CN115044935B - 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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Abstract
The invention provides a preparation method and application of a nano high-entropy oxide. The high-entropy oxide comprises five metal elements Fe, co, ni, cr, mn and non-metal elements O, wherein the metal elements Fe, co, ni, cr, mn are composed in different molar ratios, and each metal atom accounts for 5-40% of the total metal atoms; 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 synthesizes the nano high-entropy oxide with uniform components and adjustable proportion under the high-pressure non-equilibrium reaction condition by a microwave-assisted solvothermal method by means of the characteristics of rapidness, controllability and uniformity of a microwave reactor, thereby providing a novel preparation method for synthesizing the nano high-entropy oxide. The nanometer high entropy oxide prepared by the method has ultra-small particle size, multielement 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 causes a series of environmental pollution problems, and thus, humans have to rapidly seek and utilize various clean and sustainable energy sources. Hydrogen is considered a promising clean energy carrier because of its zero carbon content, non-contaminating product and highest gravimetric energy density. Currently, the main methods of industrial hydrogen production are methane steam reforming and coal gasification (> 95%), however, the methods of methane steam reforming and coal gasification hydrogen production not only exacerbate fossil fuel consumption, but also increase global carbon dioxide emissions, which is not an ideal hydrogen production pathway. In order to accelerate the steps of carbon neutralization and carbon standard reaching, green and environment-friendly water electrolysis hydrogen production is considered as a promising strategy for renewable energy conversion. However, the electrochemical water decomposition process includes half reactions of two cores, a cathodic Hydrogen Evolution Reaction (HER) and an anodic Oxygen Evolution Reaction (OER), wherein the OER half reaction involves a four electron transfer process, whose slow kinetics results in increased energy consumption and lower conversion efficiency. In order to improve the hydrogen production efficiency by electrochemical water splitting and overcome the problem of slow OER reaction kinetics, a large number of electrocatalysts are widely studied.
High Entropy Oxides (HEOs) are single phase "multicomponent" solid solutions of five and more elemental compositions, with many properties beneficial to electrocatalysis, such as inherent thermodynamic stability, high lattice distortion, high structural stability, and super ionic conductivity. The high entropy oxide exhibits excellent electrocatalytic activity due to excellent synergistic effects exhibited by the combined action of various cations, as compared to conventional metal oxides. In addition, the large surface area of the nanoparticle not only exposes more active sites on the catalyst surface, but also accelerates the electron conduction velocity. However, the metal element composition of the HEOs is complex, and phase separation is easily caused, so that the HEOs catalyst reported so far is few. Researchers have tried various methods (flame spray pyrolysis, atomized spray pyrolysis, co-precipitation, reverse 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 a relatively high reaction temperature, resulting in a large particle size of HEO, which is disadvantageous in exerting catalytic activity. Therefore, there is an urgent need to develop a simple, efficient and low-cost method for synthesizing nano high-entropy oxide.
Disclosure of Invention
Aiming at the problems existing in the current high-entropy oxide synthesis technology, the invention provides a preparation method and application of a nano high-entropy oxide. The nano high-entropy oxide has 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 synthesizes the nano high-entropy oxide with uniform components and adjustable proportion under the high-pressure non-equilibrium reaction condition by a microwave-assisted solvothermal method by means of the characteristics of rapidness, controllability and uniformity of a microwave reactor, thereby providing a novel preparation method for synthesizing the nano high-entropy oxide.
The technical scheme adopted for solving the technical problems is as follows: the preparation method of the nano high-entropy oxide comprises five metal elements Fe, co, ni, cr, mn and non-metal elements O, wherein the metal elements Fe, co, ni, cr, mn are formed by equimolar ratio or different molar ratios, and each metal atom accounts for 5-40% of the total atomic percentage of the metal;
the preparation method of the nano high-entropy oxide comprises the following steps:
step 1, preparing a metal salt solution:
weighing Fe, co, ni, cr, mn metal salts of five elements, adding the metal salts into the polyol, 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 in a high-pressure closed environment by utilizing microwaves, and stirring simultaneously in the reaction process to obtain a solution B after the reaction is finished;
step 3, centrifugal washing:
adding a washing solvent into the solution B for centrifugal washing for a plurality of times to wash out unreacted metal salt and reaction solvent, thus obtaining a solid C;
step 4, drying:
placing the obtained solid C in a constant temperature drying oven, and drying to obtain powder D;
step 5, calcining:
and (3) placing the powder D in a muffle furnace for calcination to finally obtain the nano high-entropy oxide.
