CN113061934B - High-entropy perovskite hollow nanotube efficient oxygen evolution reaction catalytic material and preparation method thereof - Google Patents
High-entropy perovskite hollow nanotube efficient oxygen evolution reaction catalytic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-entropy perovskite hollow nanotube high-efficiency oxygen evolution reaction catalytic material and a preparation method thereof, belonging to the technical field of electrocatalysis. The perovskite oxide nano particles are used as catalytic active sites, the hollow tubular structure not only increases the contact area with the electrolyte, is beneficial to the diffusion of the electrolyte and the desorption of gas, improves the catalytic reaction efficiency, has excellent catalytic oxygen evolution performance under the alkaline condition, and has the oxygen evolution rate superior to that of commercial RuO2And has good application prospect.
Description
Technical Field
The invention relates to a high-entropy perovskite hollow nanotube high-efficiency oxygen evolution reaction catalytic material and a preparation method thereof, belonging to the technical field of electrocatalysis.
Background
In recent years, as the population continues to increase to cause rapid consumption of energy and the problem of environmental pollution due to the use of fossil fuels is becoming more serious, there is an urgent need to develop more environmentally friendly energy sources. Research has shown that hydrogen combustion per unit mass produces energy up to 2.5 times that of gasoline and water is the only product of hydrogen combustion, and hydrogen has proven to be an ideal energy carrier.
Electrocatalytic hydrolysis technology is of great interest because of its purity of product, high conversion efficiency, simple equipment, etc. The theoretical voltage of water decomposition at room temperature is 1.23V, but the catalytic reaction is easily influenced by temperature, electrolyte, electrode materials and the like, the actually required voltage is often higher than 1.23V, and the existence of overvoltage can cause excessive energy consumption. The high-efficiency catalyst can reduce the reaction energy barrier and accelerate the electrocatalytic hydrolysis process. At present, Ru and Ru oxides are the most efficient electrocatalysts for oxygen evolution reaction, however, the noble metal catalysts are high in price and are scarce in content, which greatly limits the commercial application of the noble metal catalysts. Therefore, the development of a non-noble metal oxygen evolution catalyst which is abundant in reserves, low in price, efficient and durable is a research hotspot of oxygen evolution reaction.
High activity non-noble metal OER catalysts have been studied in the last decade, including carbon-based catalysts, metal oxides, metal carbides, and all appear to be comparable to RuO2、IrO2Among these non-noble metal catalysts, perovskite oxides have gained wide attention in the field of OER catalysis due to their simple preparation and good thermal stability.
Disclosure of Invention
Technical problem
The existing noble metal oxygen evolution reaction catalyst has good performance but higher cost, and the catalytic activity and the stability of a non-noble metal catalyst are relatively poorer.
Technical scheme
The invention provides a catalyst based on (La)xSr1-x)(FeyCozNi1-y-z)O3The method comprises the steps of constructing five-membered LaSrFeCoNi organic nano-fibers by an electrostatic spinning method, and then controlling an oxidation process to obtain the high-entropy perovskite type (La) hollow nano-tube high-efficiency catalytic oxygen evolution reaction materialxSr1-x)(FeyCozNi1-y-z)O3the/H-NTs electrolyzes the water catalytic material. The method has low cost, is simple and easy to obtain, and obtains the (La)xSr1-x)(FeyCozNi1-y-z)O3the/H-NTs catalytic oxygen evolution reaction material has excellent oxygen evolution activity under an alkaline condition and good stability.
The chemical composition, morphology and other factors of the catalyst have a crucial influence on the catalytic performance. The catalytic activity of the catalyst can be improved by adjusting the chemical composition of the catalyst and designing a special nano structure. On one hand, the nano structure of the material is regulated and controlled by controlling the ratio of the catalyst precursor to the metal salt, and the special nano structure is formed, so that the active specific surface area of the material is improved. On the other hand, by regulating and controlling the composition of the metal at the AB site of the perovskite material, the composition of different defect structures and oxygen vacancies can be promoted so as to improve the catalytic activity of the catalyst. The hollow nanotube structure can effectively improve the mass transfer capacity and the electron transfer efficiency of the catalyst in the oxygen evolution reaction process, thereby improving the catalytic activity.
