEM image of an MOF-composited copper-based nanorod array @ copper foam composite electrode material prepared in step d of this example. From fig. 1 and fig. 2, it can be seen that the lamellar structure array in the composite material is obvious, and has a 3D structure, and from fig. 3, it can be seen that the composite material still maintains a good rod structure array after dehydration treatment, which indicates that the material has good thermal stability and porosity.
Example 2
The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material comprises the following steps:
a. pretreatment of the copper foam: cutting the foam copper into the size of 1cm multiplied by 2cm, placing the foam copper in a beaker, adding absolute ethyl alcohol until the foam copper is immersed, performing ultrasonic treatment for 15min, pouring the absolute ethyl alcohol out, adding 1mol/L diluted hydrochloric acid until the foam copper is immersed, and performing ultrasonic treatment for 20min, and then washing the foam copper with water for later use.
b. Firstly, preparing a precursor solution: measuring 30mL of deionized water, placing the deionized water in a beaker, adding 1.64g (7.2mmol) of ammonium persulfate, stirring and ultrasonically treating for 15min until the ammonium persulfate is completely dissolved for later use; measuring 30mL of deionized water, placing the deionized water in a beaker, adding 20.2g (360mmol) of potassium hydroxide, stirring and ultrasonically treating for 15min, adding an ammonium persulfate solution after completely dissolving, and uniformly stirring to obtain the precursor solution. Then, adding the foam copper treated in the step a into the precursor solution, reacting for 10min at normal temperature, separating, washing and drying to obtain the product with Cu (OH)2Foam copper of nanorods (Cu (OH)2@ copper foam).
c. Measuring 25mL of methanol, placing the methanol in a beaker, adding 0.29g (1mmol) of cobalt nitrate, and carrying out ultrasonic treatment until the cobalt nitrate is completely dissolved for later use; 25mL of methanol was weighed into a beaker, 0.66g (8mmol) of dimethylimidazole was added, after sonication to complete dissolution, a solution of cobalt nitrate in methanol was added, followed by addition of the Cu (OH) from step b2@ foam copper, stirring at normal temperature for 5min, standing in the dark for reaction for 20h, separating after reaction, washing with water, and drying to obtain the non-dehydrated MOF composite copper-based nanorod array @ foam copper-based composite electrode material (ZIF-67@ Cu (OH))2@ copper foam).
d. Putting the non-dehydrated MOF composite copper-based nanorod array @ foamy copper prepared in the step c into a tube furnace, introducing argon for 15min, heating to 300 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature at the speed of 5 ℃/min to obtain dehydrated ZIF-67@ Cu (OH)2@ foamed copper composite.
Example 3
The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material comprises the following steps:
a. pretreatment of the copper foam: cutting the foam copper into the size of 1cm multiplied by 2cm, placing the foam copper in a beaker, adding absolute ethyl alcohol until the foam copper is immersed, performing ultrasonic treatment for 15min, pouring the absolute ethyl alcohol out, adding 1mol/L diluted hydrochloric acid until the foam copper is immersed, and performing ultrasonic treatment for 20min, and then washing the foam copper with water for later use.
b. Firstly, preparing a precursor solution: measuring 30mL of deionized water, placing the deionized water in a beaker, adding 1.64g (7.2mmol) of ammonium persulfate, stirring and ultrasonically treating for 15min until the ammonium persulfate is completely dissolved for later use; measuring 30mL of deionized water, placing the deionized water in a beaker, adding 20.2g (360mmol) of potassium hydroxide, stirring and ultrasonically treating for 15min, adding an ammonium persulfate solution after completely dissolving, and uniformly stirring to obtain the precursor solution. Then, adding the foam copper treated in the step a into the precursor solution, reacting for 20min at normal temperature, separating, washing and drying to obtain the product with Cu (OH)2Foam copper of nanorods (Cu (OH)2@ copper foam).
