CN115044935A - Preparation method and application of nano high-entropy oxide - Google Patents
Preparation method and application of nano high-entropy oxide Download PDFInfo
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- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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Abstract
The invention provides a preparation method and application of a nanometer high-entropy oxide. The high-entropy oxide comprises five metal elements of Fe, Co, Ni, Cr and Mn and a non-metal element of O, wherein the metal elements of Fe, Co, Ni, Cr and Mn are composed in different molar ratios, and each metal atom accounts for 5-40% of the total atomic percent of the metal; the nano high-entropy oxide has a spinel structure; the particle size is 2-10 nm. The preparation method utilizes the wave-absorbing performance of different materials, and by means of the characteristics of rapidity, controllability and uniformity of the microwave reactor, the nano high-entropy oxide with uniform components and adjustable proportion is synthesized by a microwave-assisted solvothermal method under the condition of high-pressure non-equilibrium reaction, so that a novel preparation method is provided for synthesizing the nano high-entropy oxide. The nanometer high-entropy oxide prepared by the method has the advantages of ultra-small particle size, multi-element synergistic effect, a large number of active sites and structural stability.
Description
Technical Field
The invention belongs to the technical field of electrocatalyst synthesis, and particularly relates to a preparation method and application of a nano high-entropy oxide.
Background
In recent years, excessive combustion of fossil fuels has caused a series of environmental pollution problems, and thus, humans must rapidly seek and utilize various clean and sustainable energy sources. Hydrogen is considered a promising clean energy carrier due to the advantages of zero carbon content, no pollution of the product and highest weight energy density. Currently, the main methods for industrial hydrogen production are methane steam reforming and coal gasification (> 95%), however, the methane steam reforming and coal gasification hydrogen production methods not only increase the consumption of fossil fuels, but also increase the global carbon dioxide emission, and are not ideal hydrogen production approaches. In order to accelerate the steps of 'carbon neutralization' and 'carbon reaching standards', the hydrogen production by electrolyzing water, which is green, environment-friendly and pollution-free, is considered as a promising strategy for renewable energy conversion. However, the electrochemical water splitting process includes two core half reactions of cathodic Hydrogen Evolution Reaction (HER) and anodic Oxygen Evolution Reaction (OER), where the OER half reaction involves a four electron transfer process with slow kinetics leading to increased energy consumption and lower conversion efficiency. In order to improve the efficiency of hydrogen production by electrochemical water decomposition and overcome the problem of slow reaction kinetics of OER, a large number of electrocatalysts are widely researched.
High Entropy Oxides (HEO) are single phase "multi-component" solid solutions of five or more elements with many electrocatalytic properties, such as intrinsic thermodynamic stability, high lattice distortion, high structural stability, and super ionic conductivity. The high-entropy oxide exhibits excellent electrocatalytic activity due to excellent synergistic effect exhibited by the combined action of a plurality of cations, as compared to conventional metal oxides. In addition, the large surface area of the nanoparticles not only can expose more active sites on the surface of the catalyst, but also can accelerate the electron conduction speed. However, since the metal element composition of HEOs is complicated and tends to cause phase separation, few HEOs catalysts have been reported so far. Researchers have tried various methods (flame spray pyrolysis, atomized spray pyrolysis, co-precipitation, anti-co-precipitation, solvothermal synthesis, and solid phase sintering) to prepare HEO and explore OER catalytic performance. However, most of the preparation processes are relatively complicated or involve high reaction temperature, resulting in large particle size of HEO, which is not favorable for exerting catalytic activity. Therefore, the development of a method for synthesizing the nano high-entropy oxide with simplicity, high efficiency and low cost is urgently needed.