The first purpose of the invention is to provide a method for preparing a non-noble metal element-based high-entropy perovskite type hollow nanotube catalytic oxygen evolution reaction material, which comprises the following steps:
(1) dispersing lanthanum salt, strontium salt, ferric salt, cobalt salt, nickel salt and a nanofiber precursor in an organic solvent to prepare a spinning solution; then preparing a nanofiber membrane through electrostatic spinning;
(2) and (2) carrying out calcination pre-oxidation on the nanofiber membrane obtained in the step (1), and then carrying out calcination oxidation in air by temperature programming to obtain the high-entropy perovskite hollow nanotube efficient catalytic oxygen evolution reaction material.
In an embodiment of the present invention, the nanofiber precursor in step (1) is one or more of polyacrylonitrile, polyvinylpyrrolidone, and polyvinyl alcohol.
In one embodiment of the invention, the mass fraction of the nanofiber precursor in the spinning solution in the step (1) is 8-20 wt%.
In one embodiment of the present invention, the lanthanum salt in step (1) is one or more of lanthanum nitrate and lanthanum chloride.
In one embodiment of the present invention, the strontium salt in step (1) is one or more of strontium nitrate and strontium chloride.
In one embodiment of the present invention, the iron salt in step (1) is one or more of ferric nitrate, ferric chloride and ferric acetate.
In one embodiment of the present invention, the cobalt salt in step (1) is one or more of cobalt nitrate, cobalt chloride and cobalt acetate.
In one embodiment of the present invention, the nickel salt in step (1) is one or more of nickel nitrate, nickel chloride and nickel acetate.
In one embodiment of the invention, the molar ratio of the lanthanum metal salt at the A site to the strontium salt in the spinning solution in the step (1) is 1 (0.5-2). One of 1:1, 1:2, 1:0.5 and 1:1.5 can be selected specifically, and the preferred ratio is 1: 1; the molar ratio of the metal iron salt, the cobalt salt and the nickel salt at the B site is 1 (0.2-3) to 0.2-3, and one of 1:1:1, 1:2:1, 1:3:1, 1:1:2, 1:2:2, 1:0.5:0.5 and 1:1:0.5 can be selected specifically, wherein the preferable ratio is 1:3: 1.
In one embodiment of the invention, the total molar concentration of metal salts (lanthanum salt, strontium salt, iron salt, cobalt salt and nickel salt) in the spinning solution in the step (1) is 0.1-0.3 mmol/g; preferably 0.2 mmol/g.
In one embodiment of the invention, the electrostatic spinning in step (1) has parameters of 15-25 kV spinning voltage, 10-20 cm distance between the receiving device and the spinning needle, and 0.01-0.10 mL/min solution flow rate.
In one embodiment of the present invention, the solvent in step (1) is one or more selected from N, N-dimethylformamide, dimethyl sulfoxide, ethanol, water, and acetone.
In one embodiment of the invention, the calcination pre-oxidation in the step (2) is performed by heating to 180-300 ℃ at a heating rate of 2-20 ℃/min, and performing heat preservation calcination for 2-4 h.
In one embodiment of the present invention, the heating rate is preferably one or more of 2 ℃/min, 5 ℃/min, 10 ℃/min, and 20 ℃/min.
In one embodiment of the present invention, the temperature of the maintained calcination temperature for the calcination and pre-oxidation in the step (2) is preferably 200 ℃.
In one embodiment of the present invention, the calcination pre-oxidation in step (2) is performed in an air atmosphere.
In an embodiment of the present invention, the calcining and oxidizing in step (2) refers to calcining at 400-1000 ℃ for 2-4 hours.
In one embodiment of the present invention, the temperature of the calcination carbonization is preferably 800 ℃.
