阅读说明：本技术 一种高效氧析出高熵非晶氧化物纳米催化剂及其制备方法和应用 (High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst and preparation method and application thereof ) 是由 王志远 李兴龙 姜顺达 刘延国 郑润国 王丹 孙宏宇 于 2021-08-11 设计创作，主要内容包括：一种高效氧析出高熵非晶氧化物纳米催化剂及其制备方法和应用,属于催化剂技术领域,本发明方法结合温和的低温液相还原方法拓展非平衡合成策略,利用过量的硼氢化钠溶于多元醇构建一个极端的还原性环境,将多达十种的金属盐前体快速还原为高熵非晶氧化物纳米颗粒,为纳米高熵氧化物合成领域提供了一种新的制备工艺。采用本发明方法制备出的高熵非晶氧化物有高熵的鸡尾酒效应以及无定型的结构,改善了氧化物表面与氧中间体之间的相互作用,并且提供大量的活性位点,大大提高了催化活性。(The invention relates to a high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst, a preparation method and application thereof, belonging to the technical field of catalysts. The high-entropy amorphous oxide prepared by the method has a high-entropy cocktail effect and an amorphous structure, improves the interaction between the surface of the oxide and an oxygen intermediate, provides a large number of active sites, and greatly improves the catalytic activity.)

1. The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst is characterized in that elements in the catalyst consist of Fe, Co, Ni, Mn, Cu, Sn, Sb, Cr, Ru, Ir and B, O, wherein metal elements can consist of any five or more than five elements of Fe, Co, Ni, Mn, Cu, Sn, Sb, Cr, Ru and Ir, the atomic concentration of each metal atom is 5-60%, and the catalyst has an amorphous structure; the particle size is 5-30 nm.

2. The preparation method of the high-efficiency oxygen evolution high-entropy amorphous oxide nano-catalyst according to claim 1, characterized by comprising the following steps:

step 1, preparation of solution precursor:

(1) preparation of metal salt precursor: selecting five or more elements from Fe, Co, Ni, Mn, Cu, Sn, Sb, Cr, Ru and Ir, weighing metal salts corresponding to the selected elements, completely dissolving the metal salts in polyhydric alcohol, and stirring at room temperature until the solution is completely clear and uniform to obtain a solution A, wherein the atomic concentration of each metal atom is 5-60%;

(2) preparation of reducing agent solution: dissolving polyvinylpyrrolidone in polyalcohol, performing ultrasonic treatment to obtain clear and transparent solution, freezing the solution in ice water bath, and adding NaBH₄Stirring to obtainObtaining a clear solution which is marked as solution B;

and 2, reduction reaction:

under the air condition, the solution A is dripped into the stirred reducing agent solution B to carry out reduction reaction, and a solution C is obtained after the reaction is finished;

step 3, centrifugal washing:

adding a solvent into the solution C for centrifugal washing, and washing out residual organic solvent and impurities to obtain a solid D;

and 4, drying:

and drying the obtained solid to obtain the high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst.

3. The method for preparing the high-efficiency oxygen evolution high-entropy amorphous oxide nano-catalyst according to claim 2, wherein in the step 1(1), the metal salt is a chloride salt of a metal; the polyhydric alcohol is diethylene glycol; the concentration of the metal salt in the polyol is 0.05 to 0.2 mol.L^-1(ii) a The amount of the polyhydric alcohol is an amount greater than or equal to the amount that brings the metal salt into solubility; the stirring time is 2-10 hours at room temperature.

4. The method for preparing the high-efficiency oxygen evolution high-entropy amorphous oxide nano-catalyst according to claim 2, wherein in the step 1(2), the concentration of polyvinylpyrrolidone in the polyol is 0.1-0.25 mol-L^-1(ii) a The polyhydric alcohol is diethylene glycol solution; the ultrasonic time is 80-150 minutes, and the ice-water bath freezing time is 10-30 minutes; NaBH₄The concentration in the polyol is 0.1 to 0.25 mol.L^-1。

5. The method for preparing the high-efficiency oxygen evolution high-entropy amorphous oxide nano-catalyst according to claim 2, wherein in the step 2, the reaction stirring time is 30 minutes; the dropping speed of the solution A dropwise into the solution B is 1-5 mL/min^-1。

6. The method for preparing the high-entropy amorphous oxide nano-catalyst by high-efficiency oxygen precipitation according to claim 2, wherein in the step 3, a solvent adopted by centrifugal washing is one or a mixed solution of several of deionized water, absolute ethyl alcohol and acetone.