Disclosure of Invention
Aiming at the problems of the current high-entropy oxide synthesis technology, the invention provides a preparation method and application of a nanometer high-entropy oxide. The nanometer high-entropy oxide has the advantages of ultra-small particle size, multi-element synergistic effect, a large number of active sites and structural stability. The preparation method utilizes the wave-absorbing performance of different materials, and by means of the characteristics of rapidity, controllability and uniformity of a microwave reactor, the nano high-entropy oxide with uniform components and adjustable proportion is synthesized by a microwave-assisted solvothermal method under the condition of high-pressure non-equilibrium reaction, thereby providing a novel preparation method for synthesizing the nano high-entropy oxide.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a nanometer high-entropy oxide comprises five metal elements of Fe, Co, Ni, Cr, Mn and a nonmetal element of O, wherein the metal elements of Fe, Co, Ni, Cr and Mn are composed in equal molar ratio or different molar ratios, and each metal atom accounts for 5 to 40 percent of the total atomic percent of metal;
the preparation method of the nanometer high-entropy oxide comprises the following steps:
weighing metal salts of five elements of Fe, Co, Ni, Cr and Mn, adding the metal salts into polyol, stirring at room temperature for 1-10 h, and obtaining a solution A after the metal salts are completely dissolved;
adding the solution A into a polytetrafluoroethylene reaction kettle, heating and reacting by using microwaves in a high-pressure closed environment, stirring simultaneously in the reaction process, and obtaining a solution B after the reaction is finished;
adding a washing solvent into the solution B for centrifugal washing for multiple times, and washing away unreacted metal salt and the reaction solvent to obtain a solid C;
and 4, drying:
putting the obtained solid C in a constant-temperature drying box, and drying to obtain powder D;
and 5, calcining:
and placing the powder D in a muffle furnace for calcining to finally obtain the nano high-entropy oxide.
Further, the nanometer high-entropy oxide is (Fe) a Co b Ni c Cr d Mn e ) 3 O 4-x The values of a, b, c, d and e are 1/20-2/5 respectively, the sum of a, b, c, d and e is 1, and the nano high-entropy oxide has a spinel structure; the particle size is 2-10 nm.
Further, the nanometer high-entropy oxide is used for the high-efficiency oxygen evolution electrocatalyst.
Further, in the step 1, the metal salt is a metal nitrate; the polyhydric alcohol is diethylene glycol; the concentration of the total amount of the metal nitrate in diethylene glycol is 0.05-0.3 mol.L -1 。
Further, in the step 2, the heating temperature is 180-.
Further, in the step 3, the centrifugal washing solvent is one or a mixed solution of two of deionized water and absolute ethyl alcohol.
Further, in the step 4, the drying temperature is 40-80 ℃, and the drying time is 4-12 hours.
Further, in the step 5, the calcination temperature is 200-600 ℃, and the calcination time is 2-4 hours.
The invention also provides an application of the nanometer high-entropy oxide or the nanometer high-entropy oxide prepared by the preparation method as a working electrode in catalyzing oxygen evolution reaction under alkaline conditions (0.1M,0.5M and 1M KOH).
The application of the nanometer high-entropy oxide specifically comprises the following steps:
(1) weighing the nano high-entropy oxide and the conductive carbon black according to the mass ratio of 3:1, grinding and uniformly mixingAfter homogenizing, adding a dispersant, wherein the concentration of the nano high-entropy oxide in the dispersant is 5-20 mg/mL -1 Then adding 5% of Nafion solution by mass, wherein the volume ratio of the dispersing agent to the 5% of Nafion solution is 50: 1;
(2) ultrasonically treating for 30-60 min to obtain uniformly dispersed suspension, dripping 10-20 μ L of suspension onto carbon paper electrode, wherein the load of nanometer high-entropy oxide is 0.55-1.1mg cm -2 。
Further, in the step (1), the dispersant is one or a mixture of N, N-Dimethylformamide (DMF), absolute ethyl alcohol, deionized water, isopropanol and acetone; the carbon black is refluxed for 3-8 hours at the temperature of 60-90 ℃ by nitric acid before use.
Further, in the step (2), the area of the carbon paper electrode is 0.18cm 2 。
Compared with the prior art, the invention has the beneficial effects that:
1. the synthesis method of the nanometer high-entropy oxide utilizes the wave-absorbing performance of materials, synthesizes ultra-small nanoparticles with uniform components and adjustable element proportion by a microwave-assisted liquid-phase chemical non-equilibrium reaction strategy, is a simple, high-efficiency, low-cost and universal synthesis strategy, and provides a new idea for breaking the bottleneck of the synthesis of the nanometer high-entropy oxide.