Further, the nano high entropy oxide is (Fe a Co b Ni c Cr d Mn e ) 3 O 4-x A, b, c, d, e has a value of 1/20-2/5 and a, b, c, d, e sum of 1, and the nano high entropy oxide has a spinel structure; the particle size is 2-10 nm.
Further, the nano high entropy oxide is used for high-efficiency oxygen evolution electrocatalyst.
Further, in the step 1, the metal salt is a metal nitrate; the polyol is diethylene glycol; the concentration of the total metal nitrate in diethylene glycol is 0.05-0.3 mol.L -1 。
Further, in the step 2, the heating temperature is 180-240 ℃, the heating rate is 5-30 ℃/min, the heat preservation time is 10-60min, the microwave heating power is 800-1500W, and the stirring rotating speed is 50-600r/min.
Further, in the step 3, the centrifugal washing solvent is one or 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 nano high-entropy oxide or the nano high-entropy oxide prepared by the preparation method as a working electrode in catalyzing oxygen precipitation reaction under alkaline conditions (0.1M, 0.5M and 1M KOH).
The application of the nano high-entropy oxide specifically comprises the following steps:
(1) Weighing and grinding the nano high-entropy oxide and the conductive carbon black according to the mass ratio of 3:1 to uniformly mix, and adding a dispersing agent, wherein the concentration of the nano high-entropy oxide in the dispersing agent is 5-20 mg/mL -1 Adding Nafion solution with the mass fraction of 5%, wherein the volume ratio of the dispersing agent to the 5% Nafion solution is 50:1;
(2) Preparing uniformly dispersed suspension by ultrasonic treatment for 30-60 min, and dripping 10-20 μl of suspension onto carbon paper electrode, wherein the nanometer high entropy oxide loading is 0.55-1.1mg cm -2 。
Further, in the step (1), the dispersing agent is one or a mixed solution of a plurality of N, N-Dimethylformamide (DMF), absolute ethyl alcohol, deionized water, isopropanol and acetone; the carbon black is refluxed for 3 to 8 hours at the temperature of between 60 and 90 ℃ by nitric acid before being used.
Further, in the step (2), the electrode area of the carbon paper is 0.18cm 2 。
Compared with the prior art, the invention has the beneficial effects that:
1. the method for synthesizing the nano high-entropy oxide utilizes the wave absorbing performance of the material, synthesizes the ultra-small nano particles with uniform components and adjustable element proportion by using a microwave-assisted liquid-phase chemical non-equilibrium reaction strategy, is a simple, efficient, low-cost and universal synthesis strategy, and provides a new thought for breaking the bottleneck of synthesizing the nano high-entropy oxide.
2. The nanometer high entropy oxide prepared by the synthesis method of the invention has 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 the electrocatalytic reaction, resulting in improved catalyst activity. In addition, the entropy driving phase stabilization structure of the high-entropy oxide provides guarantee for long-time catalytic stability of the catalyst in the reaction process.
3. The nano high-entropy oxide has rapid reaction kinetics, and the nano morphology enables the surface of the catalyst to expose a large number of active sites, so that the nano high-entropy oxide has excellent catalytic performance. Nano high entropy oxide (Fe a Co b Ni c Cr d Mn e ) 3 O 4-x Wherein, when the mole ratio of Fe, co, ni, cr and Mn of the raw materials is 1:1:2:1:1, the raw materials show the optimal catalytic activity at 10mA cm -2 At a current density of 10mA cm, the overpotential was only 260mV, while also exhibiting excellent stability -2 The potential was changed by only 0.9% for 95h stability test. The catalyst prepared is superior to the commercial RuO 2 An electrocatalyst.
Drawings
FIG. 1 is an XRD pattern of the nano high entropy oxide prepared in examples 1-6;
FIG. 2 is an SEM image of the nano high entropy oxide prepared according to examples 1-6;
FIG. 3 is a graph showing the atomic percent metal of the nano-scale 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 an LSV plot of the nano-high entropy oxides prepared in examples 1-6;
FIG. 7 is a graph of the timing voltage (. Eta.10) of the nano-high entropy oxide prepared in example 4.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A nanometer high entropy oxide is composed of Fe, co, ni, cr, mn, O, and the raw materials are prepared according to the molar ratio of metal elements Fe, co, ni, cr and Mn of 1:1:1:1; the nano high-entropy oxide has a spinel structure, and the granularity is less than 10nm.