7. The preparation method of the high-efficiency oxygen precipitation high-entropy amorphous oxide nano-catalyst according to claim 2, wherein in the step 4, the drying temperature is 40-60 ℃ and the drying time is 10-12 hours.

8. The application of the high-efficiency oxygen evolution high-entropy amorphous oxide nano-catalyst disclosed by claim 1, wherein the catalyst is used as a working electrode and is applied to catalyzing oxygen evolution reaction under alkaline conditions.

Technical Field

The invention belongs to the technical field of catalysts, and particularly relates to a high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst, and a preparation method and application thereof.

Background

The electrically driven water splitting involves two half-reactions, the cathodic Hydrogen Evolution Reaction (HER) and the anodic Oxygen Evolution Reaction (OER). OER kinetics are slower compared to HER involving four electron transfer, each of which requires a high overpotential to overcome the high kinetic energy barrier, and therefore OER is a key process to control the overall efficiency of electrochemical water splitting. Currently Ru, Ir and their oxides are the most advanced OER catalysts, but scarcity and high cost limit their wide application and RuO at high anodic potential₂IrO, very unstable in acidic and alkaline electrolytes₂Similar stability issues exist, so it is important to design and prepare rich transition metal-based electrocatalysts.

The high-entropy oxide is a single-phase solid solution containing five or more element types, and has the characteristic of entropy-driven phase stability, compared with the traditional oxide, the entropy, the enthalpy and the synergistic effect generated by interaction of multiple cations show strong advantages, the existence of the multiple cations enables the regulation of an electronic structure to be more flexible, the band gap energy of some high-entropy oxides is similar to the effect driven by a single element, but the high-entropy oxide shows more excellent performance, and the activity of the high-entropy oxide is further improved. It is worth noting that amorphous materials with short-range order and long-range disorder exhibit better OER electrocatalytic activity than the corresponding crystalline materials, and are gradually recognized by researchers. The advantages of the amorphous material are mainly reflected in three aspects: firstly, the amorphous material has a large number of unsaturated coordination sites, so that more active sites can be provided; secondly, the amorphous material has a large number of randomly oriented bonds, so that the structure is more flexible; third, the amorphous material can adjust the electronic structure in a wide range. These advantages contribute to the high-entropy oxide, so that the high-entropy oxide exhibits excellent activity.

The synthesis method of the high-entropy oxide reported at present comprises the following steps: spray pyrolysis, sol-gel combustion, solid-phase synthesis methods, wet chemistry methods, coprecipitation methods and the like, although the methods are numerous, the synthesis methods are often harsh in conditions and poor in component expansibility, so that development of a new process which is simple in process, low in cost and capable of preparing high-entropy oxide amorphous nanoparticles in batches is imperative.

Disclosure of Invention

Aiming at the technical problems, the invention provides a high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst and a preparation method and application thereof. The method provided by the invention is combined with a mild low-temperature liquid phase reduction method to expand a non-equilibrium synthesis strategy, an extreme reducing environment is constructed by dissolving excessive sodium borohydride in polyhydric alcohol, up to ten metal salt precursors are rapidly reduced into high-entropy amorphous oxide nanoparticles, and a novel preparation process is provided for the field of synthesis of nano high-entropy oxides. The high-entropy amorphous oxide prepared by the method has a high-entropy cocktail effect and an amorphous structure, improves the interaction between the surface of the oxide and an oxygen intermediate, provides a large number of active sites, and greatly improves the catalytic activity.

The technical scheme of the invention is as follows:

a high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst comprises elements of Fe, Co, Ni, Mn, Cu, Sn, Sb, Cr, Ru, Ir and B, O, wherein metal elements can be any five or more of Fe, Co, Ni, Mn, Cu, Sn, Sb, Cr, Ru and Ir, the atomic concentration of each metal atom is 5-60%, and the catalyst has an amorphous structure; the particle size is 5-30 nm.

The invention also provides a preparation method of the high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst, which comprises the following steps:

step 1, preparation of solution precursor:

(1) preparation of metal salt precursor: selecting five or more elements from Fe, Co, Ni, Mn, Cu, Sn, Sb, Cr, Ru and Ir, weighing metal salts corresponding to the selected elements, completely dissolving the metal salts in polyhydric alcohol, and stirring at room temperature until the solution is completely clear and uniform to obtain a solution A, wherein the atomic concentration of each metal atom is 5-60%;

(2) preparation of reducing agent solution: dissolving polyvinylpyrrolidone in polyalcohol, performing ultrasonic treatment to obtain clear and transparent solution, freezing the solution in ice water bath, and adding NaBH₄Stirring to obtain a clear solution, and recording the clear solution as a solution B;

and 2, reduction reaction:

under the air condition, the solution A is dripped into the stirred reducing agent solution B to carry out reduction reaction, and a solution C is obtained after the reaction is finished;

step 3, centrifugal washing:

adding a solvent into the solution C for centrifugal washing, and washing out residual organic solvent and impurities to obtain a solid D;

and 4, drying:

and drying the obtained solid to obtain the high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst.