In an embodiment of the present invention, the method specifically includes the following steps:
(1) preparing a nanofiber membrane containing lanthanum, strontium, iron, cobalt and nickel: adding lanthanum salt, strontium salt, ferric salt, cobalt salt and nickel salt into an N, N-dimethylformamide/ethanol solution (DMF/ethanol mass ratio is 1:1) of polyvinylpyrrolidone, uniformly stirring, and spinning the solution by adopting an electrostatic spinning method to obtain a LaSrFeCoNi/PVP nano fiber membrane;
(2) calcining the LaSrFeCoNi/PVP nanofiber membrane prepared in the step (1), heating to 180-300 ℃ at a heating rate of 2-20 ℃/min, and preserving heat for 2-4 hours in an air atmosphere to perform pre-oxidation; after the heat preservation is finished, heating to 400-1000 ℃ at the speed of 2-20 ℃/min in the air atmosphere, and preserving the heat for 2-4 hours; after the heat preservation is finished, naturally cooling to room temperature to obtain the high-entropy perovskite hollow nanotube oxygen evolution reaction catalytic material (La)xSr1-x)(FeyCozNi1-y-z)O3/H-NTs。
In one embodiment of the invention, the calcination in step (2) is to place the nano-fiber in a corundum boat and place the corundum boat in the middle of a tube furnace for calcination.
The second purpose of the invention is to provide a high-entropy perovskite type hollow nanotube structure catalytic oxygen evolution reaction material (La) based on non-noble metal LaSrFeCoNi by utilizing the preparation methodxSr1-x)(FeyCozNi1-y-z)O3/H-NTs。
In one embodiment of the present invention, the LaSrFeCoNi element is present in the form of a perovskite oxide (ABO) in the electrolyzed water catalytic material3)。
In one embodiment of the present invention, the multi-stage structure includes one-dimensional carbon nanofibers, in-situ grown carbon nanotubes, and metal nanoparticles.
The third purpose of the invention is to apply the high-entropy perovskite hollow nanotube material to the field of catalytic oxygen evolution reaction.
The fourth purpose of the invention is to provide a method for catalyzing oxygen evolution reaction, which uses the high-entropy perovskite hollow nanotube catalytic material as a catalyst.
The invention has the beneficial effects that:
according to the invention, multiple AB-site metals are introduced, the organic nano-fiber with multi-element doping is obtained by an electrostatic spinning method, and the high-temperature calcination is carried out to obtain the perovskite type hollow nano-tube catalytic oxygen evolution reaction material with a high-entropy structure, so that the experimental method is simple and has repeatability.
The invention prepares the high-entropy perovskite type hollow nanotube electrocatalyst by combining an electrostatic spinning method and controllable high-temperature calcination, wherein perovskite oxide nanoparticles are used as catalytic active sites, the hollow tubular structure not only increases the contact area with electrolyte and improves the catalytic reaction efficiency, but also the crystal form of the high-entropy perovskite has higher stability. And the doping of AB site metal enables the hollow tube to generate a large amount of oxygen vacancies, and the close contact of the vacancies among the nano particles also enhances the electron transmission rate in the catalytic reaction, thereby being beneficial to improving the catalytic activity.
The invention can obtain the high-entropy perovskite hollow nanotube catalyst with different shapes and catalytic performances by flexibly regulating and controlling different reaction parameters.
Drawings
FIG. 1 shows (La) obtained in example 10.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Scanning electron micrographs of/H-NTs electrocatalytic material.
FIG. 2 shows (La) obtained in example 10.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Transmission electron microscopy of the/H-NTs electrocatalytic material.
FIG. 3 shows (La) obtained in example 10.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3X-ray diffraction pattern of/H-NTs electrocatalytic material.
FIG. 4 shows (La) obtained in example 10.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs and commercial RuO0.2Electrocatalytic performance test in alkaline electrolyte in 1M KOH. (a) Is (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs and commercial RuO2Polarization curve of oxygen evolution reaction of the electrode; (b) is (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs and commercial RuO2Tafel slope plot of oxygen evolution reaction of the electrode; (c) is (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The electrochemical impedance diagram of the/H-NTs, and the test voltage is open-circuit voltage; (d) is (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The overpotential of the test is 10mV according to the time current response curve of/H-NTs.