2. The nano high-entropy oxide prepared by the synthetic method has a spinel structure (Fe) a Co b Ni c Cr d Mn e ) 3 O 4-x The unique oxide reduction electron pair provides sufficient active sites for electrocatalytic reaction, so that the catalyst activity is improved. In addition, the entropy of the high-entropy oxide drives a phase stable structure, and guarantees the long-term catalytic stability of the catalyst in the reaction process.
3. The nanometer high-entropy oxide has rapid reaction kinetics, and the nanometer morphology enables a large number of active sites to be exposed on the surface of the catalyst, thereby showing excellent catalytic performance. Nano high entropy oxide (Fe) a Co b Ni c Cr d Mn e ) 3 O 4-x Wherein the raw materials of Fe, Co, Ni, Cr and MnThe best catalytic activity is shown when the molar ratio is 1:1:2:1:1, and the catalyst is 10mA cm -2 Has an overpotential of 260mV and exhibits excellent stability at a current density of 10mA cm -2 The potential of the test piece is changed by only 0.9% after the stability test for 95 h. The catalyst prepared is superior to commercial RuO 2 An electrocatalyst.
Drawings
FIG. 1 is an XRD pattern of nano high entropy oxides prepared in examples 1-6;
FIG. 2 is an SEM image of nano high-entropy oxides prepared in examples 1-6;
FIG. 3 is a graph of the metal atomic percentages of the nano-sized high entropy oxides prepared in examples 1-6;
FIG. 4 is an XPS spectrum of the nano high entropy oxide prepared in example 1;
FIG. 5 is an XPS spectrum of the nano high entropy oxide prepared in example 4;
FIG. 6 is a graph of LSV of the nano high entropy oxides prepared in examples 1-6;
FIG. 7 is a graph of the chronoamperometric voltage (. eta.10) of the nano-sized high-entropy oxide prepared in example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A nanometer high-entropy oxide is composed of Fe, Co, Ni, Cr, Mn and O, and is prepared from the raw materials according to the molar ratio of metallic elements Fe, Co, Ni, Cr and Mn of 1:1:1: 1; the nanometer high-entropy oxide has a spinel structure and the granularity is less than 10 nm.
The preparation method of the nanometer high-entropy oxide comprises the following steps:
0.4102g of ferric nitrate nonahydrate, 0.2940g of cobalt nitrate hexahydrate, 0.2967g of nickel nitrate hexahydrate, 0.404g of chromium nitrate nonahydrate and 0.2561g of manganese nitrate tetrahydrate are weighed, dissolved in 50mL of diethylene glycol, and stirred for 3 hours to obtain a clear and transparent solution A.
solution A was transferred to a 100mL Teflon lined autoclave and the temperature was raised to 190 ℃ at a ramp rate of 10 ℃/min, then raised to 200 ℃ at a ramp rate of 5 ℃/min and held at 200 ℃ for 10 min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
and washing the liquid B with water and ethanol, centrifuging for several times, and washing away unreacted metal salt and reaction solvent to obtain a solid C.
And 4, drying:
and (3) placing the obtained solid C in a constant-temperature drying box, drying for 12 hours at the temperature of 40 ℃, and drying to obtain powder D.
And 5, calcining:
and placing the powder D in a muffle furnace to calcine for 4 hours at 300 ℃ to finally obtain the nano high-entropy oxide.
In the nano high-entropy oxide prepared in this example, XRD is shown in fig. 1(a), SEM is shown in fig. 2(a), metal atom percentage is shown in fig. 3(a), and XPS is shown in fig. 4; from the XRD result of fig. 1(a), the nano high-entropy oxide is a single-phase spinel structure. Fig. 2(a) is an SEM image of the synthesized sample, and it can be seen that the particles are fine (less than 10nm), which is beneficial to expose more active sites and improve the catalytic activity. The results of fig. 3(a) show that the ratio of the metal elements is close to the experimental design ratio, which proves that the synthesis method can realize accurate adjustment. The results in FIG. 4 indicate that multiple valences of each element coexist.
