CN110773233B - Preparation method of electrocatalytic full-hydrolytic nanosheet array material - Google Patents

Preparation method of electrocatalytic full-hydrolytic nanosheet array material Download PDF

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CN110773233B
CN110773233B CN201910802095.1A CN201910802095A CN110773233B CN 110773233 B CN110773233 B CN 110773233B CN 201910802095 A CN201910802095 A CN 201910802095A CN 110773233 B CN110773233 B CN 110773233B
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precursor solution
nanosheet array
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CN110773233A (en
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曹澥宏
尹瑞连
刘文贤
施文慧
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Zhejiang University of Technology ZJUT
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Abstract

The invention relates to the technical field of nano materials, in particular to a preparation method of an electrocatalytic full-hydrolytic nanosheet array material. It includes: 1) Preparing a precursor solution: dissolving two metal compounds containing different metal elements and an organic ligand in water, and uniformly mixing to obtain a precursor solution; 2) In-situ synthesis: and (3) placing the pretreated conductive substrate in a precursor solution, carrying out hydrothermal treatment on the conductive substrate, and preparing the electrocatalytic full-hydrolytic nanosheet array material on the surface of the conductive substrate after the hydrothermal treatment is finished. The product prepared by the invention has excellent electrocatalytic full-hydrolytic performance; the preparation method is simple and efficient, and can realize the rapid preparation of the electrocatalytic full-hydrolytic nanosheet array material on the conductive substrate; low requirement on equipment, wide raw material source and contribution to industrial production.

Description

Preparation method of electrocatalytic full-hydrolytic nanosheet array material
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of an electrocatalytic full-hydrolytic nanosheet array material.
Background
With the increasing demand for energy from human beings, the preparation of renewable energy by electrocatalysis has been widely studied as a promising approach to solve environmental crisis and energy problems. Currently, noble metals (e.g., pt) and noble metal oxides (e.g., ruO) 2 、IrO 2 ) As a highly active electrocatalyst, excellent electricity is exhibited in the full hydrolysis half-reactions of the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER), respectivelyCatalytic performance. However Pt and RuO 2 /IrO 2 Has high cost, low storage capacity and poor stability, so that it is necessary to find a low-cost catalyst with high earth storage capacity as a substitute catalyst for noble metals. At present, high-efficiency bifunctional electrocatalysts such as metal oxides, sulfides and composite materials have attracted considerable attention in an alkaline medium to catalyze OER and HER. Although great progress has been made at present, these materials are often complicated in preparation process and harsh in preparation conditions.
The metal organic framework compound (MOF) is formed by coordinating metal ions and organic ligands through covalent bonds, has the characteristics of high porosity, large specific surface area, adjustable pore structure and the like, is widely applied to the fields of medical treatment, sensing, catalysis and the like in recent years, however, the development of the MOF in the field of electrochemical catalysis is severely limited by the defects of poor conductivity, low catalytic activity and the like of a single metal MOF material. Bimetallic MOF materials can effectively improve the catalytic activity and the conductivity of the MOF materials through the synergistic coordination effect between metal ions, and the extensive research is caused in recent years. The two-dimensional nanosheet has a higher specific surface area and more active sites than the three-dimensional block, and the application value of the two-dimensional nanosheet is higher, but the two-dimensional material is easy to stack in the application process, and the surface active sites cannot be fully exposed, so that the further development of the two-dimensional nanosheet is severely limited. In the array structure, the nano sheets are mutually staggered, so that the stacking problem between the sheets can be effectively inhibited. In conclusion, the construction of the bimetallic MOF nanosheet array structure and the application of the bimetallic MOF nanosheet array structure in electrocatalysis of total water decomposition are of great significance. However, most of the current synthesis methods of two-dimensional MOF nanosheet array materials are top-to-bottom or use surfactants and toxic organic solvents, and the preparation process is complex and the conductivity is poor. Therefore, the preparation process needs to be improved.
