CN113981487B - High-entropy carbonate electrocatalyst and preparation method thereof - Google Patents

High-entropy carbonate electrocatalyst and preparation method thereof Download PDF

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CN113981487B
CN113981487B CN202111243143.1A CN202111243143A CN113981487B CN 113981487 B CN113981487 B CN 113981487B CN 202111243143 A CN202111243143 A CN 202111243143A CN 113981487 B CN113981487 B CN 113981487B
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CN113981487A (en
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卢超
李明明
张傲
汪玉洁
杨智
孔清泉
冯威
王小炼
安旭光
吴小强
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Chengdu University
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention provides a high-entropy carbonate electrocatalyst and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving inorganic salts of five metals of cobalt, chromium, iron, manganese and molybdenum in deionized water, adding a precipitator into the solution under the condition of stirring, and stirring for reaction to obtain a mixed solution; carrying out hydrothermal treatment on the mixed solution; washing the hydrothermal product, and drying to obtain high-entropy carbonate material (Co)αCrβFeγMnδMoε)CO3. The catalyst has the advantages of simple synthesis, low price, high catalytic activity, excellent catalytic stability and the like, and can effectively solve the problems of high price and poor catalytic activity of the existing catalyst.

Description

High-entropy carbonate electrocatalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a high-entropy carbonate electrocatalyst and a preparation method thereof.
Background
With the increasing global energy crisis and the environmental pollution problem, renewable clean energy is facing a great development opportunity, and people are dedicated to developing various novel energy storage devices (such as metal air batteries and fuel cells) to realize energy storage and conversion between chemical energy and electric energy. As a green, environment-friendly, clean and efficient secondary energy source, hydrogen is an ideal substitute for the traditional fossil fuelAnd (5) substituting the product. The hydrogen production by water electrolysis is an important way for obtaining hydrogen, the cathode hydrogen production efficiency mainly depends on the kinetic characteristics of the anode Oxygen Evolution Reaction (OER), and the method has the problems of slow reaction kinetics, high OER overpotential and the like, so that the speed and efficiency of the water electrolysis reaction are greatly inhibited, and the large-scale commercial application of the water electrolysis reaction is hindered. The OER electrocatalyst can effectively reduce the overpotential of the electrochemical reaction, reduce energy consumption and improve the electrode reaction rate, thereby improving the energy storage and conversion efficiency. The water electrolysis OER process relates to electron transfer, and the rapid electron conduction can ensure that the catalyst has good conductivity and is beneficial to the implementation of each element reaction in the electrocatalysis process; the more oxygen-containing intermediates ([ O ], [ OH ] and [ OOH ]) are formed on the surface of the catalyst and O2The faster the desorption, the higher the catalytic activity; the more active sites of the catalyst, the better the catalytic performance.
Conventional noble metal oxides such as IrO2And RuO2Although the excellent OER electrocatalytic activity is shown, the large-scale application of the OER electrocatalytic activity is limited by the expensive price and the scarcity of raw materials, so that the development of the OER electrocatalytic with high efficiency, stability, low price, easy availability and low overpotential becomes the key for hydrogen production by water electrolysis. In addition to the above noble metal-based electrocatalysts, electric catalysts such as alloys, phosphides, sulfides, carbides, metal oxides, metal hydroxides, carbon materials (graphene, carbon nanotubes, etc.), metal organic framework compounds (MOFs), etc. have been widely studied. However, the above materials have a problem that catalytic activity or catalytic stability is not desirable.