The prepared nano high-entropy oxide is used as a working electrode and applied to an electrocatalytic oxygen evolution reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) after grinding 5mg of the nano-sized high-entropy oxide with 1.5mg of carbon black treated with nitric acid at 60 ℃ for 5 hours, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution (5 wt%) were added.
(2) Subjecting the liquid obtained in (1) to ultrasonic treatment for 30min to obtain suspension, and suspending 10 μ LDropping in 0.18cm of turbid liquid 2 The catalyst loading on the carbon paper electrode of (2) was 0.55mg cm -2 The electrode is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the electrolyte is 1M KOH; on the Shanghai Chenhua CHI760E electrochemical workstation, electrochemical performance tests were performed: the sweeping speed of the LSV is 1mV s -1 。
The reaction performance of the nano high-entropy oxide in catalyzing oxygen evolution is measured in a 1M KOH solution, the LSV is shown in figure 6, and the current is 10 mA-cm -2 The overpotential measured was 271 mV.
Example 2
A nanometer high-entropy oxide is composed of Fe, Co, Ni, Cr, Mn and O, and is prepared from the raw materials according to the molar ratio of metal elements Fe, Co, Ni, Cr and Mn of 2:1:1: 1; the nanometer high-entropy oxide has a spinel structure and the granularity is less than 10 nm.
The preparation method of the nanometer high-entropy oxide comprises the following steps:
0.8203g of ferric nitrate nonahydrate, 0.2940g of cobalt nitrate hexahydrate, 0.2967g of nickel nitrate hexahydrate, 0.404g of chromium nitrate nonahydrate and 0.2561g of manganese nitrate tetrahydrate are weighed, dissolved in 50mL of diethylene glycol, and stirred for 3 hours to obtain a clear and transparent solution A.
solution A was transferred to a 100mL Teflon lined autoclave and the temperature was raised to 190 ℃ at a ramp rate of 10 ℃/min, then to 200 ℃ at a ramp rate of 5 ℃/min and held at 200 ℃ for 20 min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
and washing the liquid B with water and ethanol, centrifuging for several times, and washing away unreacted metal salt and reaction solvent to obtain a solid C.
And 4, drying:
and (3) placing the obtained solid C in a constant-temperature drying box, drying for 8 hours at the temperature of 40 ℃, and drying to obtain powder D.
and placing the powder D in a muffle furnace to calcine for 3 hours at 400 ℃, and finally obtaining the nano high-entropy oxide.
In the nano high-entropy oxide prepared in the embodiment, XRD is shown in fig. 1(b), SEM is shown in fig. 2(b), and the percentage of metal atoms is shown in fig. 3 (b); from the XRD result of fig. 1(b), the high-entropy oxide is a single-phase spinel structure. Fig. 2(b) is an SEM image of the synthesized sample, and it can be seen that the morphology is fine nanoparticles (less than 10nm), which is beneficial to expose more active sites and improve the catalytic activity. The results of fig. 3(b) show that the ratio of the metal elements is close to the experimental design ratio, which proves that the synthesis method can realize accurate adjustment.
The prepared nano high-entropy oxide is used as a working electrode and applied to an electrocatalytic oxygen evolution reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) after 5mg of the high-entropy oxide precipitated with high-efficiency oxygen and 1.5mg of carbon black treated with nitric acid at 80 ℃ for 5 hours were ground, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution (5 wt%) were added.
(2) Subjecting the liquid obtained in (1) to ultrasonic treatment for 30min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm 2 The catalyst loading on the carbon paper electrode of (1.1 mg cm) -2 The electrode is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the electrolyte is 1M KOH; on the Shanghai Chenhua CHI760E electrochemical workstation, electrochemical performance tests were performed: the sweeping speed of the LSV is 1mV s -1 。
The reaction performance of the nano high-entropy oxide in catalyzing oxygen evolution is measured in a 1M KOH solution, the LSV is shown in figure 6, and the current is 10 mA-cm -2 The overpotential was measured at 293 mV.