In the step 1(1), the metal salt is a chloride salt of a metal; the polyhydric alcohol is diethylene glycol; the concentration of the metal salt in the polyol is 0.05 to 0.2 mol.L^-1(ii) a The amount of the polyhydric alcohol is greater than or equal to the amount that causes the metal salt to reach solubility, in order to cause the metal salt to be completely dissolved; the stirring time is 2-10 hours at room temperature.

In the step 1(2), the concentration of polyvinylpyrrolidone in the polyol is 0.1-0.25 mol.L^-1(polyvinylpyrrolidone is a high polymer, calculated as the molar mass of the monomer equal to 111 when calculating the addition); the polyhydric alcohol is diethylene glycol solution; the ultrasonic time is 80-150 minutes, and the ice-water bath freezing time is 10-30 minutes; NaBH₄The concentration in the polyol is 0.1 to 0.25 mol.L^-1。

In the step 2, the reaction stirring time is 30 minutes; dropwise adding the solution A into the solution B through a peristaltic pump, wherein the dropping speed is 1-5 mL/min^-1。

In the step 3, the solvent adopted for centrifugal washing is one or a mixture of deionized water, absolute ethyl alcohol and acetone.

In the step 4, the drying temperature is 40-60 ℃, and the drying time is 10-12 hours. The molar ratio of the metal elements in the prepared high-entropy amorphous oxide nano catalyst is basically consistent with that of the metal elements in the material weighing.

The invention also provides an application method of the high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst as a working electrode in catalyzing oxygen precipitation reaction under alkaline conditions, which specifically comprises the following steps:

(1) weighing the high-entropy amorphous oxide nano catalyst precipitated by high-efficiency oxygen and carbon black according to the mass ratio of 10:3, uniformly mixing, grinding, and adding a dispersing agent and a Nafion solution (ethanol solution of perfluorosulfonic acid-polytetrafluoroethylene copolymer) with the mass fraction of 5% for mixing.

(2) Carrying out ultrasonic treatment on the mixed solution for 30-100 minutes to prepare a suspension, and dripping the suspension on a carbon paper electrode, wherein the loading capacity of the high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst is 1.1 mg-cm^-2And after drying, the electrode is used as a working electrode for catalyzing oxygen precipitation reaction under an alkaline condition.

In the step (1), the dispersant is one or a mixture of N, N-Dimethylformamide (DMF), absolute ethyl alcohol and deionized water; the carbon black is refluxed for 4-8 hours at 80-90 ℃ by nitric acid before use. The mass-volume ratio of the dispersing agent to the high-entropy amorphous oxide nano catalyst precipitated by the high-efficiency oxygen to the dispersing agent is 10 mg/mL^-1Controlling the amount of the active ingredient; the mass-volume ratio of the Nafion solution to the high-entropy amorphous oxide nano catalyst precipitated by the high-efficiency oxygen to the Nafion solution with the mass fraction of 5 percent is 0.5 mg.mu.L^-1The amount of the control.

In the step (2), the area of the carbon paper electrode is 0.18cm²。

The invention has the beneficial effects that:

1. the method for synthesizing the high-entropy amorphous oxide nano catalyst utilizes a liquid-phase chemical non-equilibrium strategy, can synthesize high-entropy amorphous oxide nano particles with uniform components at room temperature, is a universal synthesis strategy, and has simple preparation process and low cost. Provides a new idea for the batch preparation of the high-entropy amorphous oxide.

2. The reducing agent selected in the invention is NaHB₄And the metal salt precursor and the alcohol with reducibility form a strong reducing environment together, so that the difference between the reduction potentials of the metal salt precursor is overcome, and different metal precursors are reduced into isolated atom monomers simultaneously. The energy of the system is at its highest initially and the supersaturation of the monomer is at its highest. The moment that the metal salt precursor gets into reducing solution, destroyed the high energy state that reducing solution is stable relatively, limited atomic monomer diffusion carries out fast nucleation in the very short time, because various monomer concentrations are nearly unanimous, the even and element random distribution of component of the nuclear that consequently forms, along with the going on of reaction, system energy further reduces, along with the consumption of precursor is totally up, the reaction finishes, system energy is finally in the metastable state, the nonequilibrium synthesis of the multicomponent amorphous oxide of chemical supersaturation driven has been realized.