c. Measuring 25mL of methanol, placing the methanol in a beaker, adding 0.29g (1mmol) of cobalt nitrate, and carrying out ultrasonic treatment until the cobalt nitrate is completely dissolved for later use; 25mL of methanol was weighed into a beaker, 0.33g (4mmol) of dimethylimidazole was added, after sonication to complete dissolution, a solution of cobalt nitrate in methanol was added, followed by addition of the Cu (OH) from step b2@ foam copper, stirring at normal temperature for 5min, standing in the dark for reaction for 12h, separating after reaction, washing with water, and drying to obtain the non-dehydrated MOF composite copper-based nanorod array @ foam copper-based composite electrode material (ZIF-67@ Cu (OH))2@ copper foam).
d. Putting the non-dehydrated MOF composite copper-based nanorod array @ foamy copper prepared in the step c into a tube furnace, introducing argon for 15min, heating to 300 ℃ at the speed of 5 ℃/min, preserving heat for 3h, and cooling to room temperature at the speed of 5 ℃/min to obtain dehydrated ZIF-67@ Cu (OH)2@ foamed copper composite.
Example 4
The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material comprises the following steps:
a. pretreatment of the copper foam: cutting the foam copper into the size of 1cm multiplied by 2cm, placing the foam copper in a beaker, adding absolute ethyl alcohol until the foam copper is immersed, performing ultrasonic treatment for 15min, pouring the absolute ethyl alcohol out, adding 1mol/L diluted hydrochloric acid until the foam copper is immersed, and performing ultrasonic treatment for 15min, and then washing the foam copper with water for later use.
b. Firstly, preparing a precursor solution: 30mL of deionized water was measured and placed in a beaker, then addedAmmonium persulfate 1.64g (7.2mmol), stirring and ultrasonic treating for 15min until completely dissolved for later use; measuring 30mL of deionized water, placing the deionized water in a beaker, adding 10.1g (180mmol) of potassium hydroxide, stirring and ultrasonically treating for 15min, adding an ammonium persulfate solution after completely dissolving, and uniformly stirring to obtain the precursor solution. Then, adding the foam copper treated in the step a into the precursor solution, reacting for 20min at normal temperature, separating, washing and drying to obtain the product with Cu (OH)2Foam copper of nanorods (Cu (OH)2@ copper foam).
c. Measuring 25mL of methanol, placing the methanol in a beaker, adding 0.29g (1mmol) of cobalt nitrate, and carrying out ultrasonic treatment until the cobalt nitrate is completely dissolved for later use; 25mL of methanol was weighed into a beaker, 0.33g (4mmol) of dimethylimidazole was added, after sonication to complete dissolution, a solution of cobalt nitrate in methanol was added, followed by addition of the Cu (OH) from step b2@ foam copper, stirring at normal temperature for 5min, standing in the dark for reaction for 10h, separating after reaction, washing with water, and drying to obtain the non-dehydrated MOF composite copper-based nanorod array @ foam copper-based composite electrode material (ZIF-67@ Cu (OH))2@ copper foam).
d. Putting the non-dehydrated MOF composite copper-based nanorod array @ foamy copper prepared in the step c into a tube furnace, introducing argon for 15min, heating to 300 ℃ at the speed of 5 ℃/min, preserving heat for 1h, and cooling to room temperature at the speed of 5 ℃/min to obtain dehydrated ZIF-67@ Cu (OH)2@ foamed copper composite.
Application example 1
The final product prepared in example 1, ZIF-67@ Cu (OH)2The @ foamy copper composite material was used as an anodic oxygen evolution reaction electrode (may also be referred to as a catalyst) in an electrolytic water device, and an electrochemical oxygen evolution experiment was performed thereon. The method comprises the following specific steps:
controlling the test temperature to be 25 ℃; mixing said ZIF-67@ Cu (OH) in a size of 0.5cm by 0.5cm2The @ foamy copper composite material is directly used as a working electrode, a saturated calomel electrode is used as a reference electrode, a graphite electrode is used as a counter electrode to assemble a three-electrode system, and the three-electrode system is respectively put into a three-way electrolytic cell; preparing 1mol/L potassium hydroxide solution, and adding the solution into a three-way electrolytic cell; the electrode is activated by cyclic voltammetry at a curve scanning speedThe concentration is 50mV/s, and the number of scanning turns is 30 turns; the polarization curve was tested at a curve scan speed of 2mV/s with an IR compensation of 85% before testing.