The invention discloses a carbon-based bimetal composite material, preparation and application thereof, and discloses an invention patent application with application publication number of CN107803207A, which is disclosed by Chinese patent office in 2018, 3, and 16.A comprises a carbon-based shell, wherein the inner surface of the carbon-based shell is compounded with a sulfide of a transition metal A, and the outer surface of the carbon-based shell is compounded with an oxide of a transition metal B; the transition metals A and B are selected from different metals. The invention also discloses a preparation method of the carbon-based bimetallic composite material, which comprises the steps of carrying out hydrothermal reaction on a mixed solution containing transition metal A salt, transition metal B salt, an organic ligand and alcohol at the temperature of 60-180 ℃ to obtain bimetallic MOF; and mixing the obtained bimetallic MOF with sublimed sulfur, and roasting at 300-800 ℃ in a protective atmosphere to obtain the carbon-based bimetallic composite material. According to the technical scheme, the carbon-based bimetallic composite material is obtained through hydrothermal and protective calcination in sequence, but the MOF nanosheet array cannot be prepared controllably, the microstructure of the prepared composite material cannot be regulated, and the electrocatalytic full-hydrolytic performance is not achieved.
Disclosure of Invention
In order to solve the problems of high difficulty, poor controllability, complex preparation process, pollution and the like of the traditional MOF nano-structure array, the invention provides a preparation method of an electrocatalytic full-hydrolytic nano-sheet array material. The purpose is as follows: 1. the preparation process is simplified, the requirement on equipment is reduced, and the preparation cost is reduced; 2. the prepared nano-sheet array has complete and controllable structure and strong orderliness; 3. the nano-sheet structure has uniform size and stable structure, and the tri-metal components are uniformly distributed; 4. the constructed bimetallic MOF nanosheet array has excellent full-hydrolytic property.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of an electrocatalytic full-hydrolytic nanosheet array material,
the method comprises the following steps:
1) Preparing a precursor solution: dissolving two metal compounds containing different metal elements and an organic ligand in water, and uniformly mixing to obtain a precursor solution;
2) In-situ synthesis: and (3) placing the pretreated conductive substrate in a precursor solution, carrying out hydrothermal treatment on the conductive substrate, and preparing the electrocatalytic full-hydrolytic nanosheet array material on the surface of the conductive substrate after the hydrothermal treatment is finished.
The invention realizes the rapid and simple preparation of the electrocatalytic full-hydrolytic nanosheet array material by simply preparing a precursor solution containing two metal elements and an organic ligand and performing hydrothermal reaction by utilizing the coordination of a conductive substrate. The whole method is simple and efficient, and the efficient preparation of the ordered bimetallic MOF nanosheet array can be realized. And the prepared nanosheet array has excellent electrocatalytic full-hydrolytic performance due to the synergistic effect between the MOF framework and the bimetal, the bimetal and the organic framework.
As a matter of preference,
step 1) the metal elements comprise nickel, manganese, molybdenum, iron, zinc and cobalt;
the organic ligand in the step 1) is 2-methylimidazole.
The precursor solution contains any two of the six metal elements for preparing the electrocatalytic full-hydrolytic nanosheet array material, the organic ligand is beneficial to the preparation of the nanosheet array, and the 2-methylimidazole is beneficial to the uniform growth of the bimetallic nanosheet, so that the prepared nanosheet array is more uniform and ordered.
As a preference, the first and second liquid crystal compositions are,
in the precursor solution of the step 1), the total concentration of two metal compounds containing different metal elements is 0.05-0.5 mol/L;
in the precursor solution in the step 1), the concentration of the organic ligand is 0.05-0.5 mol/L.
The total concentration of the metal compound is controlled, the phenomenon that the nanometer sheet array structure cannot be formed due to the fact that the nanometer sheet pores are filled due to too high concentration of the metal compound is avoided, and the problem that the nanometer sheet cannot be formed or is formed unevenly due to too low concentration of the metal compound is avoided. The appearance of the nanosheet array can be effectively controlled by controlling the concentration of the organic ligand. The total concentration of the metal compound and the concentration of the organic ligand are both 0.10-0.12 mol/L optimally.
As a preference, the first and second liquid crystal compositions are,
in the precursor solution of the step 1), the molar ratio of two metal elements is 1: (2.5-3.5);
in the precursor solution in the step 1), the ratio of the total molar concentration of two metal elements to the molar concentration of the organic ligand is (1-5): (1-5).