The preparation method of the nano high-entropy oxide comprises the following steps:
step 1, preparing a metal salt solution:
0.4102g of ferric nitrate nonahydrate, 0.2940g of cobalt nitrate hexahydrate, 0.2967g of nickel nitrate hexahydrate, 0.404g of chromium nitrate nonahydrate, 0.2561g of manganese nitrate tetrahydrate, dissolved in 50mL of diethylene glycol, and stirred for 3 hours to obtain a clear and transparent solution A.
Step 2, microwave solvothermal reaction:
solution a was transferred to a 100mL polytetrafluoroethylene-lined autoclave and the temperature was raised to 190 ℃ at a rate of rise of 10 ℃/min, followed by a temperature rise of 200 ℃ at a rate of rise of 5 ℃/min and incubation at 200 ℃ for 10min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
Step 3, centrifugal washing:
washing the liquid B with water and ethanol, centrifuging for several times, and washing unreacted metal salt and reaction solvent to obtain solid C.
Step 4, drying:
the obtained solid C is placed in a constant temperature drying oven and dried for 12 hours at 40 ℃ to obtain powder D.
Step 5, calcining:
and placing the powder D in a muffle furnace, and calcining for 4 hours at 300 ℃ to finally obtain the nano high-entropy oxide.
The nano high-entropy oxide prepared in the embodiment has XRD shown in figure 1 (a), SEM shown in figure 2 (a), metal atom percentage shown in figure 3 (a) and XPS shown in figure 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 10 nm), which is beneficial to expose more active sites and improve the catalytic activity. The result in fig. 3 (a) shows that the metal element proportion is close to the experimental design proportion, which proves that the synthesis method can realize accurate adjustment. The results in FIG. 4 show that various valence states of the elements coexist.
The prepared nano high-entropy oxide is used as a working electrode and is applied to electrocatalytic oxygen precipitation reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) After grinding 5mg of nano 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) Ultrasonic treating the liquid obtained in step (1) for 30min to obtain suspension, and dripping 10 μl of suspension into 0.18cm 2 Catalyst loading was 0.55mg cm on carbon paper electrode -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; electrochemical performance testing was performed on the Shanghai Chen Hua 760E electrochemical workstation: LSV sweep speed is 1 mV.s -1 。
Measuring the reaction performance of catalyzing oxygen precipitation by nanometer high entropy oxide in 1M KOH solution, and measuring the LSV as shown in FIG. 6 at current of 10mA.cm -2 The overpotential measured was 271mV.
Example 2
A nanometer high entropy oxide is composed of Fe, co, ni, cr, mn, O, and the raw materials are prepared according to the molar ratio of metal elements Fe, co, ni, cr and Mn of 2:1:1:1:1; the nano high-entropy oxide has a spinel structure, and the granularity is less than 10nm.
The preparation method of the nano high-entropy oxide comprises the following steps:
step 1, preparing a metal salt solution:
0.8203g of ferric nitrate nonahydrate, 0.2940g of cobalt nitrate hexahydrate, 0.2967g of nickel nitrate hexahydrate, 0.404g of chromium nitrate nonahydrate, 0.2561g of manganese nitrate tetrahydrate, dissolved in 50mL of diethylene glycol, and stirred for 3 hours to obtain a clear and transparent solution A.
Step 2, microwave solvothermal reaction:
solution a was transferred to a 100mL polytetrafluoroethylene-lined autoclave and the temperature was raised to 190 ℃ at a rate of rise of 10 ℃/min, followed by a temperature rise of 200 ℃ at a rate of rise of 5 ℃/min and incubation at 200 ℃ for 20min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
Step 3, centrifugal washing:
washing the liquid B with water and ethanol, centrifuging for several times, and washing unreacted metal salt and reaction solvent to obtain solid C.
Step 4, drying:
the obtained solid C is placed in a constant temperature drying oven and dried for 8 hours at 40 ℃ to obtain powder D.