Testing and result analysis:
using commercial RuO2@ foamy copper as control group experiment, among others, commercial RuO2(ruthenium dioxide) was purchased from Shanghai Allantin Biotech Co., Ltd., content of 99.9%, RuO2The @ foamy copper is prepared by a drop coating drying method, and the specific steps are as follows: 4mg of commercial RuO2Dissolving in 1mL ethanol dispersion, ultrasonic dispersing for 1h, dripping 500 μ L dispersion on 0.5cm × 0.5cm foamy copper, naturally drying, and using RuO2The supported amount of (A) was 4 mg. cm-2。
Electrochemical oxygen evolution experiment, commercial RuO using catalyst prepared in example 12The polarization curve of electrochemical oxygen evolution experiment of @ foamy copper is shown in figure 4. Comparing the two curves, it can be seen that the catalyst prepared in the application example 1 of the present invention reaches 10mA/cm in the oxygen evolution experiment3The overpotential required by the current density of 250mV, which is far lower than the overpotential of 324mV of commercial foam nickel, shows good oxygen evolution catalytic performance, and indicates that the catalyst has strong application potential in industry.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (10)

1. A preparation method of an MOF composite copper-based nanorod array @ foam copper-based composite electrode material is disclosed, wherein the MOF composite copper-based nanorod array @ foam copper-based composite electrode material takes foam copper as a substrate; growing a copper hydroxide nanorod array with MOF (metal organic framework) composition on the surface of the copper foam; the MOF is ZIF-67, and is characterized by comprising the following steps:
1) preparing a precursor solution from an ammonium persulfate aqueous solution and a potassium hydroxide aqueous solution, immersing the foamy copper into the precursor solution for reaction, and after the reaction is finished, washing and drying to obtain the foamy copper with a metal copper hydroxide nanorod array growing on the surface;
2) putting the foamy copper with the copper hydroxide nanorod array growing on the surface obtained in the step 1) into a precursor solution of ZIF-67, reacting for a period of time, washing with water and drying to obtain an undehydrated MOF composite copper-based nanorod array @ foamy copper-based composite electrode material;
3) and (3) annealing the non-dehydrated MOF-compounded copper-based nanorod array @ foamed copper-based composite electrode material obtained in the step 2) to obtain a final product MOF-compounded copper-based nanorod array @ foamed copper-based composite electrode material.
2. The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material as claimed in claim 1, wherein a molar ratio of the ammonium persulfate to the potassium hydroxide in step 1) is 0.5-4: 20 to 50.
3. The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material as claimed in claim 2, wherein the molar ratio of the ammonium persulfate to the potassium hydroxide in step 1) is 1: 25.
4. the preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material as claimed in claim 1, wherein the concentration of the ammonium persulfate aqueous solution in the step 1) is 0.1-1 mol/L; the concentration of the potassium hydroxide aqueous solution is 6-15 mol/L.
5. The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material as claimed in claim 1, wherein the reaction in the step 1) is performed at normal temperature for 10-60 min.
6. The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material as claimed in claim 1, wherein in the step 2), the precursor solution of the ZIF-67 is prepared by the following method:
respectively dissolving cobalt salt and dimethyl imidazole in methanol to prepare A, B solution, and mixing the AB solution to obtain the precursor solution of the ZIF-67.
7. The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material as claimed in claim 6, wherein a molar ratio of the cobalt salt to the dimethyl imidazole is 1-2: 4-8; the cobalt salt is one or more of cobalt nitrate, cobalt chloride and cobalt sulfate.
8. The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material as claimed in claim 6, wherein the concentration range of the solute in the solution A is 0.01-0.1 mol/L, and the concentration range of the solute in the solution B is 0.1-0.4 mol/L.
9. The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material as claimed in claim 1, wherein in the step 2), the reaction is specifically: stirring for 1-10min at normal temperature, stopping stirring, and standing in the dark for 10-24 h.
10. The preparation method of the MOF composite copper-based nanorod array @ foam copper-based composite electrode material as claimed in claim 1, wherein in the step 3), the annealing treatment specifically comprises the following steps: and (3) under the condition of introducing Ar gas, heating to 280-320 ℃ at the speed of 5 ℃/min, preserving the heat for 1-3 h, and cooling to room temperature at the speed of 5 ℃/min.
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