FIG. 5 shows (La) obtained in example 20.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3/H-NTs-600、(La0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs-700 and (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Polarization curve of the oxygen evolution reaction of/H-NTs-900 in 1M KOH.
FIG. 6 is a scanning electron micrograph of LaSrFeCoNi/CNFs obtained in comparative example 1.
FIG. 7 is a polarization curve of oxygen evolution reaction of the LaSrFeCoNi/CNFs electro-catalytic material obtained in comparative example 1 in 1M KOH.
Detailed Description
For a better understanding of the present invention, the following further illustrates the contents of the invention with reference to examples, but the contents of the invention are not limited to the examples given below.
The H-NTs referred to in the present invention are hollow carbon nanotubes.
Example 1:
(1) adding 1mmol of lanthanum nitrate, 1mmol of strontium nitrate, 0.4mmol of ferric nitrate, 1.2mmol of cobalt nitrate and 0.4mmol of nickel nitrate into 20g of a mixed solution of polyvinylpyrrolidone with the mass fraction of 10 wt% (namely, the total metal molar ratio concentration is 0.2mmol/g) and ethanol (DMF: ethanol mass ratio is 1:1), uniformly stirring by magnetic force, spinning the solution by an electrostatic spinning method, controlling the spinning voltage to be 18KV, controlling the distance from a roller of a receiving device to a spinning needle point to be 16cm, and controlling the solution flow rate to be 0.2mL/min, thereby obtaining the LaSroNi/PVP nano fiber membrane.
(2) 0.2g of the prepared LaSrFeCoNi/PVP nanofiber membrane is placed in a corundum boat and is placed in the middle of a tube furnace. The temperature is raised to 200 ℃ at the heating rate of 5 ℃/min, and the pre-oxidation is carried out by keeping the temperature for 3 hours in the air atmosphere. After the heat preservation is finished, the temperature is raised to 800 ℃ at the speed of 5 ℃/min, and after the temperature reaches 800 ℃, the heat preservation is carried out for 3 hours. After the heat preservation is finished, naturally cooling to room temperature to obtain (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3the/H-NTs electrocatalytic material.
For the (La) obtained0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3the/H-NTs electrocatalytic material is shot by a scanning electron microscope, and figure 1 is (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Scanning Electron microscopy of/H-NTs, as can be seen from FIG. 1, (La) prepared by electrospinning and subsequent thermal treatment0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Nanoparticle assembled hollow nanotubes. The length of the clear hollow nanotube is hundreds of nanometers, and the average diameter of the clear hollow nanotube is 70-120 nm.
For the (La) obtained0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The transmission electron microscope is shot by the/H-NTs electrocatalytic material, and figure 2 is (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3In the transmission electron microscope image of/H-NTs, as can be seen from FIG. 2, all the carbon in the organic nanofibers is removed, a one-dimensional hollow nanotube structure with a hierarchical structure is formed by connecting nanoparticles with the size of 20-40nm, and the caliber of the tube is 100 nm.
For the (La) obtained0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The electro-catalytic material/H-NTs was subjected to X-ray diffraction test, and FIG. 3 shows (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3X-ray diffraction pattern of/H-NTs, as can be seen from FIG. 3, (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Diffraction peaks of/H-NTs and LaCoO3、La0.7Sr0.3Co0.8Fe0.2O3Diffraction peaks of the perovskite crystal forms are basically consistent, and the prepared material is a perovskite oxide.
To prepare (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The catalyst ink prepared from the/H-NTs electro-catalysis material is dripped on a glassy carbon electrode to be used as a working electrode, and the activity of the oxygen evolution reaction is tested in a 1M KOH solution by using a standard three-electrode system.