3. The high-entropy oxide catalyst prepared by the synthesis method disclosed by the invention has an amorphous structure, and the amorphous structure with stable entropy driving phase not only has a large amount of unsaturated coordination sites, so that the activity of the catalyst is improved, but also the structure of the catalyst is more stable, and the catalytic activity can be provided for a long time.

4. The high-entropy amorphous oxide nano catalyst has excellent conductivity, a rough surface can expose a large number of active sites, and excellent catalytic performance is shown. Fe as measured under alkaline conditions₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xThe high-entropy amorphous oxide nano catalyst catalyzes oxygen precipitation reaction at the current of 10 mA-cm^-2The measured overpotential was 259mV, and the Tafel slope was 66.1mV dec^-1Is superior to RuO under the same condition₂Electrocatalytic performance of oxygen evolution (304mV @10mA · cm)^-2Tafel slope 112.3mV dec^-1) At 10mA · cm^-2The voltage of the E-t stability test was not significantly increased by 55 hours of continuous operation at the current density of (1).

In conclusion, the invention is the development of a general synthesis strategy of the high-entropy amorphous oxide nano catalyst, and can realize mass production due to low cost and simple and effective process of low-temperature reduction. Is a novel high-entropy amorphous oxide nano-catalyst synthesis strategy.

Drawings

Fig. 1 is an SEM image of the prepared high efficiency oxygen precipitation high entropy amorphous oxide nano catalyst: wherein (a) is the high entropy amorphous oxide catalyst Fe of example 1₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xSEM picture of (a); (b) is the high entropy amorphous oxide catalyst Fe of example 2_26.7Co_26.65Ni_26.65Mn₁₀Cu₁₀BO_xSEM picture of (a); (c) is the high entropy amorphous oxide catalyst Fe of example 3₄₀Co₂₀Ni₂₀Mn₁₀Cu₁₀BO_xSEM picture of (a); (d) is the high entropy amorphous oxide catalyst Fe of example 4_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xSEM picture of (a); (e) is the high entropy amorphous oxide catalyst FeCoNiMnCuBO of example 5_xSEM picture of (a); (f) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnBO of example 6_xSEM picture of (a); (g) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbBO of example 7_xSEM picture of (a); (h) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbRuBO of example 8_xSEM picture of (a); (i) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbRuCrBO of example 9_xSEM picture of (a); (j) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbRuCrIrBO of example 10_xSEM pictures of (d).

FIG. 2 is an XPS survey spectrum of the prepared high efficiency oxygen precipitation high entropy amorphous oxide nano-catalyst: wherein (a) is the high entropy amorphous oxide catalyst Fe of example 1₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xXPS full spectrum of (a); (b) is the high entropy amorphous oxide catalyst Fe of example 4_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xXPS survey spectrum of (1).

FIG. 3 is a high-entropy amorphous oxide nanocatalyst prepared by efficient oxygen precipitationMetal atomic ratio of the reagent example: wherein (a) is the high entropy amorphous oxide catalyst Fe of example 1₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xThe metal atom ratio picture of (a); (b) is the high entropy amorphous oxide catalyst Fe of example 4_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xThe metal atom ratio picture of (a); (c) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbRuBO of example 8_xThe metal atom ratio picture of (a); (d) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbRuCrBO of example 9_xThe atomic ratio of metal of (1).

Fig. 4 is a distribution diagram of metal elements in the prepared high-efficiency oxygen precipitation high-entropy amorphous oxide nano-catalyst: wherein (a) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnBO of example 6_xThe distribution diagram of the metal elements in (1); (b) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbBO of example 7_xThe distribution diagram of the metal elements in (1); (c) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbRuBO of example 8_xThe distribution diagram of the metal elements in (1); (d) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbRuCrBO of example 9_xThe distribution diagram of the metal elements in (1); (e) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbRuCrIrBO of example 10_xDistribution diagram of metal elements in (1).