Example 3
A nanometer high-entropy oxide is composed of Fe, Co, Ni, Cr, Mn and O, and is prepared from the raw materials according to the molar ratio of metallic elements Fe, Co, Ni, Cr and Mn of 1:2:1:1: 1; the nanometer high-entropy oxide has a spinel structure and the granularity is less than 10 nm.
The preparation method of the nanometer high-entropy oxide comprises the following steps:
0.4102g of ferric nitrate nonahydrate, 0.588g of cobalt nitrate hexahydrate, 0.2967g of nickel nitrate hexahydrate, 0.404g of chromium nitrate nonahydrate and 0.2561g of manganese nitrate tetrahydrate are weighed and dissolved in 50mL of diethylene glycol, and stirred for 3 hours to obtain a clear and transparent solution A.
solution A was transferred to a 100mL Teflon lined autoclave and the temperature was raised to 190 ℃ at a ramp rate of 20 ℃/min, then to 200 ℃ at a ramp rate of 5 ℃/min and held at 200 ℃ for 30 min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
and washing the liquid B with water and ethanol, centrifuging for several times, and washing away unreacted metal salt and reaction solvent to obtain a solid C.
And 4, drying:
and (3) placing the obtained solid C in a constant-temperature drying box, drying for 10 hours at the temperature of 40 ℃, and drying to obtain powder D.
And 5, calcining:
and placing the powder D in a muffle furnace to calcine for 2 hours at 500 ℃ to finally obtain the nano high-entropy oxide.
The XRD of the nano high-entropy oxide prepared in this example is shown in fig. 1(c), the SEM is shown in fig. 2(c), and the atomic percentage of the metal is shown in fig. 3 (c); from the XRD result of fig. 1(c), the high-entropy oxide is a spinel structure. Fig. 2(c) is an SEM image of the synthesized sample, and it can be seen that the particles are fine (less than 10nm), which is beneficial to expose more active sites and improve the catalytic activity. The results of fig. 3(c) show that the ratio of the metal elements is close to the experimental design ratio, which proves that the synthesis method can realize accurate adjustment. .
The prepared nano high-entropy oxide is used as a working electrode and applied to an electrocatalytic oxygen evolution reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) after 5mg of the high-entropy oxide precipitated with high-efficiency oxygen and 1.5mg of carbon black treated with nitric acid at 90 ℃ for 5 hours were ground, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution (5 wt%) were added.
(2) Subjecting the liquid obtained in (1) to ultrasonic treatment for 30min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm 2 The catalyst loading on the carbon paper electrode of (1.1 mg cm) -2 The electrode is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the electrolyte is 1M KOH; on the Shanghai Chenhua CHI760E electrochemical workstation, electrochemical performance tests were performed: the sweeping speed of the LSV is 1mV s -1 。
The reaction performance of the nano high-entropy oxide in catalyzing oxygen evolution is measured in a 1M KOH solution, the LSV is shown in figure 6, and the current is 10 mA-cm -2 The overpotential was measured to be 281 mV.
Example 4
A nanometer high-entropy oxide is composed of Fe, Co, Ni, Cr, Mn and O, and is prepared from the raw materials according to the molar ratio of metallic elements Fe, Co, Ni, Cr and Mn of 1:1:2:1: 1; the nanometer high-entropy oxide has a spinel structure and the granularity is less than 10 nm.
The preparation method of the nanometer high-entropy oxide comprises the following steps:
0.4102g of ferric nitrate nonahydrate, 0.2940g of cobalt nitrate hexahydrate, 0.5934g of nickel nitrate hexahydrate, 0.404g of chromium nitrate nonahydrate and 0.2561g of manganese nitrate tetrahydrate are weighed, dissolved in 50mL of diethylene glycol, and stirred for 3 hours to obtain a clear and transparent solution A.
solution A was transferred to a 100mL Teflon lined autoclave and the temperature was raised to 190 ℃ at a ramp rate of 30 ℃/min, then raised to 200 ℃ at a ramp rate of 5 ℃/min and held at 200 ℃ for 40 min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
and washing the liquid B with water and ethanol, centrifuging for several times, and washing away unreacted metal salt and reaction solvent to obtain a solid C.