Step 5, calcining:
and (3) placing the powder D in a muffle furnace, and calcining for 3 hours at 400 ℃ to finally obtain the nano high-entropy oxide.
The nano high entropy oxide prepared in this example has XRD shown in FIG. 1 (b), SEM shown in FIG. 2 (b), and metal atom percentage 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 10 nm), which is beneficial to exposing more active sites and improving catalytic activity. The result in fig. 3 (b) shows 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 is applied to electrocatalytic oxygen precipitation reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) After grinding 5mg of high-efficiency oxygen-precipitated nano high-entropy oxide with 1.5mg of carbon black treated with nitric acid at 80℃for 5 hours, 0.5mL of N, N-Dimethylformamide (DMF) and 10. Mu.L of Nafion solution (5 wt%) were added.
(2) Ultrasonic treating the liquid obtained in step (1) for 30min to obtain suspension, and dripping 20 μl of the suspension into 0.18cm 2 Catalyst loading of 1.1mg cm on carbon paper electrode -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; electrochemical performance is carried out on an electrochemical workstation of Shanghai Chen Hua CHI760EThe method can test: LSV sweep speed is 1 mV.s -1 。
Measuring the reaction performance of catalyzing oxygen precipitation by nanometer high entropy oxide in 1M KOH solution, and measuring the LSV as shown in FIG. 6 at current of 10mA.cm -2 The overpotential measured was 293mV.
Example 3
A nanometer high entropy oxide is composed of Fe, co, ni, cr, mn, O, and the raw materials are prepared according to the molar ratio of metal elements Fe, co, ni, cr and Mn of 1:2:1:1:1; the nano high-entropy oxide has a spinel structure, and the granularity is less than 10nm.
The preparation method of the nano high-entropy oxide comprises the following steps:
step 1, preparing a metal salt solution:
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, dissolved in 50mL of diethylene glycol and stirred for 3 hours to obtain a clear and transparent solution A.
Step 2, microwave solvothermal reaction:
solution a was transferred to a 100mL polytetrafluoroethylene-lined autoclave and the temperature was raised to 190 ℃ at a rate of rise of 20 ℃/min, followed by a temperature rise of 200 ℃ at a rate of rise of 5 ℃/min and incubation at 200 ℃ for 30min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
Step 3, centrifugal washing:
washing the liquid B with water and ethanol, centrifuging for several times, and washing unreacted metal salt and reaction solvent to obtain solid C.
Step 4, drying:
the obtained solid C was placed in a constant temperature oven and dried at 40℃for 10 hours to obtain powder D.
Step 5, calcining:
and (3) placing the powder D in a muffle furnace, and calcining for 2 hours at 500 ℃ to finally obtain the nano high-entropy oxide.
The nano high entropy oxide prepared in this example has XRD shown in FIG. 1 (c), SEM shown in FIG. 2 (c), and metal atom percentage shown in FIG. 3 (c); from the XRD result of fig. 1 (c), the high entropy oxide is 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 10 nm), which is beneficial to expose more active sites and improve the catalytic activity. The result in fig. 3 (c) shows 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 is applied to electrocatalytic oxygen precipitation reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) After grinding 5mg of high-efficiency oxygen-precipitated nano high-entropy oxide with 1.5mg of carbon black treated with nitric acid at 90℃for 5 hours, 0.5mL of N, N-Dimethylformamide (DMF) and 10. Mu.L of Nafion solution (5 wt%) were added.
(2) Ultrasonic treating the liquid obtained in step (1) for 30min to obtain suspension, and dripping 20 μl of the suspension into 0.18cm 2 Catalyst loading of 1.1mg cm on carbon paper electrode -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; electrochemical performance testing was performed on the Shanghai Chen Hua 760E electrochemical workstation: LSV sweep speed is 1 mV.s -1 。
Measuring the reaction performance of catalyzing oxygen precipitation by nanometer high entropy oxide in 1M KOH solution, and measuring the LSV as shown in FIG. 6 at current of 10mA.cm -2 The overpotential measured was 281mV.
Example 4
A nanometer high entropy oxide is composed of Fe, co, ni, cr, mn, O, and the raw materials are prepared according to the molar ratio of metal elements Fe, co, ni, cr and Mn of 1:1:2:1:1; the nano high-entropy oxide has a spinel structure, and the granularity is less than 10nm.
