CN116240575A - Self-supporting catalyst and preparation method and application thereof - Google Patents
Self-supporting catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a self-supporting catalyst, a preparation method and application thereof, wherein the self-supporting catalyst comprises a foam nickel substrate and Cu supported on the foam nickel substrate 2 S particles, wherein the Cu 2 S particles are in a micron flower sphere shape; the preparation method comprises the following steps: and (3) using an electrochemical three-electrode system, taking foam nickel as a working electrode and a reaction substrate, and respectively carrying out reduction of copper ions and sulfuration of copper by a potentiostatic method and a cyclic voltammetry according to oxidation-reduction potential of copper to obtain the self-supported catalyst. The self-supporting material Cu 2 S@NF shows excellent catalytic activity and stability in HER and OER as a bifunctional electrocatalyst, has great advantages compared with other non-noble metal electrocatalysts, and has good application prospect in electrolyzed water.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a self-supporting catalyst, in particular to a self-supporting catalyst and a preparation method and application thereof.
Background
The development of modern economy promotes the increasing demand of people for energy, so that the problems of exhaustion of fossil energy, environmental pollution and the like are increasingly serious. The development of sustainable clean energy is an important means for relieving energy crisis and environmental problems caused by the large-scale use of primary energy such as medium, petroleum and natural gas. Hydrogen has the characteristics of high energy density (120-140 MJ/kg), low production cost, no pollution and the like, is one of the most promising clean energy sources, and is an ideal way for obtaining energy in the future, however, the research and development of the technology for obtaining hydrogen fuel has a plurality of difficulties.
Electrocatalytic total water splitting is a green and efficient method for large-scale production of hydrogen, and the system consists of two half reactions, namely Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). The overpotential driving HER is typically less than 100mV, while OER requires a higher overpotential @ and>300 mV). Currently, pt metal and Ir/RuO x Reference electrocatalysts for HER and OER, respectively. However, the practical application of the reference electrocatalyst in the electrolytic cell has the problem of unmatched working conditions, and meanwhile, the traditional noble metal electrocatalyst material has the defects of high cost, low storage capacity, non-reproducibility and the like. To solve the above problems, it is critical to develop a dual-function electrocatalyst for HER and OER with low noble metal ratio or non-noble metal in the same electrolyte.
The transition metal sulfide has the advantages of good electron conduction capability, low cost, adjustable components, high electrocatalytic activity and the like, and has great development potential in the fields of fuel cells, solar cells, biosensors, supercapacitors and the like. In addition, it is abundant in resources and low in price, mainly exists in nature in the form of ores, and common transition metal sulfide ores include pyrite, sphalerite, chalcocite and the like, accounting for about 1.5% of the sulfur content of the crust. However, the electrocatalytic performance of the common transition metal sulfide is not ideal, and the main reason is that the specific surface area is not large enough, and the active sites are not rich enough, so that research and development of the transition metal sulfide electrocatalytic material with a special structure is a popular field of research at present.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention discloses a self-supporting catalyst, a preparation method and application thereof, in particular to a method for selecting Cu 2 S is a research object, and micron flower-shaped spherical Cu grows on a foam nickel substrate in situ by adopting an electrochemical two-step synthesis method for the first time 2 S particles, utilizing the three-dimensional open nano structure of foam nickel to improve the number of active sites and the utilization rate of active substances, and obtaining Cu 2 S@NF self-supporting electrode and is used for electrocatalytic full water decomposition. The invention solves the problems of high price, low reserve and only single reaction of the traditional electrocatalyst, and obtains the low-cost double-function electrocatalyst with high catalytic efficiency.
It is an object of the present invention to provide a self-supporting catalyst comprising a foamed nickel substrate and Cu supported on the foamed nickel substrate 2 S particles, wherein the Cu 2 The S particles are in the shape of micron flower spheres.
The invention uses the excellent conductivity and unique three-dimensional open nano structure of foam nickel as a substrate to carry out electrochemical in-situ load of cuprous sulfide so as to improve the quantity of active sites of the material and the utilization rate of active substances. Meanwhile, the inherent processability of the foam nickel is utilized to reduce the use of additives such as adhesives and the like so as to avoid the influence on the catalytic activity of the material.
In a preferred embodiment, the Cu 2 The average particle diameter of the S particles is 5.+ -. 3. Mu.m, preferably 5.+ -. 2. Mu.m.