FIG. 4 shows (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs and commercial RuO2Graph of electrocatalytic performance test in 1M KOH. Wherein, FIG. 4(a) is (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs and commercial RuO2Polarization curve of oxygen evolution reaction of electrode in 1M KOH, current density of 10mA cm-2Next, commercial RuO2And (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The overpotentials for the oxygen evolution reaction of the/H-NTs are 405mV and 350mV (vs. RHE), (La.R.) (0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The oxygen evolution performance of the/H-NTs electrocatalytic material is superior to that of the commercial RuO2。
FIG. 4(b) shows (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Tafel slope plot for/H-NTs and commercial RuO2, as can be seen in FIG. 4(b), (La-NTs0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs at 10mA cm-2The Tafel slope of the nearby oxygen evolution reaction is only 78mV dec-1Far below commercial RuO2138mV dec-1. FIGS. 4(a) and 4(b) show (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The basic oxygen evolution performance of the/H-NTs electro-catalytic material is far superior to that of the commercial RuO2。
FIG. 4(c) is a graph showing the test under the open circuit voltage (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Electrochemical Impedance Spectroscopy (EIS) of/H-NTs, as can be seen from FIG. 4(c), (La-NTs)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The charge transfer resistance (Rct) value of/H-NTs is only 36.5. omega. indicating (La-NTs)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3the/H-NTs has higher electron transmission rate.
FIG. 4(d) shows (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Time current response curve of/H-NTs at an overpotential of 10mV (vs. RHE), as can be seen in FIG. 4(d), after 20 hours of reaction (La. RHE)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The catalytic activity of the/H-NTs catalytic material is still maintained by 70 percent, which shows that the (La) is0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3the/H-NTs catalytic material has good stability.
Example 2 investigation of the effect of calcination temperature on catalytic materials
Step (1) is the same as in example 1;
and (2) putting 0.2g of the prepared LaSrFeCoNi/PVP nanofiber membrane into a corundum boat, and placing the corundum boat in the middle of a tube furnace. The temperature is raised to 200 ℃ at the heating rate of 5 ℃/min, and the pre-oxidation is carried out by keeping the temperature for 3 hours in the air atmosphere. After the heat preservation is finished, the temperature is raised to 600 ℃, 700 ℃ and 900 ℃ at the speed of 5 ℃/min in the argon atmosphere, and the heat preservation is carried out for 3 hours. After the heat preservation is finished, naturally cooling to room temperature to obtain (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3/H-NTs-600、(La0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs-700 and (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3the/H-NTs-900 catalytic material.
Tested as in example 1 (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3/H-NTs-600、(La0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs-700 and (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The basic oxygen evolution performance of the/H-NTs-800 catalytic material.
FIG. 5 shows (La) respectively0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3/H-NTs-600、(La0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs-700 and (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Polarization curve of the oxygen evolution reaction of/H-NTs-900 in 1M KOH. As can be seen from FIG. 5, the current density was 10mA cm-2Below, (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3/H-NTs-600、(La0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs-700 and (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The overpotentials for the oxygen evolution reaction of/H-NTs-900 were 390mV, 380mV and 405mV (vs. RHE), respectively. FIG. 5 shows that (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3H-NTs-600 and (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The oxygen evolution reaction activity of the/H-NTs-700 electrocatalytic material is higher than that of the commercial RuO2. But the catalytic material obtained has weaker catalytic oxygen evolution reaction performance (the overpotential is 350mV) compared with the catalytic material obtained in example 1 at 800 ℃.
Example 3 investigation of the Effect of the Metal salt dosage ratio conditions on the catalytic Material
Step (ii) of(1) With reference to example 1, La was produced by replacing the molar ratios of the B-site metals of iron nitrate, cobalt nitrate and nickel nitrate with 3:4:3(0.24g of iron nitrate, 0.23g of cobalt nitrate and 0.17g of nickel nitrate) and 1:1:1(0.27g of iron nitrate, 0.19g of cobalt nitrate and 0.19g of nickel nitrate), respectively, and keeping the other conditions unchanged0.5Sr0.5Fe0.3Co0.4Ni0.3PVP nanofiber membrane and La0.5Sr0.5Fe0.33Co0.33Ni0.33PVP nanometer fiber film.
