CN114635155A - Self-supporting core-shell structure catalyst and preparation method and application thereof - Google Patents
Self-supporting core-shell structure catalyst and preparation method and application thereof Download PDFInfo
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- CN114635155A CN114635155A CN202210168956.7A CN202210168956A CN114635155A CN 114635155 A CN114635155 A CN 114635155A CN 202210168956 A CN202210168956 A CN 202210168956A CN 114635155 A CN114635155 A CN 114635155A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
Abstract
The invention discloses a self-supporting core-shell structure catalyst, and a preparation method and application thereof, and belongs to the technical field of preparation of electrocatalysis materials. The invention solves the problem of poor activity and stability of the existing urea oxidation catalyst. According to the invention, nickel sulfide grown in situ on the self-supporting substrate is taken as a core, and the nickel sulfide is completely wrapped by sulfide, so that the Fermi level of a shell material is improved by a heterojunction formed by the nickel sulfide and the sulfide, and the catalytic activity is improved; and a built-in electric field at the interface provides a higher electron barrier to prevent electrons from entering a nuclear part, so that nickel sulfide is protectedThe structure can not be damaged in the electrochemical reaction, the catalyst can work for a long time, and the unification of high activity and high stability of the catalyst is realized, so that the catalyst has high urea oxidation catalytic activity and excellent stability at 10mA cm‑2Only 1.33V is needed at the current density of (2), and the activity is not obviously changed after the continuous operation for 24 hours.
Description
Technical Field
The invention relates to a self-supporting core-shell structure catalyst, a preparation method and application thereof, and belongs to the technical field of preparation of electrocatalysis materials.
Background
Fossil fuels have brought scientific culture to human beings, but they also bring environmental pollution and greenhouse effect. The use of fossil fuels by mankind is now on the rise daily, and the urgency for developing new clean energy sources is self-evident. The traditional primary fossil fuel (coal, petroleum, natural gas and the like) is still used as a main application energy source in the world to date, and particularly has an extremely high energy source proportion in developing countries. The problems of high use cost, low energy efficiency and high pollution caused by the method are used as an energy restriction bottleneck, the industrial development is greatly limited, and the inevitable influence on the global economy is generated.
The urea oxidation reaction is an anode reaction of direct urea fuel cells and a cathode reaction of urea electrolysis, the urea oxidation reaction can directly use urea as a fuel source of the fuel cells, the urea oxidation reaction provides a method for producing hydrogen by electrolysis, the urea oxidation reaction and the urea electrolysis reaction belong to novel energy technologies, and the urea oxidation reaction is a key for determining the performances of the urea oxidation reaction and the urea electrolysis reaction. Noble metal catalysts are generally considered the benchmark for urea oxidation, but with recent advances, non-noble metal catalysts stand out and the relatively lower cost can match or even exceed the performance of noble metal catalysts. However, the increased performance is still difficult to meet the current demand, and one reason for limiting the performance of the catalyst is derived from the number of catalytically active sites and the stability of the catalyst itself. The current mainstream urea oxidation catalysts mainly comprise nickel-based catalysts such as nickel phosphide, nickel nitride and the like, but their oxidation potential is still high and is accompanied by poor stability.
In order to enhance the activity of the catalyst, a great deal of researchers find that the activity of the catalyst can be improved by introducing the dissimilar metal elements, such as a nickel-molybdenum catalyst and a nickel-cobalt catalyst, the catalytic approach of the bimetal is helpful for improving the catalytic activity of urea oxidation, but the different activities among the metals always bring lower catalytic stability along with the rapid corrosion of materials.
In summary, it is important to provide a catalyst which has high catalytic activity for urea oxidation and does not cause structural damage in an electrochemical reaction and can be operated for a long period of time.
Disclosure of Invention
The invention provides a self-supporting core-shell structure catalyst, a preparation method and application thereof, aiming at solving the problems in the prior art.