Fig. 5 is an XRD pattern of the prepared high-efficiency oxygen precipitation high-entropy amorphous oxide nano-catalyst: wherein (a) is the high entropy amorphous oxide catalyst Fe of example 1₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xXRD pictures of (1); (b) is the high entropy amorphous oxide catalyst Fe of example 2_26.7Co_26.65Ni_26.65Mn₁₀Cu₁₀BO_xXRD pictures of (1); (c) is the high entropy amorphous oxide catalyst Fe of example 3₄₀Co₂₀Ni₂₀Mn₁₀Cu₁₀BO_xXRD pictures of (1); (d) is the high entropy amorphous oxide catalyst Fe of example 4_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xXRD pictures of (1); (e) to implementHigh entropy amorphous oxide catalyst FeCoNiMnCuBO of example 5_xXRD pictures of (1); (f) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnBO of example 6_xXRD pictures of (1); (g) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbBO of example 7_xXRD pictures of (1); (h) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbRuBO of example 8_xXRD pictures of (1); (i) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbRuCrBO of example 9_xXRD pictures of (1); (j) is the high entropy amorphous oxide catalyst FeCoNiMnCuSnSbRuCrIrBO of example 10_xXRD pictures of (a).

FIG. 6 is a LSV plot of the high efficiency oxygen evolution high entropy amorphous oxide nanocatalysts prepared in examples 1-10.

FIG. 7 shows the high efficiency oxygen precipitating high entropy amorphous oxide catalyst Fe prepared in example 1₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xTiming voltage (η 10) diagram.

Detailed Description

The present invention will be further described with reference to the following detailed description and the accompanying drawings, but the present invention is not limited to these embodiments.

Example 1

High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xThe catalyst consists of Fe, Co, Ni, Mn, Cu, B and O, wherein the molar ratio of metal elements Fe, Co, Ni, Mn and Cu is 16: 32: 32: 10: 10; in an amorphous structure, the catalyst Fe₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xThe particle size is 5-30 nm.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xThe preparation method comprises the following steps:

step 1, solution preparation:

(1) preparation of metal salt precursor solution: weighing 0.25mmol of metal salt precursor of ferrous chloride tetrahydrate (0.0080g), cobalt chloride hexahydrate (0.0194g), nickel chloride hexahydrate (0.0194g), manganese chloride tetrahydrate (0.0050g) and copper chloride dihydrate (0.0043g), completely dissolving the weighed metal salt in 5mL of diethylene glycol, sealing the diethylene glycol with a preservative film, and stirring for 2 hours with a magnetic stirrer until the solution is completely clarified and uniform to obtain a solution A;

(2) preparation of reducing agent solution: 0.2775g of polyvinylpyrrolidone was dissolved in 20mL of diethylene glycol solution, sonicated for 80 minutes until a clear and transparent solution was obtained, which was frozen in an ice water bath for 10 minutes, and 0.0965g of NaBH was added₄Stirring at low speed to obtain clear solution, and recording the clear solution as solution B;

and 2, reduction reaction:

under air conditions, solution A was pumped through a peristaltic pump at 3.5 mL. min^-1Dropping the solution into the reducing agent solution B which is rapidly stirred drop by drop to carry out reduction reaction for 30 minutes to obtain a solution C;

step 3, centrifugal washing:

pouring the solution C into a centrifuge tube, adding absolute ethyl alcohol and deionized water for centrifugal washing, and thoroughly washing off residual organic solvent and impurities in the solution C to obtain a solid D;

and 4, drying:

drying the solid D in an oven at 40 ℃ for 10 hours to obtain the high-efficiency oxygen-separated high-entropy amorphous oxide nano catalyst Fe₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xThe molar ratio of the metal elements in the prepared high-entropy amorphous oxide nano catalyst is basically consistent with that of the metal elements in the material weighing.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xThe application method of the working electrode in catalyzing oxygen evolution reaction under alkaline conditions specifically comprises the following steps:

(1) 5mg of high-efficiency oxygen is separated out of the high-entropy amorphous oxide nano catalyst Fe₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xWas homogeneously mixed with 1.5mg of carbon black treated with nitric acid at 90 ℃ for 5 hoursAfter mixing and grinding, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution were added and mixed.