The molar ratio of the two metal ions is controlled, so that the proportion of the two components in the MOF nanosheet can be regulated, wherein the optimal molar ratio of the two metal ions is 3:1. the growth of the MOF nanosheet can be regulated and controlled by controlling the molar concentration ratio of the total molar concentrations of the two metal ions to the molar concentration of the organic ligand, the uniformity and the complete morphology of the MOF nanosheet are further ensured, and the optimal ratio of the total molar concentrations of the three metal ions to the molar concentration of the organic ligand is 1:1.
as a matter of preference,
the conductive substrate in the step 2) comprises metal copper, metal nickel, metal titanium and graphene.
The substrates all have the advantages of wide sources, low cost and easy obtainment.
As a preference, the first and second liquid crystal compositions are,
the conditions of the hydrothermal treatment in the step 2) are as follows:
the hydrothermal temperature is 100-180 ℃, and the hydrothermal time is 6-48 h.
The hydrothermal temperature has direct influence on the growth and the growth rate of the nano structure, the growth rate is too low or the nano structure is incomplete due to too low temperature, the nano sheet array collapses or disordered growth is caused due to too high temperature, and the hydrothermal duration has more visual influence on the size of the nano sheet.
As a preference, the first and second liquid crystal compositions are,
the conditions of the hydrothermal treatment in the step 2) are as follows:
the hydrothermal temperature is 125-135 ℃, and the hydrothermal time is 9-11 h.
The hydrothermal temperature and the hydrothermal time are selected optimally, and the generated nanosheets are stable in structure, uniform in components and uniform in size.
The beneficial effects of the invention are:
1) The prepared product has excellent electrocatalytic full-hydrolytic performance;
2) The preparation method is simple and efficient, and can realize the rapid preparation of the electrocatalytic full-hydrolytic nanosheet array material on the conductive substrate;
3) The requirement on equipment is low, the raw material source is wide, and the industrial production is facilitated;
4) The nano sheets have uniform size and uniform component distribution, and the nano sheet array has a complete structure, ordered and dense growth;
5) The overall performance is excellent in OER performance and constant current stability.
Drawings
FIG. 1 is a structural diagram of the morphology of CoNi-MOF-NF prepared in example 1 of the present invention;
FIG. 2 is a diagram of the electrochemical performance test of CoNi-MOF-NF prepared in example 1 of the present invention;
FIG. 3 is a structural diagram of the morphology of CoMo-MOF-NF prepared in example 2 of the present invention;
FIG. 4 is a graph showing the electrochemical properties of CoMo-MOF-NF prepared in example 2 of the present invention;
FIG. 5 is a structural diagram of the NiMo-MOF-NF prepared in example 3 of the present invention;
FIG. 6 is a graph showing the electrochemical properties of NiMo-MOF-NF prepared in example 3 of the present invention.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawing figures. Those skilled in the art will be able to implement the invention based on these teachings. Furthermore, the embodiments of the present invention described in the following description are generally only a part of the embodiments of the present invention, and not all of the embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art. The following description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Example 1
A preparation method of an electrocatalytic full-hydrolytic nanosheet array material comprises the following steps:
1) Weighing 1.26g Co (NO) 3 ) 2 ·6H 2 O and 0.42g Ni (NO) 3 ) 2 ·6H 2 O, adding the mixture into 50mL of deionized water, simultaneously weighing 0.475g of 2-methylimidazole, adding the mixture into the deionized water, dissolving the mixture by ultrasonic waves to prepare a precursor solution, and adding Co (NO) in the precursor solution 3 ) 2 ·6H 2 O molar concentration of 0.0866mol/L, ni (NO) 3 ) 2 ·6H 2 The molar concentration of O is 0.0289mol/L, and the molar concentration of 2-methylimidazole is 0.116mol/L;
2) Cutting a 2cm multiplied by 4cm foam nickel sheet, sequentially placing the foam nickel sheet in acetone, ethanol and deionized water for ultrasonic cleaning for 5min to finish pretreatment, then placing the pretreated foam nickel sheet and precursor solution in a 100mL reaction kettle together, placing the reaction kettle in an oven, heating to 130 ℃ for hydrothermal reaction for 10h, naturally cooling to room temperature after the reaction is finished, namely preparing the electrocatalytic fully-hydrolyzed nanosheet array material on the surface of the foam nickel sheet, and marking the electrocatalytic fully-hydrolyzed nanosheet array material as CoNi-MOF-NF. And (3) placing CoNi-MOF-NF in deionized water for ultrasonic treatment for 30s, removing surface deposits, placing the obtained product in a vacuum drying condition at 60 ℃ for 12h, and characterizing and testing the CoNi-MOF-NF.