The preparation method of the nano high-entropy oxide comprises the following steps:
step 1, preparing a metal salt solution:
0.4102g of ferric nitrate nonahydrate, 0.2940g of cobalt nitrate hexahydrate, 0.5934g of nickel nitrate hexahydrate, 0.404g of chromium nitrate nonahydrate, 0.2561g of manganese nitrate tetrahydrate, dissolved in 50mL of diethylene glycol, and stirred for 3 hours to obtain a clear and transparent solution A.
Step 2, microwave solvothermal reaction:
solution a was transferred to a 100mL polytetrafluoroethylene-lined autoclave and the temperature was raised to 190 ℃ at a rate of rise of 30 ℃/min, followed by a temperature rise of 200 ℃ at a rate of rise of 5 ℃/min and incubation at 200 ℃ for 40min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
Step 3, centrifugal washing:
washing the liquid B with water and ethanol, centrifuging for several times, and washing unreacted metal salt and reaction solvent to obtain solid C.
Step 4, drying:
the obtained solid C is placed in a constant temperature drying oven and dried for 6 hours at 60 ℃ to obtain powder D.
Step 5, calcining:
and (3) placing the powder D in a muffle furnace, and calcining for 4 hours at 500 ℃ to finally obtain the nano high-entropy oxide.
The nano high entropy oxide prepared in this example has XRD shown in FIG. 1 (d), SEM shown in FIG. 2 (d), metal atom percentage shown in FIG. 3 (d) and XPS shown in FIG. 5; from the XRD result of fig. 1 (d), the high entropy oxide is 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 10 nm), which is beneficial to expose more active sites and improve the catalytic activity. The result in fig. 3 (d) shows that the metal element proportion is close to the experimental design proportion, which proves that the synthesis method can realize accurate adjustment. The results in FIG. 5 show that various valence states of the elements coexist.
The prepared nano high-entropy oxide is used as a working electrode and is applied to electrocatalytic oxygen precipitation reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) After grinding 5mg of high-efficiency oxygen-precipitated nano high-entropy oxide with 1.5mg of carbon black treated with nitric acid at 80℃for 3 hours, 0.5mL of N, N-Dimethylformamide (DMF) and 10. Mu.L of Nafion solution (5 wt%) were added.
(2) Ultrasonic treating the liquid obtained in step (1) for 30min to obtain suspension, and dripping 20 μl of the suspension into 0.18cm 2 Catalyst loading of 1.1mg cm on carbon paper electrode -2 The electrode is used asThe method comprises the steps of taking an Hg/HgO electrode as a reference electrode, a platinum sheet as a counter electrode and 1M KOH as electrolyte; electrochemical performance testing was performed on the Shanghai Chen Hua 760E electrochemical workstation: LSV sweep speed is 1 mV.s -1 。
Measuring the reaction performance of catalyzing oxygen precipitation by nanometer high entropy oxide in 1M KOH solution, and measuring the LSV as shown in FIG. 6 at current of 10mA.cm -2 The overpotential measured was 260mV. FIG. 7 is a graph of the timing voltage (. Eta.10) of a nano high entropy oxide catalyst, showing that the voltage was not significantly increased, and good activity and stability were achieved after 95 hours of stability testing.
Example 5
A nanometer high entropy oxide catalyst is composed of Fe, co, ni, cr, mn, O, and the raw materials are prepared according to the molar ratio of metal elements Fe, co, ni, cr and Mn of 1:1:1:2:1; the nano high-entropy oxide has a spinel structure, and the granularity is less than 10nm.
The preparation method of the nano high-entropy oxide comprises the following steps:
step 1, preparing a metal salt solution:
0.4102g of ferric nitrate nonahydrate, 0.2940g of cobalt nitrate hexahydrate, 0.2967g of nickel nitrate hexahydrate, 0.808g of chromium nitrate nonahydrate, 0.2561g of manganese nitrate tetrahydrate, dissolved in 50mL of diethylene glycol, and stirred for 3 hours to obtain a clear and transparent solution A.