And 4, drying:
and (3) placing the obtained solid C in a constant-temperature drying box, drying for 6 hours at the temperature of 60 ℃, and drying to obtain powder D.
And 5, calcining:
and placing the powder D in a muffle furnace to calcine for 4 hours at 500 ℃ to finally obtain the nano high-entropy oxide.
In the nano high-entropy oxide prepared in this example, XRD is shown in fig. 1(d), SEM is shown in fig. 2(d), metal atom percentage is shown in fig. 3(d), and XPS is shown in fig. 5; from the XRD result of fig. 1(d), the high-entropy oxide is a spinel structure. Fig. 2(d) is an SEM image of the synthesized sample, and it can be seen that the particles are fine (less than 10nm), which is beneficial to expose more active sites and improve the catalytic activity. The results in fig. 3(d) show that the ratio of the metal elements is close to the experimental design ratio, which proves that the synthesis method can realize accurate adjustment. The results of FIG. 5 indicate that multiple valence states of each element coexist.
The prepared nano high-entropy oxide is used as a working electrode and applied to an electrocatalytic oxygen evolution reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) after 5mg of the high-entropy oxide precipitated with high-efficiency oxygen and 1.5mg of carbon black treated with nitric acid at 80 ℃ for 3 hours were ground, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution (5 wt%) were added.
(2) Subjecting the liquid obtained in (1) to ultrasonic treatment for 30min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm 2 The catalyst loading on the carbon paper electrode of (1.1 mg cm) -2 The electrode is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the electrolyte is 1M KOH; on the Shanghai Chenhua CHI760E electrochemical workstation, electrochemical performance tests were performed: the sweeping speed of the LSV is 1mV s -1 。
The reaction performance of the nano high-entropy oxide in catalyzing oxygen evolution is measured in a 1M KOH solution, the LSV is shown in figure 6, and the current is 10 mA-cm -2 The overpotential was measured to be 260 mV. FIG. 7 is a graph of the time-lapse voltage (. eta.10) of the nano high-entropy oxide catalyst, and the result shows that the voltage is not obviously increased and the nano high-entropy oxide catalyst has good activity and stability after being subjected to a stability test for 95 hours.
Example 5
A nanometer high-entropy oxide catalyst is composed of Fe, Co, Ni, Cr, Mn and O, and is prepared from the raw materials according to the molar ratio of metallic elements Fe, Co, Ni, Cr and Mn of 1:1:1:2: 1; the nanometer high-entropy oxide has a spinel structure and the granularity is less than 10 nm.
The preparation method of the nanometer high-entropy oxide comprises the following steps:
0.4102g of ferric nitrate nonahydrate, 0.2940g of cobalt nitrate hexahydrate, 0.2967g of nickel nitrate hexahydrate, 0.808g of chromium nitrate nonahydrate and 0.2561g of manganese nitrate tetrahydrate are weighed, dissolved in 50mL of diethylene glycol, and stirred for 3 hours to obtain a clear and transparent solution A.
solution A was transferred to a 100mL Teflon lined autoclave and the temperature was raised to 190 ℃ at a ramp rate of 30 ℃/min, then to 200 ℃ at a ramp rate of 5 ℃/min and held at 200 ℃ for 50 min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
and washing the liquid B with water and ethanol, centrifuging for several times, and washing away unreacted metal salt and reaction solvent to obtain a solid C.
And 4, drying:
and (3) placing the obtained solid C in a constant-temperature drying oven, drying for 4 hours at the temperature of 80 ℃, and drying to obtain powder D.
and placing the powder D in a muffle furnace to calcine for 2 hours at the temperature of 600 ℃ to finally obtain the nano high-entropy oxide.
In the nano high-entropy oxide prepared in the embodiment, XRD is shown as fig. 1(e), SEM is shown as fig. 2(e), and the percentage of metal atoms is shown as fig. 3 (e); from the XRD result of fig. 1(e), the high-entropy oxide is a spinel structure. Fig. 2(e) is an SEM image of the synthesized sample, and it can be seen that the particles are fine (less than 10nm), which is beneficial to expose more active sites and improve the catalytic activity. The results in fig. 3(e) show that the ratio of the metal elements is close to the experimental design ratio, which proves that the synthesis method can realize accurate adjustment.