Specific characterization and testing included:
(1) Topography analysis
SEM characterization was performed on a HITACHI S-4700 scanning electron microscope using the following sample preparation methods: cutting off a small piece of CoNi-MOF-NF, placing the small piece of CoNi-MOF-NF on the surface of a supporting table stuck with conductive adhesive, and then placing the small piece of CoNi-MOF-NF into an SEM chamber for testing;
(2) Electrochemical testing
(2-1) OER and HER performance tests are carried out by using a Chenghua electrochemical workstation and adopting a three-electrode system to carry out Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV) tests. Cutting CoNi-MOF-NF into 1 × 2cm self-supporting working electrode, vertically inserting into 1M KOH electrolyte, and immersing in 1 cm area 2 Testing by using a carbon rod as a counter electrode and Saturated Calomel (SCE) as a reference electrode;
(2-2) testing the electrocatalytic full-hydrolytic capacity, cutting the prepared CoNi-MOF-NF into 1 x 2cm self-supporting working electrodes serving as two poles of an electrolytic cell, placing the self-supporting working electrodes in a 1M KOH solution for testing, and immersing the electrodes in the solution with the immersion area of 1 cm 2 。
The SEM image of the CoNi-MOF-NF obtained in example 1 is shown in figure 1, and figure 1 (a, b) is the SEM image of the CoNi-MOF-NF, and it can be seen that the bimetallic MOF nanosheet array grows vertically on the foamed nickel plate substrate, and the nanosheet array has a transverse dimension of about 800 nm and is uniformly distributed.
The electrochemical performance of the CoNi-MOF-NF prepared in the example 1 is shown in figure 2, and as can be seen from figure 2 (a), the CoNi-MOF-NF nanosheet array material has good OER performance and 10mA cm -2 The corresponding overpotential at the current density was 260 mV. As can be seen from FIG. 2 (b), ciNi-MOF-NF material has good HER performance at 10mA cm -2 The corresponding overpotential at current density was 178.07 mV. As is evident from FIG. 2 (c), the current density of the alloy can reach 13.89mA cm -2 . The test result shows that the compound has good HER performance and OER performance, and has good electrocatalytic full-hydrolytic performance.
Example 2
A preparation method of an electrocatalytic full-hydrolytic nanosheet array material, the method comprising the steps of:
1) Weighing 0.42g Co (NO) 3 ) 2 ·6H 2 O and 0.624g MoO 3 Adding the mixture into 50mL of deionized water, simultaneously weighing 0.475g of 2-methylimidazole, adding the mixture into the deionized water, preparing a precursor solution after ultrasonic dissolution, and preparing Co (NO) in the precursor solution 3 ) 2 ·6H 2 The molar concentration of O is 0.0289mol/L, moO 3 The molar concentration is 0.0867mol/L, and the molar concentration of 2-methylimidazole is 0.116mol/L;
2) Cutting a 2 cm-by-4 cm foam nickel sheet, sequentially placing the foam nickel sheet in acetone, ethanol and deionized water for ultrasonic cleaning for 5min to complete pretreatment, then placing the pretreated foam nickel sheet and a precursor solution in a 100mL reaction kettle together, placing the reaction kettle in an oven, heating to 150 ℃ for hydrothermal reaction for 14h, naturally cooling to room temperature after the reaction is finished, namely preparing the electrocatalytic full-hydrolytic nanosheet array material on the surface of the foam nickel sheet, and marking the electrocatalytic full-hydrolytic nanosheet array material as CoMo-MOF-NF. And (3) placing the CoMo-MOF-NF in deionized water for ultrasonic treatment for 30s, removing surface deposits, placing the mixture in a vacuum drying condition at 60 ℃ for 12h, and performing characterization and test on the CoMo-MOF-NF.