Step 2, microwave solvothermal reaction:
solution a was transferred to a 100mL polytetrafluoroethylene-lined autoclave and the temperature was raised to 190 ℃ at a rate of rise of 30 ℃/min, followed by a temperature rise of 200 ℃ at a rate of rise of 5 ℃/min and incubation at 200 ℃ for 50min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
Step 3, centrifugal washing:
washing the liquid B with water and ethanol, centrifuging for several times, and washing unreacted metal salt and reaction solvent to obtain solid C.
Step 4, drying:
the obtained solid C is placed in a constant temperature drying oven and dried for 4 hours at 80 ℃ to obtain powder D.
Step 5, calcining:
and (3) placing the powder D in a muffle furnace, and calcining for 2 hours at 600 ℃ to finally obtain the nano high-entropy oxide.
The nano high entropy oxide prepared in this example has XRD shown in FIG. 1 (e), SEM shown in FIG. 2 (e), and metal atom percentage shown in FIG. 3 (e); from the XRD result of fig. 1 (e), the high entropy oxide is 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 10 nm), which is beneficial to expose more active sites and improve the catalytic activity. The result in fig. 3 (e) shows 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 is applied to electrocatalytic oxygen precipitation reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) After grinding 5mg of high-efficiency oxygen-precipitated nano high-entropy oxide with 1.5mg of carbon black treated with nitric acid at 90℃for 3 hours, 0.5mL of N, N-Dimethylformamide (DMF) and 10. Mu.L of Nafion solution (5 wt%) were added.
(2) Ultrasonic treating the liquid obtained in step (1) for 30min to obtain suspension, and dripping 20 μl of the suspension into 0.18cm 2 Catalyst loading of 1.1mg cm on carbon paper electrode -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; electrochemical performance testing was performed on the Shanghai Chen Hua 760E electrochemical workstation: LSV sweep speed is 1 mV.s -1 。
Measuring the reaction performance of catalyzing oxygen precipitation by nanometer high entropy oxide in 1M KOH solution, and measuring the LSV as shown in FIG. 6 at current of 10mA.cm -2 The overpotential measured was 283mV.
Example 6
A nanometer high entropy oxide is composed of Fe, co, ni, cr, mn, O, and the raw materials are prepared according to the molar ratio of metal elements Fe, co, ni, cr and Mn of 1:1:1:1:2; the nano high-entropy oxide has a spinel structure, and the granularity is less than 10nm.
The preparation method of the nano high-entropy oxide comprises the following steps:
step 1, preparing a metal salt solution:
0.4102g of ferric nitrate nonahydrate, 0.2940g of cobalt nitrate hexahydrate, 0.2967g of nickel nitrate hexahydrate, 0.404g of chromium nitrate nonahydrate, 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.
Step 2, microwave solvothermal reaction:
solution a was transferred to a 100mL polytetrafluoroethylene-lined autoclave and the temperature was raised to 190 ℃ at a rate of rise of 30 ℃/min, followed by a temperature rise of 200 ℃ at a rate of rise of 5 ℃/min and incubation at 200 ℃ for 60min. And naturally cooling to room temperature after the reaction is finished to obtain liquid B.
Step 3, centrifugal washing:
washing the liquid B with water and ethanol, centrifuging for several times, and washing unreacted metal salt and reaction solvent to obtain solid C.
Step 4, drying:
the obtained solid C is placed in a constant temperature drying oven and dried for 10 hours at 60 ℃ to obtain powder D.
Step 5, calcining:
and placing the powder D in a muffle furnace, and calcining for 4 hours at 600 ℃ to finally obtain the nano high-entropy oxide.
The nano high entropy oxide prepared in this example has XRD shown in FIG. 1 (f), SEM shown in FIG. 2 (f), and metal atom percentage shown in FIG. 3 (f); from the XRD result of fig. 1 (f), the high entropy oxide is 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 10 nm), which is beneficial to expose more active sites and improve the catalytic activity. The result in fig. 3 (f) shows 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 is applied to electrocatalytic oxygen precipitation reaction in a 1M KOH solution, and the method specifically comprises the following steps:
(1) After grinding 5mg of high-efficiency oxygen-precipitated nano high-entropy oxide with 1.5mg of carbon black treated with nitric acid at 80℃for 5 hours, 0.5mL of N, N-Dimethylformamide (DMF) and 10. Mu.L of Nafion solution (5 wt%) were added.