The technical scheme of the invention is as follows:
a self-supporting core-shell structure catalyst takes foam nickel as a substrate, nano linear core-shell structure particles are attached to the surface of the substrate, nickel sulfide is taken as a core material in the core-shell structure, and one or more than two materials of molybdenum sulfide, tungsten sulfide, selenium sulfide, copper sulfide or manganese sulfide are taken as a shell material in the core-shell structure.
Further defined, the shell material thickness is between 5 and 50 nm.
The preparation method of the self-supporting core-shell structure catalyst comprises the following steps:
and 2, adding a vulcanizing agent and a shell material precursor, carrying out ultrasonic dispersion treatment for 10-30min until solid powder is completely dissolved, sealing the polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a constant-temperature oven, heating for reaction to obtain a foamed nickel substrate product, cleaning the foamed nickel substrate product for 3-5 times by using ultrapure water, and airing the foamed nickel substrate product in the air to obtain the self-supporting core-shell structure catalyst.
Further limiting, the area of the foam nickel cut in the step 1 is 1cm2-30cm2The thickness is 1mm-5 mm.
Further limiting, the heating reaction conditions in the step 2 are as follows: the temperature is 220 ℃ and 250 ℃, and the heat preservation time is 12-24 h.
Further limited, the vulcanizing agent in the step 2 is thiourea, sulfur monochloride or sulfur.
Further limiting, the mass ratio of the adding amount of the vulcanizing agent to the foamed nickel in the step 2 is 1: (0.7-7).
And further limiting, in the step 2, the precursor of the shell layer material is one or more of sodium molybdate, sodium tungstate, selenious acid, copper oxide and manganese oxide which are mixed in any proportion.
Further limiting, in the step 2, the mass ratio of the added amount of the precursor of the shell layer material to the foamed nickel is 1: (1-10).
The self-supporting core-shell structure catalyst is applied to preparing electrodes.
The invention has the following beneficial effects:
according to the invention, nickel sulfide growing in situ on the self-supporting substrate is taken as a core, and the nickel sulfide is completely wrapped by sulfide, so that the Fermi level of a shell material is improved by a heterojunction formed by the nickel sulfide and the sulfide, and the catalytic activity is improved; and a built-in electric field at the interface provides a higher electron barrier, prevents electrons from entering a nuclear part, protects nickel sulfide, prevents the structure from being damaged in an electrochemical reaction, and ensures that the catalyst can work for a long time. The self-supporting substrate foamed nickel has a large specific surface area, a large number of active sites are provided for urea oxidation, the defects that the specific surface area of the existing commercial catalyst in a powder form is small and a large number of conductive carbon is needed to be supplemented are overcome, the unification of high activity and high stability is realized, so that the catalyst has high urea oxidation catalytic activity and excellent stability, and the urea oxidation catalytic activity is 10mAcm-2Only needs 1.33V under the current density of (2), and is continuously operatedThe activity did not change significantly after 24 h. In addition, the preparation method of the catalyst provided by the invention is simple and feasible, convenient to collect and suitable for large-scale production.
Drawings
FIG. 1 is an SEM photograph of a self-supported core-shell catalyst obtained in example 1;
FIG. 2 is a TEM photograph of a self-supported core-shell catalyst obtained in example 1;
FIG. 3 is a graph comparing electrochemical performance of the self-supported core-shell catalyst obtained in example 1 and the catalyst obtained in comparative example, wherein a is a linear voltammogram comparison graph, b is an electrochemical impedance comparison graph at 1.35V, c is a Tafel curve comparison graph, and d is a current density of 10mAcm-2Electrochemical stability comparison graph below.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1:
(1) putting foamed nickel with the thickness of 2mm and the size of 3 x 4cm into a cleaning agent for ultrasonic dispersion treatment for 30min, taking out the foamed nickel, vertically putting the foamed nickel into a 100ml polytetrafluoroethylene lining, and adding 60ml of ultrapure water;
(2) adding 200mg of thiourea and 60mg of sodium molybdate, carrying out ultrasonic dispersion treatment for 30min until solid powder is completely dissolved, sealing a polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a constant-temperature oven, continuously reacting for 18h at 240 ℃ to obtain a foamed nickel substrate product, cleaning the foamed nickel substrate product for 3-5 times by using ultrapure water, and airing the foamed nickel substrate product in the air to obtain a self-supporting core-shell structure catalyst, namely Ni for short3S2@MoS2CS。
The nickel sulfide core material of the self-supporting core-shell structure catalyst obtained in the embodiment is of a nanowire structure, the diameter of the nanowire structure is about 80nm, and the thickness of the molybdenum sulfide shell material is about 20 nm.