Step (2) was carried out in the same manner as in example 1 to obtain (La) respectively0.5Sr0.5)(Fe0.3Co0.4Ni0.3)O3H-NTs and (La)0.5Sr0.5)(Fe0.33Co0.33Ni0.33)O3the/H-NTs catalytic material.
Tested as in example 1 (La)0.5Sr0.5)(Fe0.3Co0.4Ni0.3)O3H-NTs and (La)0.5Sr0.5)(Fe0.33Co0.33Ni0.33)O3Basic Oxygen Evolution (OER) performance of the/H-NTs catalytic material.
The results are shown in Table 1.
TABLE 1 Performance results for catalyst materials obtained with different metal salt dosage ratio conditions
As is clear from the results in Table 1, it was found that the content of Co metal was high and the oxygen evolution performance of the resulting electrolyzed water material was good. Among them, preferred is Fe: co: ni ═ 1:3:1, ratio condition.
Example 4 investigation of the Effect of the Total molar concentration of Metal salts in the spin dope on the catalytic Material
Step (1): referring to example 1, the molar weight addition ratio of each metal salt is the same as that of example 1, only the total metal molar concentration is replaced by 0.1mmol/g and 0.3mmol/g respectively, and the corresponding LaSrFeCoNi-1/PVP nanofiber membrane is prepared by the electrostatic spinning technology under the same other conditions.
Step (2) was carried out in the same manner as in example 1 to obtain (La) respectively0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3-1/H-NTs and (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3-3/H-NTs catalytic material.
Tested as in example 1 (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3-1/H-NTs and (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Basic oxygen evolution performance of the-3/H-NTs catalytic material. The results are shown in Table 2.
TABLE 2 Performance results for catalyst materials obtained at different metal salt concentrations
From the results shown in Table 2, it is understood that the oxygen evolution performance of the resulting catalyst material is best when the total metal molar concentration is 0.2 mmol/g.
Comparative example 1
Step (1) is the same as in example 1;
step (2): 0.2g of the prepared LaSrFeCoNi/PVP nanofiber membrane is placed in a corundum boat and is placed in the middle of a tube furnace. The temperature is raised to 200 ℃ at the heating rate of 5 ℃/min, and the pre-oxidation is carried out by keeping the temperature for 3 hours in the air atmosphere. After the heat preservation is finished, the temperature is raised to 800 ℃ at the speed of 5 ℃/min in the argon atmosphere, and the heat preservation is carried out for 3 hours in the argon atmosphere. And after the heat preservation is finished, naturally cooling to room temperature under the argon atmosphere to obtain the LaSrFeCoNi/CNFs catalytic material.
The basic oxygen evolution performance of the LaSrFeCoNi/CNFs electrolytic water catalytic material was tested in the method of example 1.
Scanning electron microscope images of the prepared LaSrFeCoNi/CNFs electrolyzed water catalytic material, FIG. 6 is a scanning electron microscope image of LaSrFeCoNi/CNFs, and it can be observed from FIG. 6 that metal nanoparticles are all carbonized by electrostatic spinning PVP fibers at high temperature when air is not introducedUniformly supported on the carbon nano-fiber. FIG. 7 is a polarization curve of the oxygen evolution reaction of LaSrFeCoNi/CNFs in 1M KOH. As can be seen from FIG. 7, the current density was 10mA cm-2The overpotential for the oxygen evolution reaction of LaSrFeCoNi/CNFs is 490mV (vs. RHE), which is much lower than that of perovskite type (La)0.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3Oxygen evolution effect of the/H-NTs catalytic material.