Specific characterization and testing included:
(1) Topography analysis
SEM characterization was performed on a HITACHI S-4700 scanning electron microscope using the following sample preparation methods: cutting off a small piece of CoMo-MOF-NF, placing the small piece of CoMo-MOF-NF on the surface of a supporting table pasted with conductive adhesive, and then placing the small piece of CoMo-MOF-NF into an SEM chamber for testing;
(2) Electrochemical testing
(2-1) OER and HER performance tests are carried out by using a Chenghua electrochemical workstation and adopting a three-electrode system to carry out Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV) tests. Cutting CoMo-MOF-NF into 1 × 2cm self-supporting working electrode, vertically inserting into 1M KOH electrolyte, and immersing in 1 cm area 2 Testing by using a carbon rod as a counter electrode and Saturated Calomel (SCE) as a reference electrode;
(2-2) testing the electrocatalytic full-hydrolytic capacity, cutting the prepared CoMo-MOF-NF into 1 x 2cm self-supporting working electrodes which are used as two poles of an electrolytic cell and are placed in a 1M KOH solution for testing, wherein the immersion area is 1 cm 2 。
The SEM image of the CoNi-MOF-NF obtained in example 2 is shown in FIG. 3, and FIG. 3 (a, b) is the SEM image of CoMo-MOF-NF, and it can be seen that the bimetallic MOF nanosheet array grows vertically on the foamed nickel plate substrate, and the nanosheet array has a transverse dimension of about 1 μm and is uniformly distributed.
The electrochemical performance of the CoMo-MOF-NF prepared in the example 2 is shown in figure 4, and as can be seen from figure 4 (a), the CoMo-MOF-NF nanosheet array material has good OER performance at 10 mA-cm -2 The corresponding overpotential at current density is 266 mV. From FIG. 4 (b), it can be seen that the CoMo-MOF-NF material has good HER performance at 10mA cm -2 The corresponding overpotential at current density was 177.69 mV. The current density is clearly shown in FIG. 4 (c)Can reach 49.21mA cm -2 . The test result shows that the compound has good HER performance and OER performance, and has good electrocatalytic full-hydrolytic performance.
Example 3
A preparation method of an electrocatalytic full-hydrolytic nanosheet array material comprises the following steps:
1) Weighing 0.2248gNi (NO) 3 ) 2 ·6H 2 O and 0.5g MoO 3 Adding the precursor solution into 50mL of deionized water, simultaneously weighing 0.475g of 2-methylimidazole, adding the mixture into the deionized water, dissolving the mixture by ultrasonic waves to prepare a precursor solution, and adding Ni (NO) into the precursor solution 3 ) 2 ·6H 2 The molar concentration of O is 0.0155mol/L, moO 3 The molar concentration is 0.0695 mol/L, and the molar concentration of 2-methylimidazole is 0.116mol/L;
2) Cutting a 2cm multiplied by 4cm foam nickel sheet, sequentially placing the foam nickel sheet in acetone, ethanol and deionized water for ultrasonic cleaning for 5min to finish pretreatment, then placing the pretreated foam nickel sheet and precursor solution in a 100mL reaction kettle together, placing the reaction kettle in an oven, heating to 120 ℃ for hydrothermal reaction for 8h, naturally cooling to room temperature after the reaction is finished, namely preparing the electrocatalytic fully-hydrolyzed nanosheet array material on the surface of the foam nickel sheet, and marking the material as NiMo-MOF-NF. Putting NiMo-MOF-NF into deionized water, performing ultrasonic treatment for 30s, removing surface deposits, putting the NiMo-MOF-NF into the deionized water, performing vacuum drying for 12h at the temperature of 60 ℃, and performing characterization and test on the NiMo-MOF-NF.