(2) Subjecting the solution to ultrasonic treatment for 60 min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm²The catalyst loading on the carbon paper electrode of (1.1 mg cm)^-2After drying, 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, a three-electrode system is established, 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。

From the SEM result of FIG. 1(a), the high-entropy amorphous oxide nano-catalyst Fe₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xThe dispersion is uniform, the particle size is uniform, the particle surface is rough, more active sites can be exposed, and the activity of the catalyst is improved. FIG. 2(a) clearly shows the synthesized high entropy amorphous oxide nano catalyst Fe₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xContains Fe, Co, Ni, Mn, Cu, B, O and C (wherein C is derived from conductive adhesive) elements. The elemental metal ratios of fig. 3(a) demonstrate that the elemental metal ratios of the catalyst are close to the design molar ratios, demonstrating that the non-equilibrium chemical reduction strategy of the present invention achieves precise adjustment of the catalyst component ratios. The XRD results of fig. 5(a) demonstrate that the catalyst is amorphous in structure. High-entropy amorphous oxide nano catalyst Fe under alkaline condition₁₆Co₃₂Ni₃₂Mn₁₀Cu₁₀BO_xCatalyzing oxygen evolution reaction, FIG. 6 shows that at a current of 10mA cm^-2The overpotential was 259mV, FIG. 7 is 10mA cm^-2The stability test performed under the corresponding voltage shows that the voltage is not obviously increased after the stability test for 55 hours, and the stability test has good activity and stability.

Example 2

High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe_26.7Co_26.65Ni_26.65Mn₁₀Cu₁₀BO_xThe catalyst consists of Fe, Co, Ni, Mn, Cu, B and O, and the catalyst is prepared from Fe, Co, Ni, Mn, Cu, B and OThe molar ratio of the medium metal elements Fe, Co, Ni, Mn and Cu is 26.7: 26.65: 26.65: 10: 10; in an amorphous structure, the catalyst Fe_26.7Co_26.65Ni_26.65Mn₁₀Cu₁₀BO_xThe particle size is 5-30 nm.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe_26.7Co_26.65Ni_26.65Mn₁₀Cu₁₀BO_xThe preparation method comprises the following steps:

step 1, solution preparation:

(1) preparation of metal salt precursor solution: weighing 0.5mmol of metal salt precursor including ferrous chloride tetrahydrate (0.0268g), cobalt chloride hexahydrate (0.0324g), nickel chloride hexahydrate (0.0323g), manganese chloride tetrahydrate (0.0100g) and copper chloride dihydrate (0.0085g), completely dissolving the weighed metal salt in 5mL of diethylene glycol, sealing the diethylene glycol with a preservative film, and stirring for 3 hours with a magnetic stirrer until the solution is completely clear and uniform to obtain a solution A;

(2) preparation of reducing agent solution: 0.2775g of polyvinylpyrrolidone was dissolved in 20mL of diethylene glycol solution, sonicated for 100 minutes until a clear and transparent solution was obtained, which was frozen in an ice water bath for 20 minutes, and 0.0965g of NaBH was added₄Stirring at low speed to obtain clear solution, and recording the clear solution as solution B;

and 2, reduction reaction:

under air conditions, solution A was pumped through a peristaltic pump at 3 mL. min^-1Dropping the solution into the reducing agent solution B which is rapidly stirred drop by drop to carry out reduction reaction for 30 minutes to obtain a solution C;

step 3, centrifugal washing:

pouring the solution C into a centrifuge tube, adding absolute ethyl alcohol and deionized water for centrifugal washing, and thoroughly washing off residual organic solvent and impurities in the solution C to obtain a solid D;

and 4, drying:

drying the solid D in an oven at 40 ℃ for 10 hours to obtain the high-efficiency oxygen-separated high-entropy amorphous oxide nano catalyst Fe_26.7Co_26.65Ni_26.65Mn₁₀Cu₁₀BO_xThe molar ratio of the metal elements in the prepared high-entropy amorphous oxide nano catalyst is basically consistent with that of the metal elements in the material weighing.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe_26.7Co_26.65Ni_26.65Mn₁₀Cu₁₀BO_xThe application method of the working electrode in catalyzing oxygen evolution reaction under alkaline conditions specifically comprises the following steps:

(1) after 5mg of the high-entropy amorphous oxide nano-catalyst precipitated by high-efficiency oxygen and 1.5mg of carbon black treated by nitric acid at 90 ℃ for 5 hours are uniformly mixed and ground, 0.5mL of N, N-Dimethylformamide (DMF) and 10 muL of Nafion solution are added and mixed.