The prepared nano high-entropy oxide is used as a working electrode and applied to an electrocatalytic oxygen evolution reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) after 5mg of the high-entropy oxide precipitated with high-efficiency oxygen and 1.5mg of carbon black treated with nitric acid at 90 ℃ for 3 hours were ground, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution (5 wt%) were added.
(2) Subjecting the liquid obtained in (1) to ultrasonic treatment for 30min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm 2 The catalyst loading on the carbon paper electrode of (1.1 mg. cm) -2 The electrode is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the electrolyte is 1M KOH; on the Shanghai Chenhua CHI760E electrochemical workstation, electrochemical performance tests were performed: the sweeping speed of the LSV is 1mV s -1 。
The reaction performance of the nano high-entropy oxide in catalyzing oxygen evolution is measured in a 1M KOH solution, the LSV is shown in figure 6, and the current is 10 mA-cm -2 The overpotential was measured to be 283 mV.
Example 6
A nanometer high-entropy oxide is composed of Fe, Co, Ni, Cr, Mn and O, and is prepared from the raw materials according to the molar ratio of metallic elements Fe, Co, Ni, Cr and Mn of 1:1:1: 2; the nanometer high-entropy oxide has a spinel structure and the granularity is less than 10 nm.
The preparation method of the nanometer high-entropy oxide comprises the following steps:
0.4102g of ferric nitrate nonahydrate, 0.2940g of cobalt nitrate hexahydrate, 0.2967g of nickel nitrate hexahydrate, 0.404g of chromium nitrate nonahydrate and 0.5122g of manganese nitrate tetrahydrate are weighed, dissolved in 50mL of diethylene glycol, and stirred for 3 hours to obtain a clear and transparent solution A.
solution A was transferred to a 100mL Teflon lined autoclave and the temperature was raised to 190 ℃ at a ramp rate of 30 ℃/min, then raised to 200 ℃ at a ramp rate of 5 ℃/min and held at 200 ℃ for 60 min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
and washing the liquid B with water and ethanol, centrifuging for several times, and washing away unreacted metal salt and reaction solvent to obtain a solid C.
And 4, drying:
and (3) placing the obtained solid C in a constant-temperature drying box, drying for 10 hours at the temperature of 60 ℃, and drying to obtain powder D.
And 5, calcining:
and placing the powder D in a muffle furnace to calcine for 4 hours at the temperature of 600 ℃ to finally obtain the nano high-entropy oxide.
In the nano high-entropy oxide prepared in this example, XRD is shown in fig. 1(f), SEM is shown in fig. 2(f), and the percentage of metal atoms is shown in fig. 3 (f); from the XRD result of fig. 1(f), the high-entropy oxide is a spinel structure. Fig. 2(f) is an SEM image of the synthesized sample, and it can be seen that the particles are fine (less than 10nm), which is beneficial to expose more active sites and improve the catalytic activity. The results of fig. 3(f) show that the metal element proportion is close to the experimental design proportion, which proves that the synthesis method can realize accurate adjustment.
The prepared nano high-entropy oxide is used as a working electrode and applied to an electrocatalytic oxygen evolution reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) after 5mg of the high-entropy oxide precipitated with high-efficiency oxygen and 1.5mg of carbon black treated with nitric acid at 80 ℃ for 5 hours were ground, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution (5 wt%) were added.
(2) Subjecting the liquid obtained in (1) to ultrasonic treatment for 30min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm 2 The catalyst loading on the carbon paper electrode of (1.1 mg cm) -2 The electrode is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the electrolyte is 1M KOH; on the Shanghai Chenhua CHI760E electrochemical workstation, electrochemical performance tests were performed: the sweeping speed of the LSV is 1mV s -1 。
The reaction performance of the nano high-entropy oxide catalyst in catalyzing oxygen evolution is measured in a 1M KOH solution, and the LSV is shown in figure 6, and the current is 10 mA-cm -2 The overpotential was determined to be 277 mV.