The microstructure characterization results of the self-supported core-shell structure catalyst obtained in this example are shown in fig. 1 and 2, and it can be seen from fig. 1 that the obtained catalystThe oxidant presents a nano-wire structure and is stably and uniformly distributed on the surface of the foamed nickel, and the nano-wire Ni can be known from the graph of 2a-b3S2@MoS2The CS sample presents a remarkable core-shell structure, and only MoS is contained in the shell layer of the outer layer as can be seen from FIGS. 2c-f2And (4) distribution. As can be seen from FIGS. 2g-h, comparative sample Ni3S2The nanowire-like structure is also present, indicating that the loaded outer sulfide does not change the shape of the core material.
Example 2:
(1) putting foamed nickel with the thickness of 2mm and the size of 3 x 4cm into a cleaning agent for ultrasonic dispersion treatment for 30min, taking out the foamed nickel, vertically putting the foamed nickel into a 100ml polytetrafluoroethylene lining, and adding 60ml of ultrapure water;
(2) adding 200mg of thiourea and 600mg of sodium molybdate, carrying out ultrasonic dispersion treatment for 30min until solid powder is completely dissolved, sealing a polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a constant-temperature oven, continuously reacting for 18h at 240 ℃ to obtain a foamed nickel substrate product, cleaning for 3-5 times by using ultrapure water, and airing in the air to obtain the self-supporting core-shell structure catalyst.
Comparative example 1:
(1) putting foamed nickel with the thickness of 2mm and the size of 3 x 4cm into a cleaning agent for ultrasonic dispersion treatment for 30min, taking out the foamed nickel, vertically putting the foamed nickel into a 100ml polytetrafluoroethylene lining, and adding 60ml of ultrapure water;
(2) adding 200mg of thiourea, performing ultrasonic dispersion treatment for 30min until solid powder is completely dissolved, sealing a polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a constant-temperature oven, continuously reacting for 18h at 240 ℃ to obtain a foamed nickel substrate product, cleaning the foamed nickel substrate product for 3-5 times by using ultrapure water, and drying the foamed nickel substrate product in the air to obtain a self-supporting core-shell structure catalyst, namely Ni for short3S2。
Comparative example 2:
(1) mixing 600mg of sodium molybdate with 200mg of thiourea, adding 60ml of water, and carrying out ultrasonic treatment for 30min until the solid is completely dissolved;
(2) sealing the mixed solution obtained in the step 1 in a 100ml polytetrafluoroethylene lining, transferring the mixed solution into a constant-temperature oven, and continuously reacting for 18h at 240 ℃;
(3) centrifuging the product obtained in the step 2 by using water and absolute ethyl alcoholCleaning, collecting, and drying at 60 deg.C in vacuum oven to obtain powder catalyst, MoS for short2。
Effect example 1:
for the self-supporting core-shell structure catalyst obtained in example 1, Ni obtained in comparative example 13S2And MoS obtained in comparative example 22The electrochemical properties of the catalyst are characterized and compared, and the results are shown as a and b in fig. 3, it can be known from the graph a that the sample curves of the examples 1 and 2 are more than the comparative examples 1 and 2 in the linear sweep voltammetry curve, the catalytic activity is greatly improved compared with that of the core material and the shell material which are independent, and the urea oxidation capability of the catalyst is greatly improved due to the core-shell structure formed by the samples of the examples 1 and 2. As can be seen from fig. b, the charge transfer resistance of the catalyst forming the core-shell structure is smaller than that of the sample of the comparative example, which indicates that the core-shell structure contributes to the rapid transfer of charges during the catalytic reaction.