Wherein the self-supporting catalyst Cu 2 S@NF is a flower-sphere micron-sized combined array structure.
Cu according to the invention 2 Advantages of s@nf self-supporting electrode: 1. the preparation method is simple, no special experimental conditions such as high temperature, high pressure and the like are needed, the electrochemical preparation method has low cost and simple experimental conditions; 2. since the foam nickel has conductivity, cu is directly grown on the foam nickel in situ in the preparation process 2 S material is a self-supporting electrode, so that any additive or conductive agent is not needed to be added in actual use, and the influence of the use of the additive on the electrocatalytic activity of the material is effectively reduced; 3. cu prepared by the invention 2 The self-supporting electrode S@NF has lower overpotential in the processes of electrocatalytic HER, OER and full water dissolution, and has great advantages compared with the catalytic performance of other transition metal-based electrocatalytic materials.
It is a second object of the present invention to provide a process for the preparation of a self-supporting catalyst, preferably for one of the objects of the present invention, comprising: and (3) using an electrochemical three-electrode system, taking foam nickel as a working electrode and a reaction substrate, and respectively carrying out reduction of copper ions and sulfuration of copper by a potentiostatic method and a cyclic voltammetry according to oxidation-reduction potential of copper to obtain the self-supported catalyst.
In the invention, an electrochemical three-electrode system is utilized, foam nickel is used as a working electrode and a reaction substrate, and according to the oxidation-reduction potential of copper, a two-step electrochemical synthesis method (constant potential-cyclic voltammetry) is utilized to respectively reduce and vulcanize copper ions, so as to realize micron flower-shaped spherical Cu 2 S is deposited in situ on the nickel foam.
Specifically, the self-supporting catalyst Cu of the invention 2 The S@NF is prepared by taking foam nickel as a working electrode, firstly reducing and depositing copper ions on the foam nickel by an electrochemical constant potential method to construct a Cu@NF framework, and then realizing in-situ vulcanization of copper particles by a cyclic voltammetry method.
In a preferred embodiment, the method of preparation comprises:
in the step 2, electrochemical deposition is carried out, yellow substance deposition is observed on the surface of the foam nickel, and Cu@NF is obtained;
The surface morphology and the catalytic activity of the self-supporting catalyst can be optimized by adjusting electrochemical parameters, so that the hydrogen evolution reaction and the oxygen evolution reaction can be catalyzed in alkaline solution at the same time and the catalyst has good catalytic stability. The preparation process designed by the invention is simple and convenient to operate, economical and efficient, has excellent material catalytic performance and better application prospect, and can be applied to an electrochemical full water dissolving system.
In a preferred embodiment, the nickel foam has a size of (0.5 to 1.5) × (1 to 5) cm 2 Thickness of 0.25 to 1.5 mm, preferably 1X 3cm 2 The thickness was 0.5mm.
In a preferred embodiment, a pretreatment of Nickel Foam (NF) is performed prior to step 1.
In a further preferred embodiment, the pretreatment comprises: the nickel foam is respectively ultrasonically cleaned in acid solution, alcohol solvent (such as ethanol) and distilled water.
In a still further preferred embodiment, the acid solution is 0.1M hydrochloric acid; and/or, the distilled water is double distilled water; and/or the ultrasonic cleaning time is 1-10 min, preferably 3-8 min.
In a preferred embodiment, in step 1, the electrolyte solution is a neutral solution, preferably a neutral salt solution, such as a potassium chloride solution; preferably, the molar concentration of the neutral salt solution is 0.1M.
In a further preferred embodiment, in step 1, copper ions (Cu 2+ ) Derived from water-soluble copper salts, such as copper chloride; preferably, the molar concentration of the water-soluble copper salt in the electrolyte solution is 5-30mM, for example 5mM, 10mM, 15mM, 20mM, 25mM and 30mM.
In a preferred embodiment, in step 1, the reference electrode is selected from one of an Ag/AgCl electrode, a saturated calomel electrode, and an Hg/HgO electrode.
In a preferred embodiment, in step 1, the counter electrode is selected from one of Pt wire and graphite rod.
In a preferred embodiment, in step 2, the time of the potentiostatic treatment is 1800 to 9000s, preferably 3600 to 7200s, more preferably 5400s.
For example, in step 2, the time of the potentiostatic treatment is 1800s, 2700s, 3600s, 4500s, 5400s, 6300s, 7200s, 8100s, or 9000s.