(2) Ultrasonic treating the liquid obtained in step (1) for 30min to obtain suspension, and dripping 20 μl of the suspension into 0.18cm 2 Catalyst loading of 1.1mg cm on carbon paper electrode -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; electrochemical performance testing was performed on the Shanghai Chen Hua 760E electrochemical workstation: LSV sweep speed is 1 mV.s -1 。
Measuring the reaction performance of the nanometer high entropy oxide catalyst for catalyzing oxygen to separate out in 1M KOH solution, and LSV is shown in FIG. 6, and the current is 10mA cm -2 The overpotential measured was 277mV.
The technical scheme of the invention is explained in the technical scheme, the protection scope of the invention cannot be limited by the technical scheme, and any changes and modifications to the technical scheme according to the technical substance of the invention belong to the protection scope of the technical scheme of the invention.
Claims (8)
1. The preparation method of the nano high-entropy oxide is characterized in that the high-entropy oxide comprises five metal elements Fe, co, ni, cr, mn and non-metal elements O, wherein the metal elements Fe, co, ni, cr, mn are composed in different molar ratios, and each metal atom accounts for 5% -40% of the total metal atoms;
the nanometer high entropy oxide is (Fe) a Co b Ni c Cr d Mn e ) 3 O 4-x A, b, c, d, e has a value of 1/20-2/5 and a, b, c, d, e sum of 1, and the nano high entropy oxide has a spinel structure; the particle size is 2-10 nm;
the molar ratio of Fe, co, ni, cr, mn is 1:1:2:1:1, a step of;
the preparation method of the nano high-entropy oxide comprises the following steps:
step 1, preparing a metal salt solution:
weighing Fe, co, ni, cr, mn metal salts of five elements, adding the metal salts into the polyol, 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 in a high-pressure closed environment by utilizing microwaves, and stirring simultaneously in the reaction process to obtain a solution B after the reaction is finished;
the heating temperature is 180-240 ℃, the heating rate is 5-30 ℃/min, and the heat preservation time is 10-60min;
step 3, centrifugal washing:
adding a washing solvent into the solution B for centrifugal washing for a plurality of times to wash out unreacted metal salt and reaction solvent, thus obtaining a solid C;
step 4, drying:
placing the obtained solid C in a constant temperature drying oven, and drying to obtain powder D;
step 5, calcining:
and (3) placing the powder D in a muffle furnace for calcination to finally obtain the nano high-entropy oxide.
2. The method for preparing nano high entropy oxide according to claim 1, wherein the nano high entropy oxide is used for high efficiency oxygen evolution electrocatalyst.
3. The method for preparing nano high-entropy oxide according to claim 1, wherein in the step 1, the metal salt is metal nitrate; the polyol is diethylene glycol; the concentration of the total metal nitrate in diethylene glycol is 0.05-0.3 mol.L -1 。
4. The method for preparing 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.
5. The method for preparing nano high entropy oxide according to claim 1, wherein in the step 5, the calcination temperature is 200-600 ℃ and the calcination time is 2-4 hours.
6. Use of a nano high entropy oxide prepared according to the preparation method of any one of claims 1-5 as a working electrode for catalyzing oxygen evolution reactions under alkaline conditions.
7. The use of a nano high entropy oxide according to claim 6, comprising in particular:
(1) Weighing and grinding the nano high-entropy oxide and the conductive carbon black according to the mass ratio of 3:1 to uniformly mix, and adding a dispersing agent, wherein the concentration of the nano high-entropy oxide in the dispersing agent is 5-20 mg/mL -1 Adding Nafion solution with the mass fraction of 5%, wherein the volume ratio of the dispersing agent to the 5% Nafion solution is 50:1;
(2) Preparing uniformly dispersed suspension by ultrasonic treatment for 30-60 min, and dripping 10-20 μl of suspension onto carbon paper electrode, wherein the nanometer high entropy oxide loading is 0.55-1.1mg cm -2 。
8. The application of the nano high-entropy oxide according to claim 7, wherein in the step (1), the dispersing agent is one or a mixed solution of a plurality of N, N-dimethylformamide, absolute ethyl alcohol, deionized water, isopropanol and acetone; before use, the carbon black is refluxed for 3 to 8 hours at the temperature of between 60 and 90 ℃ by nitric acid; in the step (2), the area of the carbon paper electrode is 0.18cm 2 。
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