For the self-supporting core-shell structure catalyst obtained in example 1, Ni obtained in comparative example 13S2And MoS obtained in comparative example 22The catalytic performance of the catalyst is characterized and compared, the results are shown as c and d in fig. 3, the Tafel slope of the core-shell structure catalyst is far smaller than that of the comparative example, which shows that the core-shell structure catalyst is more beneficial to urea oxidation reaction in the reaction process, and the core-shell structure catalyst has excellent electrochemical stability at 10 mA/cm-2After 24 hours of continuous operation at current density, no significant voltage decay occurred, and the performance was more stable than the two samples of the comparative example.
Effect example 2:
the electrochemical properties and the catalytic properties of the catalysts obtained in example 1, example 2, comparative example 1 and comparative example 2 were compared, and the results are shown in the following table:
as is clear from the table, examples 1 and 2 exhibited a current density of 10mAcm-2The potential is much lower than that of comparative examples 1 and 2, which shows that the energy required for the catalyst of the example to start the catalytic reaction is much lower; the electrochemical impedance of the examples at 1.35vvs. rhe is much lower than the comparative sample, indicating that the charge transfer rate is higher on the example sample at this voltage; the Tafel slopes of examples 1, 2 are lower than comparative examples 1, 2, indicating that urea oxidation reactions are more likely to occur on the example samples.
Claims (10)
1. The self-supporting core-shell structure catalyst is characterized in that foam nickel is used as a substrate, nano linear core-shell structure particles are attached to the surface of the substrate, nickel sulfide is used as a core material of the core-shell structure, and one or more than two materials of molybdenum sulfide, tungsten sulfide, selenium sulfide, copper sulfide or manganese sulfide are used as shell materials of the core-shell structure.
2. The self-supporting core-shell structured catalyst according to claim 1, wherein the shell material has a thickness of 5 to 50 nm.
3. A process for the preparation of a self-supporting core-shell structured catalyst according to claim 1, comprising the steps of:
step 1, placing the cut foam nickel into a cleaning agent for ultrasonic dispersion treatment for 30-60min, taking out the foam nickel, vertically placing the foam nickel into a polytetrafluoroethylene lining, adding ultrapure water which submerges the top end of the foam nickel, and keeping the solution to reach 60% -80% of the total volume of the polytetrafluoroethylene lining;
and 2, adding a vulcanizing agent and a shell material precursor, performing ultrasonic dispersion treatment for 10-30min until solid powder is completely dissolved, sealing the polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining into a constant-temperature oven, performing heating reaction to obtain a foamed nickel substrate product, cleaning the foamed nickel substrate product for 3-5 times by using ultrapure water, and drying the foamed nickel substrate product in the air to obtain the self-supporting core-shell structure catalyst.
4. The method for preparing the self-supporting core-shell structure catalyst according to claim 3, wherein the area of the foam nickel cut in the step 1 is 1cm2-30 cm2The thickness is 1mm-5 mm.
5. The preparation method of the self-supporting core-shell structure catalyst according to claim 3, wherein the heating reaction conditions in the step 2 are as follows: the temperature is 220 ℃ and 250 ℃, and the heat preservation time is 12-24 h.
6. The method for preparing a self-supporting core-shell structure catalyst according to claim 3, wherein the vulcanizing agent in the step 2 is thiourea, sulfur monochloride or sulfur.
7. The preparation method of the self-supporting core-shell structure catalyst according to claim 3 or 6, wherein the mass ratio of the addition amount of the vulcanizing agent to the nickel foam is 1: (0.7-7).
8. The method for preparing a self-supporting core-shell catalyst according to claim 3, wherein the precursor of the shell layer material in the step 2 is sodium molybdate, and one or more of sodium tungstate, selenious acid, copper oxide and manganese oxide are mixed in any proportion.
9. The preparation method of the self-supporting core-shell structure catalyst according to claim 3 or 8, wherein the mass ratio of the addition amount of the precursor of the shell layer material to the nickel foam in the step 2 is 1 (1-10).
10. Use of a self-supporting core-shell structured catalyst according to claim 1 for the preparation of an electrode.
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