In a preferred embodiment, in step 2, a voltage of-0.2V is used.
In a preferred embodiment, in step 3, the sulfur-containing mineral is selected from NaHS, na 2 At least one of S.
In a preferred embodiment, in step 3, the electrolyte solution is an aqueous alkaline solution having a molar concentration of 0.1M.
In a further preferred embodiment, in step 3, the electrolyte solution is an aqueous sodium hydroxide solution.
In a preferred embodiment, in step 3, the molar concentration of the sulfur-containing inorganic substance in the electrolyte solution is 1 to 15mM, preferably 3 to 8mM, for example 1mM, 2mM, 3mM, 5mM, 7mM, 9mM, 12mM or 15mM.
In a preferred embodiment, in step 3, cyclic voltammetry is used to scan in the potential range of-1.0 to-0.5V.
In a preferred embodiment, in step 3, cyclic voltammetric scans are performed for 20 to 60, preferably 30 to 50, cycles during the vulcanization process.
In a preferred embodiment, the resulting Cu is treated after the sulfidation treatment 2 S@NF self-supporting catalyst is cleaned.
When the self-supporting catalyst is prepared, cu is realized by changing the application potential, the reaction time and the cycle voltammetry turns in the preparation process 2 S@NF morphology regulation and control, and further optimizing electrocatalytic activity. As a bifunctional electrocatalyst, the material can simultaneously reduce the overpotential of hydrogen evolution and oxygen evolution reaction, has good stability and has good application prospect in electrolyzed water.
Meanwhile, the invention adopts the two-step electrochemical method to prepare the Cu 2 S is in a micron flower sphere shape, and the experimental repeatability is high.
It is a further object of the present invention to provide a self-supported catalyst obtainable by the process of the second aspect of the present invention.
The fourth object of the present invention is to provide the use of the self-supported catalyst according to one of the objects of the present invention or the self-supported catalyst obtained by the two preparation methods according to the second object of the present invention in full water splitting, preferably in alkaline conditions.
In a preferred embodiment, an electrochemical three-electrode system comprising a working electrode, a reference electrode and a counter electrode is constructed to perform hydrogen evolution reaction and oxygen evolution reaction, wherein the self-supported catalyst is used as the working electrode; alternatively, a two-electrode system comprising a working electrode and a counter electrode is constructed for full water dissolution, wherein the self-supporting catalyst is used as the working electrode and the counter electrode.
In a further preferred embodiment, the reference electrode is selected from one of an Ag/AgCl electrode, a saturated calomel electrode, an Hg/HgO electrode; and/or the counter electrode is selected from one of Pt wires and graphite rods.
In a still further preferred embodiment, the electrolyte solutions of the electrochemical three-electrode system and the two-electrode system are alkaline aqueous solutions, such as aqueous KOH solutions; preferably, the molar concentration of the electrolyte solution is 1M; and/or the electrolyte solution of the electrochemical two-electrode system is an alkaline aqueous solution, such as an aqueous KOH solution; preferably, the molar concentration of the electrolyte solution is 0.1M.
For example: cu to be prepared 2 Cutting S@NF material to an effective area of 1X 1cm 2 As working electrode, ag/AgCl and Pt are respectively used as reference electrode and counter electrode, an electrochemical three-electrode system is constructed, and HER and OER performances are tested in 1MKOH aqueous solution. Construction of a two electrode SystemTesting its full water splitting performance, wherein: the self-supporting electrode Cu 2 S@NF current density reached 10mA/cm in HER reaction 2 The optimal overpotential at this time is 105mV, the self-supporting electrode Cu 2 The current density of S@NF reaches 10mA/cm in OER reaction 2 The optimal overpotential is 194mV, the self-supporting electrode Cu 2 The current density of S@NF in the two-electrode water decomposition system reaches 10mA/cm 2 The potential at the time is 1.64V, the self-supporting electrode Cu 2 S@NF has good catalytic stability in water splitting reaction.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention is characterized in that an electrochemical two-step synthesis method, namely a constant potential-cyclic voltammetry method is adopted for the first time, thereby realizing the micron flower-shaped spherical Cu 2 S in situ controlled growth on a foam nickel substrate. Compared with the traditional methods such as a hydrothermal method, an anion exchange method and a chemical vapor deposition method, the method has the advantages of simplicity in operation, low cost, environmental friendliness and the like. Meanwhile, the controllable preparation of the morphology and the dimension of the material can be realized by changing electrochemical parameters, so that the application performance of the material is optimized.