The technical idea of the present invention is described in the above technical solutions, and the protection scope of the present invention is not limited thereto, and any changes and modifications made to the above technical solutions according to the technical essence of the present invention belong to the protection scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a nanometer high-entropy oxide is characterized in that the high-entropy oxide comprises five metal elements of Fe, Co, Ni, Cr, Mn and a non-metal element O, wherein the metal elements of Fe, Co, Ni, Cr and Mn are composed according to equal molar ratio or different molar ratios, and each metal atom accounts for 5-40% of the total atomic percent of metal; the preparation method of the nanometer high-entropy oxide comprises the following steps:
step 1, preparing a metal salt solution:
weighing metal salts of five elements of Fe, Co, Ni, Cr and Mn, adding the metal salts into polyhydric alcohol, stirring for 1-10 h at room temperature, and obtaining a solution A after the metal salts are completely dissolved;
step 2, microwave solvothermal reaction:
adding the solution A into a polytetrafluoroethylene reaction kettle, heating and reacting by using microwaves in a high-pressure closed environment, stirring simultaneously in the reaction process, and obtaining a solution B after the reaction is finished;
step 3, centrifugal washing:
adding a washing solvent into the solution B for centrifugal washing for multiple times, and washing away unreacted metal salt and the reaction solvent to obtain a solid C;
and 4, drying:
putting the obtained solid C in a constant-temperature drying box, and drying to obtain powder D;
and 5, calcining:
and placing the powder D in a muffle furnace for calcining to finally obtain the nano high-entropy oxide.
2. The method for preparing a nano high-entropy oxide according to claim 1, wherein the nano high-entropy oxide is (A)Fe a Co b Ni c Cr d Mn e ) 3 O 4-x The values of a, b, c, d and e are 1/20-2/5 respectively, the sum of a, b, c, d and e is 1, and the nano high-entropy oxide has a spinel structure; the particle size is 2-10 nm.
3. The method for preparing a nano high-entropy oxide according to claim 1, wherein the nano high-entropy oxide is used for a high-efficiency oxygen evolution electrocatalyst.
4. The method for preparing a nano high-entropy oxide according to claim 1, wherein in the step 1, the metal salt is a metal nitrate; the polyhydric alcohol is diethylene glycol; the concentration of the total amount of the metal nitrate in diethylene glycol is 0.05-0.3 mol.L -1 。
5. The method for preparing a nano high-entropy oxide according to claim 1, wherein in the step 2, the heating temperature is 180-240 ℃, the heating rate is 5-30 ℃/min, and the holding time is 10-60 min.
6. The method for preparing a nano high-entropy oxide according to claim 1, wherein, in the step 4, the drying temperature is 40-80 ℃ and the drying time is 4-12 hours.
7. The method as claimed in claim 1, wherein in step 5, the calcination temperature is 200-600 ℃ and the calcination time is 2-4 hours.
8. Use of a nano high-entropy oxide prepared according to any one of the preparation methods of claims 1 to 7 as a working electrode in catalyzing oxygen evolution reaction under alkaline conditions.
9. The application of the nanometer high-entropy oxide as claimed in claim 8, specifically comprising:
(1) weighing the nano high-entropy oxide and the conductive carbon black according to the mass ratio of 3:1, grinding to uniformly mix the nano high-entropy oxide and the conductive carbon black, and adding a dispersing agent, wherein the concentration of the nano high-entropy oxide in the dispersing agent is 5-20 mg/mL -1 Then adding 5% of Nafion solution by mass, wherein the volume ratio of the dispersing agent to the 5% of Nafion solution is 50: 1;
(2) ultrasonically treating for 30-60 min to obtain uniformly dispersed suspension, dripping 10-20 μ L of suspension onto carbon paper electrode, wherein the load of nanometer high-entropy oxide is 0.55-1.1mg cm -2 。
10. The application of the nano high-entropy oxide is characterized in that in the step (1), the dispersing agent is one or a mixture of N, N-dimethylformamide, absolute ethyl alcohol, deionized water, isopropanol and acetone; refluxing the carbon black for 3-8 hours at 60-90 ℃ by nitric acid before use; in the step (2), the area of the carbon paper electrode is 0.18cm 2 。
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