In recent years, high-entropy materials with high-entropy effects have attracted great attention of researchers. The components of the high-entropy material are metal elements, the high-entropy material generally refers to a multi-principal-element solid solution formed by 5 or more components, the elements are in an equimolar ratio or nearly equimolar ratio relationship, the multi-principal-element structural forming formula breaks through the single-principal-element forming concept of the traditional material, and the high-entropy material has high configuration entropy and excellent structural stability due to disordered arrangement of the principal elements. At present, high-entropy materials such as high-entropy alloy, high-entropy oxide, high-entropy carbide, high-entropy boride and high-entropy silicide are continuously explored due to excellent mechanical, electrical and magnetic properties, and become one of the research hotspots in the field of materials. However, the development of high-entropy carbonate and the research on the use of the high-entropy carbonate as an electrocatalyst are rarely reported, and if a high-entropy carbonate compound with excellent catalytic activity and catalytic stability and low production cost can be developed, the high-entropy carbonate compound has to generate a large market demand in the field of electrocatalysis.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-entropy carbonate electrocatalyst and a preparation method thereof, and the catalyst has the advantages of simple synthesis, low price, high catalytic activity, excellent catalytic stability and the like, and can effectively solve the problems of high price and poor catalytic activity of the existing catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a high-entropy carbonate electrocatalyst comprises the following steps:
(1) dissolving five metal inorganic salts of cobalt, chromium, iron, manganese and molybdenum in deionized water, then adding a precipitator into the solution under the condition of stirring, and stirring until the precipitator is dissolved to obtain a mixed solution;
(2) carrying out hydrothermal treatment on the mixed solution in the step (1);
(3) washing the hydrothermal product in the step (2), and then drying to obtain the high-entropy carbonate material (Co)αCrβFeγMnδMoε)CO3。
Further, the mole ratio of five elements of cobalt, chromium, iron, manganese and molybdenum in the step (1) is alpha: beta: γ: δ: epsilon is (1-4), (1-4) and (1-4).
Further, in the step (3), the high-entropy carbonate material (Co)αCrβFeγMnδMoε)CO3Alpha, beta, gamma, delta and epsilon are more than or equal to 8 percent and less than or equal to 40 percent.
Further, in the step (1), the precipitant is at least one of urea, ammonium bicarbonate and ammonium carbonate.
Further, the molar ratio of the precipitating agent to the total amount of the five metal ions in the step (1) is (6-15): 1.
Further, the stirring reaction time in the step (1) is 0.5-2 h.
Further, in the step (2), hydrothermal reaction is carried out for 12-24h at the temperature of 160-200 ℃.
Further, in the step (3), repeated cross-centrifugation washing is carried out on the hydrothermal product by using deionized water and absolute ethyl alcohol.
Further, in the step (3), the drying temperature is 60-80 ℃, and the drying time is 3-6 h.
A high-entropy carbonate electrocatalyst material is prepared by adopting the method.
The beneficial effect that above-mentioned scheme produced does:
1. high entropy carbonate Material (Co) in the present inventionαCrβFeγMnδMoε)CO3Has excellent OER electrocatalytic performance, and the d-charge electron configurations of the transition metal elements of Co, Cr, Fe, Mn and Mo are respectively 3d7、3d5、3d6、3d5、4d5The multi-body perturbation of the electronic structure reduces the overlap ratio of the d band and narrows the d band, the central position of the d band moves to the direction close to the Fermi level, the state density at the Fermi level is improved, the charge transfer of the carbonate material can be promoted, and the surface of the carbonate material can be enhanced to react with oxygen-containing intermediates ([ O ], [ OH ] and [ OOH ]) and O of the OER2Adsorption-desorption capacity of the adsorbent. Thus, by high entropy carbonate (Co)αCrβFeγMnδMoε)CO3The multi-body perturbation regulation of the electronic structure can endow the electronic structure with excellent OER catalytic activity and catalytic stability, so that the overpotential of the electronic structure in a 1mol/L potassium hydroxide solution is only 236.3mV, which indicates that the electronic structure is high in catalytic activity; after a long-time i-t test of 37000s, the current density is almost not attenuated, and the catalyst shows excellent stable durability.
2. High entropy carbonate Material (Co) in the present inventionαCrβFeγMnδMoε)CO3Has high thermodynamic and chemical stability, easily available raw materials, simple preparation process and convenient operationLow production cost and convenient market popularization.
Drawings
FIG. 1 is an XRD pattern of a high entropy carbonate electrocatalyst material in example 1;
FIG. 2 is a Mapping diagram of the elements of the high entropy carbonate electrocatalyst material in example 1;
FIG. 3 is an SEM image of a high entropy carbonate electrocatalyst material in example 1;
FIG. 4 is the LSV curve for the high entropy carbonate electrocatalyst material in example 1;
FIG. 5 is an i-t curve for a high entropy carbonate electrocatalyst material in example 1.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings.