(2) The second characteristic of the present invention is that the active material is carried by using the metal foam material as the substrate. The three-dimensional network structure of the foam nickel can effectively improve the specific surface area of the material, and improve the quantity of active sites and the utilization rate of active substances. The self-supporting electrode is prepared by in-situ growth on the foam nickel by using an electrochemical method, and no additional adhesive or conductive agent is needed, so that adverse effects of the additive on the catalytic activity and stability of the material are avoided.
(3) The third feature of the invention is the self-supporting material Cu 2 S@NF shows excellent catalytic activity and stability in HER and OER as a bifunctional electrocatalyst, has great advantages compared with other non-noble metal electrocatalysts, and has good application prospect in electrolyzed water.
Drawings
FIG. 1 shows Cu in example 1 2+ Cyclic voltammograms of reduction potential determination.
FIG. 2 shows Cu in example 1 2 And S@NF sulfuration potential.
FIG. 3 shows the free-standing catalyst Cu in example 1 2 X-ray diffraction pattern (XRD) of s@nf.
FIG. 4 shows the free-standing catalyst Cu in example 1 2 And (3) energy spectrum analysis (EDS) of S@NF.
FIG. 5 shows the free-standing catalyst Cu in example 1 2 X-ray photoelectron spectroscopy (XPS) of S@NF.
Fig. 6 shows SEM electron microscopy images of cu@nf in example 1.
FIG. 7 shows the free-standing catalyst Cu in example 1 2 SEM electron microscopy of s@nf.
FIG. 8 shows the free-standing catalyst Cu of examples 1 to 3 2 S@nf Hydrogen Evolution Reaction (HER) polarization curve measured at electrochemical workstation.
FIG. 9 shows the free-standing catalyst Cu of examples 1 to 3 2 Hydrogen Evolution Reaction (HER) Tafel plot measured at electrochemical workstation for s@nf.
FIG. 10 shows the free-standing catalyst Cu of examples 1 to 3 2 Oxygen Evolution Reaction (OER) polarization curve measured at electrochemical workstation by s@nf.
FIG. 11 shows the free-standing catalyst Cu in example 1 2 Oxygen Evolution Reaction (OER) Tafel plot measured at electrochemical workstation by s@nf.
FIG. 12 shows the free-standing catalyst Cu in example 1 2 Polarization curve of s@nf in a two electrode electrolyzed water system.
FIG. 13 shows the free-standing catalyst Cu in example 1 2 Stability test of S@NF.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The starting materials employed in the examples, if not particularly limited, are all those disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
Preparation of self-supporting catalyst [ example 1 ]
a) Pretreatment of foam nickel: taking the size of 1X 3cm 2 Respectively ultrasonically cleaning the foam nickel in 0.1M hydrochloric acid, ethanol and double distilled water for 5min to remove surface oxides and possibly adsorbed impurities;
b) Electrolyte solution preparation: 60mL of a 0.1M KCl solution was added to the beaker, followed by weighing 0.16g of anhydrous CuCl 2 Adding the powder into beaker, stirring at room temperature until the powder is clear to obtain 0.1M KCl and 20mM CuCl 2 As an electrolyte solution for copper deposition;
c)Cu 2+ reduction potential determination: the experiment adopts an electrochemical three-electrode system, takes a pretreated foam nickel sheet as a working electrode,the Ag/AgCl electrode and the Pt wire were used as a reference electrode and a counter electrode, respectively, and the electrodes were completely immersed in the electrolyte solution prepared in b). Scanning by electrochemical cyclic voltammetry at a voltage range of-1.2V to 0V at a scanning rate of 50mV/s, as shown in FIG. 1, the occurrence of reduction peaks is observed near-0.2V, corresponding to Cu in solution 2+ Is reduced by (2);
d) Electrochemical preparation of cu@nf: in the electrochemical system of c), adopting a potentiostatic method, applying a potential of-0.2V for 5400s, performing electrochemical deposition, and observing yellow substance deposition on the surface of the foam nickel to obtain Cu@NF;
e) Configuration of the vulcanizing solution: 60mL of 0.1M NaOH solution is added into a beaker, 0.0168g of NaHS is weighed, the mixture is added into the beaker, and stirring is carried out until the mixture is clear, so that a mixed solution of 0.1M NaOH and 5mM NaHS is obtained and is used for vulcanizing Cu@NF;
f)Cu 2 electrochemical preparation of S@NF: scanning the Cu@NF sheet prepared in c) as a working electrode and the mixed solution prepared in e) as an electrolyte solution by adopting cyclic voltammetry in the range of-1.0 to-0.5V, wherein an oxidation peak appears near-0.8V as shown in figure 2, and corresponds to Cu vulcanization; performing cyclic voltammetry scanning for 40 circles within a voltage range of-0.5V to 1.0V to finish the vulcanization process of the sample to obtain Cu 2 S@NF；
g) For the prepared Cu 2 S@NF is cleaned and stored to obtain a self-supporting catalyst Cu 2 S@NF。
As shown in fig. 3, the standard PDF card JCPDS of the partial characteristic peaks and Ni in the sample: the 04-0850 is well matched with Cu, and other characteristic peaks 2 S standard PDF card JCPDS:65-2980, so the sample prepared by the method contains Cu 2 S。
As can be seen from fig. 4 and 5, the sample contains three elements of Ni, cu and S, which proves that the electrochemical method can realize the deposition and further vulcanization of Cu on NF.