(2) Subjecting the solution to ultrasonic treatment for 60 min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm²The catalyst loading on the carbon paper electrode of (1.1 mg cm)^-2After drying, 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, a three-electrode system is established, 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。

From the SEM result of FIG. 1(b), the high-entropy amorphous oxide nano-catalyst Fe_26.7Co_26.65Ni_26.65Mn₁₀Cu₁₀BO_xThe dispersion is uniform, the particle size is uniform, the particle surface is rough, more active sites can be exposed, and the activity of the catalyst is improved. FIG. 2(b) clearly shows the synthesized high entropy amorphous oxide nano catalyst Fe_26.7Co_26.65Ni_26.65Mn₁₀Cu₁₀BO_xContains Fe, Co, Ni, Mn, Cu, B, O and C (wherein C is derived from conductive adhesive) elements. XRD results of FIG. 5(b) demonstrate Fe in the catalyst_26.7Co_26.65Ni_26.65Mn₁₀Cu₁₀BO_xThe amorphous structure is beneficial to the activity and stability of the catalyst. The nano-scale rough surface can provide rich active sites, and the Fe content is measured under the alkaline condition_26.7Co_26.65Ni_26.65Mn₁₀Cu₁₀BO_xThe high-entropy amorphous oxide nano-catalyst catalyzes the oxygen evolution reaction, and FIG. 6 shows that the current is 10mA cm^-2The overpotential was measured to be 268mV, with good activity.

Example 3

High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe₄₀Co₂₀Ni₂₀Mn₁₀Cu₁₀BO_xThe catalyst consists of Fe, Co, Ni, Mn, Cu, B and O, wherein the molar ratio of metal elements Fe, Co, Ni, Mn and Cu is 40: 20: 20: 10: 10; in an amorphous structure, the catalyst Fe₄₀Co₂₀Ni₂₀Mn₁₀Cu₁₀BO_xThe particle size is 5-30 nm.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe₄₀Co₂₀Ni₂₀Mn₁₀Cu₁₀BO_xThe preparation method comprises the following steps:

step 1, solution preparation:

(1) preparation of metal salt precursor solution: weighing 1mmol of metal salt precursor of ferrous chloride tetrahydrate (0.0803g), cobalt chloride hexahydrate (0.0486g), nickel chloride hexahydrate (0.0485g), manganese chloride tetrahydrate (0.0200g) and copper chloride dihydrate (0.0170g), completely dissolving the weighed metal salt in 5mL of diethylene glycol, sealing the diethylene glycol with a preservative film, and stirring for 5 hours by using a magnetic stirrer until the solution is completely clarified and uniform to obtain a solution A;

(2) preparation of reducing agent solution: 0.2775g of polyvinylpyrrolidone was dissolved in 20mL of diethylene glycol solution, sonicated for 100 minutes until a clear and transparent solution was obtained, which was frozen in an ice water bath for 30 minutes, and 0.0965g of NaBH was added₄Stirring at low speed to obtain clear solution, and recording the clear solution as solution B;

and 2, reduction reaction:

under air conditions, solution A was passed through a peristaltic pump at 2.5 mL. min^-1Dropping the solution into the reducing agent solution B which is rapidly stirred drop by drop to carry out reduction reaction for 30 minutes to obtain a solution C;

step 3, centrifugal washing:

pouring the solution C into a centrifuge tube, adding absolute ethyl alcohol and deionized water for centrifugal washing, and thoroughly washing off residual organic solvent and impurities in the solution C to obtain a solid D;

and 4, drying:

drying the solid D in an oven at 40 ℃ for 10 hours to obtain the high-efficiency oxygen-separated high-entropy amorphous oxide nano catalyst Fe₄₀Co₂₀Ni₂₀Mn₁₀Cu₁₀BO_xThe molar ratio of the metal elements in the prepared high-entropy amorphous oxide nano catalyst is basically consistent with that of the metal elements in the material weighing.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe₄₀Co₂₀Ni₂₀Mn₁₀Cu₁₀BO_xThe application method of the working electrode in catalyzing oxygen evolution reaction under alkaline conditions specifically comprises the following steps:

(1) 5mg of high-efficiency oxygen is separated out of the high-entropy amorphous oxide nano catalyst Fe₄₀Co₂₀Ni₂₀Mn₁₀Cu₁₀BO_xAfter uniformly mixing with 1.5mg of carbon black treated with nitric acid at 90 ℃ for 5 hours, and grinding, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution were added and mixed.