Example 1
A preparation method of the high-entropy carbonate electrocatalyst comprises the following steps:
(1) inorganic salts of five metals of cobalt, chromium, iron, manganese and molybdenum are used as raw materials, and 0.498g of Co (CH) is weighed according to the molar ratio of the five elements of cobalt, chromium, iron, manganese and molybdenum being 1:1:1:13COO)2·4H2O、0.8gCr(NO3)3·9H2O、0.808g Fe(NO3)3·9H2O、0.396g MnCl2·4H2O and 0.353g (NH)4)6Mo7O24·4H2Dissolving O in 80mL of deionized water to form an inorganic salt mixed solution; 6.6g of urea (CO (NH)2)2) Dissolving the inorganic salt into 30mL of deionized water to obtain a precipitant solution, adding the precipitant solution into the inorganic salt mixed solution under the stirring condition, and stirring for 1h to obtain a reaction solution;
(2) pouring the reaction solution obtained in the step (1) into a closed reaction kettle, and carrying out hydrothermal reaction for 20 hours at the temperature of 180 ℃ to obtain a hydrothermal product;
(3) repeatedly carrying out cross centrifugal washing on the hydrothermal product obtained in the step (2) by using deionized water and absolute ethyl alcohol, and then carrying out vacuum drying for 4 hours at the temperature of 70 ℃ to obtain the high-entropy carbonate material (Co)0.2Cr0.2Fe0.2Mn0.2Mo0.2)CO3。
Example 2
A preparation method of the high-entropy carbonate electrocatalyst comprises the following steps:
(1) inorganic salt of five metals of cobalt, chromium, iron, manganese and molybdenum is used as a raw material, and 0.291g of Co (NO) is weighed according to the molar ratio of the five elements of cobalt, chromium, iron, manganese and molybdenum of 1:3:2:3:13)2·6H2O、1.2gCr(NO3)3·9H2O、0.541g FeCl3·6H2O、0.169g MnSO4·H2O and 1.236g (NH)4)6Mo7O24·4H2Dissolving O in 80mL of deionized water to form an inorganic salt mixed solution; 7.9g of ammonium bicarbonate (NH)4HCO3) Dissolving the inorganic salt into 30mL of deionized water to obtain a precipitant solution, adding the precipitant solution into the inorganic salt mixed solution under the stirring condition, and stirring for 1.5 hours to obtain a reaction solution;
(2) pouring the reaction solution obtained in the step (1) into a closed reaction kettle, and carrying out hydrothermal reaction for 12 hours at the temperature of 200 ℃ to obtain a hydrothermal product;
(3) repeatedly carrying out cross centrifugal washing on the hydrothermal product in the step (2) by using deionized water and absolute ethyl alcohol, and then carrying out vacuum drying for 3h at the temperature of 80 ℃ to obtain the high-entropy carbonate material (Co)0.1Cr0.3Fe0.2Mn0.3Mo0.1)CO3。
Example 3
A preparation method of the high-entropy carbonate electrocatalyst comprises the following steps:
(1) taking inorganic salts of five metals of cobalt, chromium, iron, manganese and molybdenum as raw materials, and respectively weighing 0.563g of CoSO according to the molar ratio of the five elements of cobalt, chromium, iron, manganese and molybdenum of 2:1:3:2:24·7H2O、0.267gCrCl3·6H2O、1.212g Fe(NO3)3·9H2O、0.574g Mn(NO3)2·6H2O and 2.472g (NH)4)6Mo7O24·4H2O, dissolved in 80mL to removeForming an inorganic salt mixed solution in the sub-water; 9.6g of ammonium carbonate ((NH)4)2CO3) Dissolving the inorganic salt into 30mL of deionized water to obtain a precipitant solution, adding the precipitant solution into the inorganic salt mixed solution under the stirring condition, and stirring for 2 hours to obtain a reaction solution;
(2) pouring the reaction solution obtained in the step (1) into a closed reaction kettle, and carrying out hydrothermal reaction at 160 ℃ for 24 hours to obtain a hydrothermal product;
(3) repeatedly and alternately centrifugally washing the hydrothermal product in the step (2) by using deionized water and absolute ethyl alcohol, and then drying for 6 hours in vacuum at the temperature of 60 ℃ to prepare the high-entropy carbonate material (Co)0.2Cr0.1Fe0.3Mn0.2Mo0.2)CO3。
Comparative example 1
A preparation method of the high-entropy carbonate electrocatalyst comprises the following steps:
(1) inorganic salts of five metals of cobalt, chromium, iron, manganese and zinc are taken as raw materials, and 0.498g of Co (CH) is weighed according to the molar ratio of the five elements of cobalt, chromium, iron, manganese and zinc of 1:1:1:13COO)2·4H2O、0.8gCr(NO3)3·9H2O、0.808g Fe(NO3)3·9H2O、0.396g MnCl2·4H2O and 0.576g ZnSO4·7H2Dissolving O in 80mL of deionized water to form an inorganic salt mixed solution; 6.6g of urea (CO (NH)2)2) Dissolving the inorganic salt into 30mL of deionized water to obtain a precipitant solution, adding the precipitant solution into the inorganic salt mixed solution under the stirring condition, and stirring for 1h to obtain a reaction solution;
(2) adding the reaction solution obtained in the step (1) into a closed reaction kettle, and carrying out hydrothermal reaction for 20 hours at 180 ℃ to obtain a hydrothermal product;
(3) repeatedly carrying out cross centrifugal washing on the hydrothermal product obtained in the step (2) by using deionized water and absolute ethyl alcohol, and then carrying out vacuum drying for 4 hours at the temperature of 70 ℃ to obtain the high-entropy carbonate material (Co)0.2Cr0.2Fe0.2Mn0.2Zn0.2)CO3。
Comparative example 2
A preparation method of the high-entropy carbonate electrocatalyst comprises the following steps:
(1) inorganic salts of five metals of cobalt, chromium, iron, manganese and molybdenum are used as raw materials, and 0.249g of Co (CH) is weighed according to the molar ratio of the five elements of cobalt, chromium, iron, manganese and molybdenum being 1:1:6:1:13COO)2·4H2O、0.4gCr(NO3)3·9H2O、2.424g Fe(NO3)3·9H2O、0.198g MnCl2·4H2O and 1.236g (NH)4)6Mo7O24·4H2Dissolving O in 80mL of deionized water to form an inorganic salt mixed solution; 6.6g of urea (CO (NH)2)2) Dissolving the inorganic salt into 30mL of deionized water to obtain a precipitant solution, adding the precipitant solution into the inorganic salt mixed solution under the stirring condition, and stirring for 1h to obtain a reaction solution;
(2) pouring the reaction solution obtained in the step (1) into a closed reaction kettle, and carrying out hydrothermal reaction for 20 hours at the temperature of 180 ℃ to obtain a hydrothermal product;
(3) repeatedly carrying out cross centrifugal washing on the hydrothermal product obtained in the step (2) by using deionized water and absolute ethyl alcohol, and then carrying out vacuum drying for 4 hours at the temperature of 70 ℃ to obtain the high-entropy carbonate material (Co)0.1Cr0.1Fe0.6Mn0.1Mo0.1)CO3。
Test examples
Working electrodes were prepared using the high-entropy carbonate materials of examples 1-3 and comparative examples 1-2, respectively, by the specific method: weighing 5mg of high-entropy carbonate, 1mg of conductive carbon powder, 600 mu L of deionized water, 200 mu L of absolute ethyl alcohol and 50 mu L of Nafion, mixing and stirring uniformly to prepare a mixed solution, dripping 20 mu L of the mixed solution on carbon paper by using a liquid transfer gun, and drying to obtain the carbon paper with the surface loaded with the catalyst, wherein the carbon paper is used as a working electrode. And then establishing a three-electrode system by using a mercury/mercury oxide (Hg/HgO) reference electrode, a platinum counter electrode and a carbon paper working electrode (arranged in a Pt electrode clamp) of which the surface is loaded with a catalyst, and testing the electrocatalytic performance of the catalyst in the working electrode by using an electrochemical workstation. Electrolyte adopted by the test system1mol/L potassium hydroxide solution at 10mA · cm-2The overpotential of the catalyst is tested under the current density (reflecting the catalytic activity), the current density retention rate of the catalyst is tested under the voltage of 0.8V and the operation is 37000s (reflecting the cycle durability), and the test results are shown in Table 1.
Table 1: overpotential statistics for different electrocatalysts
Overpotential Current density retention ratio
Example 1 236.3mV 98.7％
Example 2 243.6mV 96.8％
Example 3 248.2mV 95.2％
Comparative example 1 288.2mV 86.5％
Comparative example 2 281.3mV 88.2％
From the data in the table, it can be known that the electrocatalysts prepared in examples 1, 2 and 3 have lower overpotentials and higher current density retention rates after long-term cycling, which indicates that the electrocatalysts of the present invention have better electrocatalytic activity and stability.
As can be seen from the attached figure 1, the prepared high-entropy carbonate material has good crystallization property and high purity.