Fig. 6 is an SEM image and a partial enlarged image of cu@nf, and it can be seen that bulk copper particles are uniformly deposited on the nickel foam under the potentiostatic method, and the adhesion is relatively stable.
FIG. 7 is Cu 2 SEM image and partial enlarged image of s@nf, the massive Cu particles were sulfidized into micrometer flower-shaped spheres of Cu after cyclic voltammetry treatment 2 S, particle size is about 5um.
Preparation of self-supporting catalyst
As in example 1, the self-supporting full-hydropower catalyst Cu was prepared by changing the number of sulfidation turns in step f) to 20 2 S@NF。
Preparation of self-supporting catalyst
As in example 1, the self-supporting full-hydropower catalyst Cu was prepared by changing the application potential in the step d) to-0.1V only 2 S@NF。
Example 4 preparation of self-supporting catalyst
As in example 1, the self-supporting full-hydropower catalyst Cu was prepared by changing the application potential in the step d) to-0.3V 2 S@NF。
[ example 5 ] full Desorption experiment one
The self-supporting full-water electrolysis catalysts Cu prepared in examples 1 to 4 were respectively 2 S@NF cuts a small section to be used as an electrode slice, and the working area of the electrode slice is controlled to be 1 multiplied by 1cm 2 The prepared electrode sheet was clamped by a clamping sheet electrode, placed in a three-electrode system, and OER and HER reactions were performed in a 1M KOH solution, and tested for LSV curve at a scan rate of 2mV/s.
The current density is calculated according to the electrode area and is plotted, and the current density is recorded to be 10mA/cm 2 The potential at that time, and linear fitting to obtain the Tafel slope. The test results are shown in FIGS. 8-11 and Table 1.
Table 1: self-supporting catalyst Cu 2 Determination of full water-splitting property of S@NF
Based on the numbers in the table above, the person skilled in the artIt can be seen that the present invention is superior to most non-noble metal electrocatalysts, whereas the self-supporting full-hydropower catalyst Cu in example 1 2 S@NF has the best catalytic activity of HER and OER.
FIGS. 8 and 9 are the self-supporting catalyst Cu of example 1 2 The HER polarization curves of S@NF, cu@NF and NF show that the catalyst prepared by the method has smaller overpotential and smaller Tafel slope under the same current density, and has better performance of catalyzing hydrogen evolution reaction in 1M KOH alkaline solution.
FIGS. 10 and 11 are self-supporting catalyst Cu of example 1 2 The OER polarization curves of S@NF, cu@NF and NF show that the catalyst prepared by the method has better performance of catalyzing oxygen evolution reaction in 1M KOH alkaline solution under the condition of smaller overpotential, namely lower voltage is needed under the same current density.
[ example 6 ] full Desorption experiment two
Constructing a two-electrode water electrolysis system, wherein an electrolyte solution is 0.1M KOH, and Cu is used for both a working electrode and a counter electrode 2 S@NF material, FIG. 12 shows the polarization curve of electrolyzed water of the system, and the current density reaches 10mA/cm 2 The voltage was 1.64V.