Comparative example 2
Step (1): referring to example 1, 1mmol of lanthanum nitrate and 1mmol of cobalt nitrate were added to 20g of a 10 wt% solution of N, N-dimethylformamide/ethanol to polyvinylpyrrolidone (DMF/ethanol mass ratio 1: 1);
1mmol of strontium nitrate and 0.1mmol of cobalt nitrate are added into 20g of a 10 wt% solution of polyvinylpyrrolidone in N, N-dimethylformamide/ethanol (DMF/ethanol mass ratio 1: 1);
1mmol of lanthanum nitrate, 1mmol of strontium nitrate and 2mmol of cobalt nitrate are added into 20g of 10 wt% N, N-dimethylformamide/ethanol solution of polyvinylpyrrolidone (DMF/ethanol mass ratio is 1: 1);
1mmol of lanthanum nitrate, 1mmol of strontium nitrate, 0.8mmol of ferric nitrate and 1.2mmol of cobalt nitrate are added into a mixed solution of 20g of polyvinylpyrrolidone with the mass fraction of 10 wt% and N, N-dimethylformamide and ethanol (DMF: ethanol mass ratio is 1: 1);
and (3) respectively preparing a LaCo/PVP nano fiber membrane, a SrCo/PVP nano fiber membrane and a LaSrCo/PVP nano fiber membrane by an electrostatic spinning technology under the same condition.
Step (2) was performed in the same manner as in example 1 to obtain LaCoO3/CNFs、SrCoO3/CNFs and (La)0.5Sr0.5CoO3/CNFs catalytic materials.
LaCoO was tested as in example 13/CNFs、SrCoO3/CNFs and (La)0.5Sr0.5)CoO3Basic oxygen evolution performance of CNFs catalytic materials. The results are shown in Table 3.
TABLE 3 Performance results for two-element metal electrolyzed water catalyst materials
As can be seen from Table 3, (La) prepared in comparison with example 10.5Sr0.5)(Fe0.2Co0.6Ni0.2)O3The oxygen evolution activity of the/H-NTs catalyst material and the non-high-entropy perovskite type catalyst material is low.
Claims (5)
1. A method for preparing a high-entropy perovskite hollow nanotube catalytic oxygen evolution reaction material is characterized by comprising the following steps:
(1) dispersing lanthanum salt, strontium salt, ferric salt, cobalt salt, nickel salt and a nanofiber precursor in an organic solvent to prepare a spinning solution; then preparing a nanofiber membrane through electrostatic spinning;
(2) calcining and pre-oxidizing the nanofiber membrane obtained in the step (1), and then heating by program to calcine and oxidize in the air to obtain a high-entropy perovskite hollow nanotube efficient catalytic oxygen evolution reaction material;
the high-entropy perovskite type of the high-entropy perovskite hollow nanotube high-efficiency catalytic oxygen evolution reaction material is (La)xSr1-x)(FeyCozNi1-y-z)O3；
The molar ratio of lanthanum salt to strontium salt in the spinning solution in the step (1) is 1: 1;
the mass ratio of ferric salt, cobalt salt and nickel salt in the spinning solution in the step (1) is 1:3: 1;
the total molar ratio concentration of lanthanum salt, strontium salt, ferric salt, cobalt salt and nickel salt in the spinning solution in the step (1) is 0.2 mmol/g;
the mass fraction of the nanofiber precursor in the spinning solution in the step (1) is 8-20 wt%;
the calcination pre-oxidation in the step (2) is to heat up to 180-300 ℃ according to the heating rate of 2-20 ℃/min, and then carry out heat preservation calcination for 2-4 h;
the calcining carbonization in the step (2) is calcining for 2-4 hours at 400-1000 ℃.
2. The method according to claim 1, wherein the nanofiber precursor in step (1) is one or more of polyacrylonitrile, polyvinylpyrrolidone and polyvinyl alcohol.
3. The high-entropy perovskite hollow nanotube catalytic oxygen evolution reaction material prepared by the preparation method of any one of claims 1-2.
4. The application of the high-entropy perovskite hollow nanotube catalytic oxygen evolution reaction material as claimed in claim 3 in the field of electrochemical oxygen evolution reaction catalysis.
5. A method for electrocatalytic oxygen evolution reaction, characterized in that the high entropy perovskite hollow nanotube catalytic material of claim 3 is used as a catalyst.
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