As can be seen from the attached figure 2, seven elements of Co, Cr, Fe, Mn, Mo, C and O in the high-entropy carbonate material are uniformly distributed and have no phenomenon of element segregation or enrichment, which shows that the material has uniform chemical components and structures, and the uniformly distributed active components become efficient active sites of OER reaction.
As can be seen from the attached figure 3, the high-entropy carbonate catalyst material has a large electrochemical activity specific surface area, and the surface exposed area and the loose structure can provide richer active sites for electrocatalytic reaction, and simultaneously provide favorable conditions for oxygen precipitation, so that the activity of the catalyst can be improved.
As can be seen from FIG. 4, the OER test was performed on a 1mol/L KOH solution with high entropy carbonate at 10mA cm-2The overpotential at the current density of (1) is only 236.3mV compared with that of Co in the prior art3O4Compared with catalysts such as (overpotential is 270mV), Co, Fe, Ni- (O) OH (overpotential is 270mV), NiP (overpotential is 309mV), Ni-MOF (overpotential is 320mV), and the like, the high-entropy carbonate in the application has lower overpotential, which shows that the high-entropy carbonate material synthesized by the one-step hydrothermal method can realize efficient electrocatalytic water decomposition under lower overpotential and has excellent OER catalytic activity.
As can be seen from FIG. 5, after 37000s long-time cycle test at 0.8V, the current density is almost not attenuated and can still reach 8.2mA cm-2This indicates that the electrocatalyst has excellent OER stability durability.

Claims (10)

1. A preparation method of a high-entropy carbonate electrocatalyst is characterized by comprising the following steps:
(1) dissolving inorganic salts of five metals of cobalt, chromium, iron, manganese and molybdenum in deionized water, adding a precipitator into the solution under the condition of stirring, and stirring for reaction to obtain a mixed solution;
(2) carrying out hydrothermal treatment on the mixed solution in the step (1);
(3) washing the hydrothermal product in the step (2), and then drying to obtain the high-entropy carbonate material (Co)αCrβFeγMnδMoε)CO3。
2. The method for preparing a high-entropy carbonate electrocatalyst according to claim 1, wherein the molar ratio of the five elements of cobalt, chromium, iron, manganese, and molybdenum in step (1) is α: beta: γ: δ: epsilon is (1-4), (1-4) and (1-4).
3. The method for preparing a high-entropy carbonate electrocatalyst according to claim 2, wherein in step (3) the high-entropy carbonate material (Co)αCrβFeγMnδMoε)CO3Alpha, beta, gamma, delta and epsilon are more than or equal to 8 percent and less than or equal to 40 percent.
4. A method of preparing a high entropy carbonate electrocatalyst according to claim 1, wherein the precipitant in step (1) is at least one of urea, ammonium bicarbonate and ammonium carbonate.
5. The method for preparing a high-entropy carbonate electrocatalyst according to claim 4, wherein the molar ratio of the precipitant to the total amount of the five metal ions in step (1) is (6-15): 1.
6. The method for preparing a high-entropy carbonate electrocatalyst according to claim 1, wherein the stirring reaction time in step (1) is from 0.5 to 2 hours.
7. The method for preparing a high-entropy carbonate electrocatalyst according to claim 1, wherein the hydrothermal reaction is performed at 160-200 ℃ for 12-24h in step (2).
8. The method for preparing a high-entropy carbonate electrocatalyst according to claim 1, wherein in step (3), the hydrothermal product is repeatedly subjected to cross-centrifugal washing with deionized water and absolute ethanol.
9. The method for preparing a high-entropy carbonate electrocatalyst according to claim 1, wherein the drying temperature in step (3) is 60 to 80 ℃ and the drying time is 3 to 6 hours.
10. A high-entropy carbonate electrocatalyst material, characterized in that it is prepared by the method for preparing a high-entropy carbonate electrocatalyst according to any one of claims 1 to 8.
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CN111701611A (en) * 2020-04-13 2020-09-25 南京工业大学 Bivalent copper carbon dioxide reduction catalyst based on carbonate synergistic effect and preparation method thereof
CN112643040A (en) * 2020-10-14 2021-04-13 南京大学 Method for preparing micro-nano medium-entropy and high-entropy material by laser ablation
CN113089135A (en) * 2021-04-08 2021-07-09 齐鲁工业大学 High-entropy zirconate inorganic fiber and preparation method thereof
CN113235115A (en) * 2021-04-20 2021-08-10 深圳大学 High-stability metal nanocluster catalyst and preparation method and application thereof

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