For the self-supporting full-water electrolysis catalyst Cu prepared in example 1 2 The stability test of S@NF is carried out, and the result is shown in FIG. 13, wherein the constant potential of 1.8V is applied, and the potential change is small after continuous operation for 20 hours, which indicates that the stability of the electrocatalyst prepared by the invention is better.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A self-supporting catalyst comprises a foam nickel substrate andcu supported on the foam nickel substrate 2 S particles, wherein the Cu 2 The S particles are in the shape of micron flower spheres.
2. The self-supporting catalyst of claim 1, wherein the Cu 2 The average particle diameter of the S particles was 5.+ -.3. Mu.m.
3. A process for the preparation of a self-supporting catalyst, preferably for the preparation of a self-supporting catalyst according to claim 1 or 2, comprising: and (3) using an electrochemical three-electrode system, taking foam nickel as a working electrode and a reaction substrate, and respectively carrying out reduction of copper ions and sulfuration of copper by a potentiostatic method and a cyclic voltammetry according to oxidation-reduction potential of copper to obtain the self-supported catalyst.
4. A method of preparation according to claim 3, characterized in that the method of preparation comprises:
step 1, cu 2+ Determination of reduction potential: immersing a working electrode foam nickel, a reference electrode and a counter electrode into an electrolyte solution containing copper ions by using an electrochemical three-electrode system, scanning in a negative voltage range by using an electrochemical cyclic voltammetry, and determining Cu 2+ The reduction peak of (a) is a;
step 2, electrochemical preparation of Cu@NF: in the electrochemical system of the step 1, adopting a potentiostatic method, and performing potentiostatic treatment by taking (a+/-0.2) and preferably (a+/-0.1) as application potentials to obtain Cu@NF;
step 3, cu 2 Electrochemical preparation of S@NF: immersing Cu@NF obtained in the step 2 serving as a working electrode into an electrolyte solution containing sulfur-containing inorganic matters, and scanning by adopting a cyclic voltammetry to obtain a sulfuration potential b of Cu; performing cyclic voltammetry scanning in the voltage range of (b+ -0.5) and preferably (b+ -0.3) to realize Cu vulcanization treatment to obtain Cu 2 S@NF self-supporting catalyst.
5. The method according to claim 4, wherein the pretreatment of the nickel foam is performed before step 1, and preferably the nickel foam is ultrasonically cleaned in an acid solution, an alcoholic solvent and distilled water, respectively.
6. The process according to claim 4, wherein,
in step 1, the electrolyte solution is a neutral solution, preferably a neutral salt solution; and/or the number of the groups of groups,
in step 1, the copper ions in the electrolyte solution originate from a water-soluble copper salt, preferably the molar concentration of the water-soluble copper salt in the electrolyte solution is 5-30mM; and/or the number of the groups of groups,
in the step 1, the reference electrode is selected from one of an Ag/AgCl electrode, a saturated calomel electrode and an Hg/HgO electrode; and/or the number of the groups of groups,
in step 1, the counter electrode is selected from one of Pt wire and graphite rod.
7. A process according to any one of claims 4 to 6, wherein,
in step 3, the sulfur-containing inorganic material is selected from NaHS, na 2 At least one of S; and/or the number of the groups of groups,
in step 3, the electrolyte solution is an alkaline aqueous solution; and/or the number of the groups of groups,
in step 3, the molar concentration of the sulfur-containing inorganic substance in the electrolyte solution is 1 to 15mM, preferably 3 to 8mM.
8. The process according to claim 7, wherein,
in the step 3, scanning is carried out within a potential range of-1.0 to-0.5V by adopting a cyclic voltammetry; and/or the number of the groups of groups,
in step 3, cyclic voltammetry scanning is performed for 20 to 60 cycles, preferably 30 to 50 cycles, during the vulcanization treatment.
9. A self-supporting catalyst obtainable by the process according to any one of claims 3 to 8.
10. Use of a self-supported catalyst according to claim 1 or 2 or a self-supported catalyst obtained by a process according to any one of claims 3 to 8 in the complete hydrolysis of water, preferably in alkaline conditions;
more preferably, an electrochemical three-electrode system comprising a working electrode, a reference electrode and a counter electrode is constructed to perform hydrogen evolution reaction and oxygen evolution reaction, wherein the self-supporting catalyst is used as the working electrode; alternatively, a two-electrode system comprising a working electrode and a counter electrode is constructed for full water dissolution, wherein the self-supporting catalyst is used as the working electrode and the counter electrode.
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