Specific characterization and testing included:
(1) Topography analysis
SEM characterization was performed on a HITACHI S-4700 scanning electron microscope using the following sample preparation methods: cutting off a small piece of NiMo-MOF-NF, placing the NiMo-MOF-NF on the surface of a supporting table stuck with conductive adhesive, and then placing the NiMo-MOF-NF into an SEM chamber for testing;
(2) Electrochemical testing
(2-1) OER and HER performance tests are carried out by Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV) by using Chenghua electrochemical workstation and adopting a three-electrode system. Cutting NiMo-MOF-NF into 1 × 2cm self-supporting working electrode, and vertically inserting into 1MIn KOH electrolyte, the immersion area was 1 cm 2 Testing by using a carbon rod as a counter electrode and Saturated Calomel (SCE) as a reference electrode;
(2-2) electrocatalytic full-water-splitting performance test, cutting the prepared NiMo-MOF-NF into 1 x 2cm self-supporting working electrodes serving as two electrodes of an electrolytic cell, placing the self-supporting working electrodes in a 1M KOH solution for testing, and testing the immersed area of the self-supporting working electrodes in the 1M KOH solution 2 。
The SEM image of the NiMo-MOF-NF obtained in example 3 is shown in FIG. 5, and FIG. 5 (a, b) is the SEM image of the NiMo-MOF-NF, and it can be seen from the SEM image that the bimetallic MOF nanosheet array grows vertically on the foamed nickel plate substrate, and the nanosheet array has a transverse dimension of about 300nm, uniform thickness and uniform distribution.
The electrochemical performance of the NiMo-MOF-NF prepared in the example 3 is shown in FIG. 6, and as can be seen from FIG. 6 (a), the NiMo-MOF-NF nanosheet array material has good OER performance and has the 10mA cm -2 The corresponding overpotential at current density was 302.34mV. As can be seen from FIG. 6 (b), the NiMo-MOF-NF material has good HER performance at 10 mA-cm -2 The corresponding overpotential at the current density was 148.04 mV. As is apparent from FIG. 6 (c), the current density of the alloy can reach 28.51mA cm -2 . The test result shows that the compound has good HER performance and OER performance, and has good electrocatalytic full-hydrolytic performance.
Example 4
The procedure was as in example 1, except that Mn (NO) was used 3 ) 2 ·4H 2 O and Ni (NO) 3 ) 2 ·6H 2 O, and the dosage of the two metal compounds is 0.36g and 1.26g respectively. Preparing the electrocatalytic full-hydrolytic nanosheet array material on the surface of the foamed nickel sheet, and marking the electrocatalytic full-hydrolytic nanosheet array material as MnNi-MOF-NF. And SEM representation is carried out on the sample prepared in the embodiment, and the representation result shows that the nanosheet grows vertically and is distributed uniformly.
Example 5
The procedure was as in example 1, except that MoO was used 3 And Mn (NO) 3 ) 2 ·4H 2 O, and the dosage of the two metal compounds is 0.5g and 0.194g respectively. On a foamed nickel sheetThe electrocatalytic full-hydrolytic nanosheet array material is prepared on the surface and is marked as MnNi-MOF-NF. And SEM representation is carried out on the sample prepared in the embodiment, and the representation result shows that the nanosheet grows vertically and is distributed uniformly.
Example 6
The procedure was as in example 1, except that MoO was used 3 And Mn (NO) 3 ) 2 ·4H 2 O two metal compounds in an amount of 0.09g and 0.47g, respectively, and 2-methylimidazole in an amount of 0.21g. Preparing the electrocatalytic full-hydrolytic nanosheet array material on the surface of the foamed nickel sheet, wherein the array material is marked as MnNi-MOF-NF. And SEM representation is carried out on the sample prepared in the embodiment, and the representation result shows that the nanosheet grows vertically and is distributed uniformly.
Example 7
The procedure was as in example 1, except that MoO was used 3 And Mn (NO) 3 ) 2 ·4H 2 O, 0.90g and 4.71g respectively, 2.05g of 2-methylimidazole, 180 ℃ of hydrothermal temperature and 6 hours of hydrothermal time. Preparing the electrocatalytic full-hydrolytic nanosheet array material on the surface of the foamed nickel sheet, and marking the electrocatalytic full-hydrolytic nanosheet array material as MnNi-MOF-NF. And SEM representation is carried out on the sample prepared in the embodiment, and the representation result shows that the nanosheet grows vertically and is distributed uniformly.
Example 8
The procedure was as in example 1, except that MoO was used 3 And Mn (NO) 3 ) 2 ·4H 2 O, 0.10g and 0.45g, and 2-methylimidazole, 0.21g. Preparing the electrocatalytic full-hydrolytic nanosheet array material on the surface of the foamed nickel sheet, wherein the array material is marked as MnNi-MOF-NF. And SEM representation is carried out on the sample prepared in the embodiment, and the representation result shows that the nanosheet grows vertically and is distributed uniformly.
Example 9
The procedure was as in example 1, except that MoO was used 3 And Mn (NO) 3 ) 2 ·4H 2 O two metal compounds with dosage of 0.08g and 0.49g respectively, 2-methylimidazole with dosage of 0.21g, hydrothermal temperatureThe temperature is 100 ℃, and the hydrothermal time is 48h. Preparing the electrocatalytic full-hydrolytic nanosheet array material on the surface of the foamed nickel sheet, and marking the electrocatalytic full-hydrolytic nanosheet array material as MnNi-MOF-NF. And SEM representation is carried out on the sample prepared in the embodiment, and the representation result shows that the nanosheet grows vertically and is distributed uniformly.
Example 10
The procedure was as in example 1, except that MoO was used 3 And Mn (NO) 3 ) 2 ·4H 2 O, 0.09g and 0.47g respectively, 1.02g of 2-methylimidazole, 135 ℃ of hydrothermal temperature and 9 hours of hydrothermal time. Preparing the electrocatalytic full-hydrolytic nanosheet array material on the surface of the foamed nickel sheet, and marking the electrocatalytic full-hydrolytic nanosheet array material as MnNi-MOF-NF. And SEM representation is carried out on the sample prepared in the embodiment, and the representation result shows that the nanosheet grows vertically and is distributed uniformly.
Example 11
The procedure was as in example 1, except that MoO was used 3 And Mn (NO) 3 ) 2 ·4H 2 O, 0.45g and 2.35g respectively, 0.21g of 2-methylimidazole, 125 ℃ of hydrothermal temperature and 11h of hydrothermal time. Preparing the electrocatalytic full-hydrolytic nanosheet array material on the surface of the foamed nickel sheet, wherein the array material is marked as MnNi-MOF-NF. And SEM representation is carried out on the sample prepared in the embodiment, and the representation result shows that the nanosheet grows vertically and is distributed uniformly.

Claims (2)

1. A preparation method of electrocatalytic full-hydrolytic nanosheet array material is characterized by comprising the following steps of,
the method comprises the following steps:
1) Preparing a precursor solution: dissolving two metal compounds containing different metal elements and an organic ligand in water, and uniformly mixing to obtain a precursor solution;
2) In-situ synthesis: placing the pretreated conductive substrate in a precursor solution, carrying out hydrothermal treatment on the conductive substrate, and preparing the electrocatalytic full-hydrolytic nanosheet array material on the surface of the conductive substrate after the hydrothermal treatment is finished;
the metal element in the step 1) is nickel, manganese, molybdenum, iron, zinc or cobalt;
step 1) the organic ligand is 2-methylimidazole;
in the precursor solution of the step 1), the total concentration of two metal compounds containing different metal elements is 0.05-0.5 mol/L;
in the precursor solution in the step 1), the concentration of the organic ligand is 0.05-0.5 mol/L;
in the precursor solution of the step 1), the molar ratio of two metal elements is 1: (2.5-3.5);
in the precursor solution in the step 1), the ratio of the total molar concentration of two metal elements to the molar concentration of an organic ligand is (1-5): (1-5);
the hydrothermal temperature is 100-180 ℃, and the hydrothermal time is 6-48 h;
and step 2) the conductive substrate is metal copper, metal nickel, metal titanium or graphene.
2. The preparation method of the electrocatalytic perhydrolysis water nanosheet array material according to claim 1,
the conditions of the hydrothermal treatment in the step 2) are as follows:
the hydrothermal temperature is 125-135 ℃, and the hydrothermal time is 9-11 h.
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