(2) Subjecting the solution to ultrasonic treatment for 60 min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm²The catalyst loading on the carbon paper electrode of (1.1 mg cm)^-2After drying, 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, a three-electrode system is established, 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。

From the SEM result of FIG. 1(c), the high-entropy amorphous oxide nano-catalyst Fe₄₀Co₂₀Ni₂₀Mn₁₀Cu₁₀BO_xThe dispersion is uniform, the particle size is uniform, the particle surface is rough, more active sites can be exposed, and the activity of the catalyst is improved. XRD results of FIG. 5(c) demonstrate Fe in the catalyst₄₀Co₂₀Ni₂₀Mn₁₀Cu₁₀BO_xThe amorphous structure is beneficial to the activity and stability of the catalyst. The nano-scale rough surface can provide rich active sites, and the Fe content is measured under the alkaline condition₄₀Co₂₀Ni₂₀Mn₁₀Cu₁₀BO_xThe high-entropy amorphous oxide nano-catalyst catalyzes the oxygen evolution reaction, and FIG. 6 shows that the current is 10mA cm^-2The measured overpotential was 280mV, with good activity.

Example 4

High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xThe catalyst consists of Fe, Co, Ni, Mn, Cu, B and O, wherein the molar ratio of metal elements Fe, Co, Ni, Mn and Cu is 53.3: 13.35: 13.35: 10: 10; in an amorphous structure, the catalyst Fe_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xThe particle size is 5-30 nm.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xThe preparation method comprises the following steps:

step 1, solution preparation:

(1) preparation of metal salt precursor solution: weighing 0.5mmol of metal salt precursor of ferrous chloride tetrahydrate (0.0535g), cobalt chloride hexahydrate (0.0162g), nickel chloride hexahydrate (0.0162g), manganese chloride tetrahydrate (0.0100g) and copper chloride dihydrate (0.0085g), completely dissolving the weighed metal salt in 5mL of diethylene glycol, sealing the diethylene glycol with a preservative film, and stirring for 7 hours with a magnetic stirrer until the solution is completely clarified and uniform to obtain a solution A;

(2) preparation of reducing agent solution: 0.333g of polyvinylpyrrolidone was dissolved in 20mL of diethylene glycol solution, sonicated for 100 minutes until a clear and transparent solution was obtained, frozen in an ice water bath for 20 minutes, and 0.0965g of NaBH was added₄Stirring at low speed to obtain clear solution, and recording the clear solution as solution B;

and 2, reduction reaction:

under air conditions, solution A was pumped through a peristaltic pump at 3.5 mL. min^-1Dropping the solution into the reducing agent solution B which is rapidly stirred drop by drop to carry out reduction reaction for 30 minutes to obtain a solution C;

step 3, centrifugal washing:

pouring the solution C into a centrifuge tube, adding absolute ethyl alcohol and deionized water for centrifugal washing, and thoroughly washing off residual organic solvent and impurities in the solution C to obtain a solid D;

and 4, drying:

drying the solid D in an oven at 40 ℃ for 10 hours to obtain the high-efficiency oxygen-separated high-entropy amorphous oxide nano catalyst Fe_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xThe molar ratio of the metal elements in the prepared high-entropy amorphous oxide nano catalyst is basically consistent with that of the metal elements in the material weighing.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst Fe_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xThe application method of the working electrode in catalyzing oxygen evolution reaction under alkaline conditions specifically comprises the following steps:

(1) 5mg of high-efficiency oxygen is separated out of the high-entropy amorphous oxide nano catalyst Fe_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xAfter uniformly mixing with 1.5mg of carbon black treated with nitric acid at 80 ℃ for 5 hours, and grinding, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution were added and mixed.

(2) Subjecting the solution to ultrasonic treatment for 60 min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm²The catalyst loading on the carbon paper electrode of (1.1 mg cm)^-2After drying, 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, a three-electrode system is established, 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。

From the SEM result of FIG. 1(d), the high entropy amorphous oxide nanocatalysisAgent Fe_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xThe dispersion is uniform, the particle size is uniform, the particle surface is rough, more active sites can be exposed, and the activity of the catalyst is improved. The elemental metal ratios of fig. 3(b) demonstrate that the elemental metal ratios of the catalyst are close to the design molar ratios, demonstrating that the non-equilibrium chemical reduction strategy of the present invention achieves precise adjustment of the catalyst component ratios. XRD results of FIG. 5(d) demonstrate Fe in the catalyst_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xThe amorphous structure is beneficial to the activity and stability of the catalyst. The nano-scale rough surface can provide rich active sites, and the Fe content is measured under the alkaline condition_53.3Co_13.35Ni_13.35Mn₁₀Cu₁₀BO_xThe high-entropy amorphous oxide nano-catalyst catalyzes the oxygen evolution reaction, and FIG. 6 shows that the current is 10mA cm^-2The overpotential was measured to be 329mV, with good activity.

Example 5

High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuBO_xThe catalyst consists of Fe, Co, Ni, Mn, Cu, B and O, wherein the molar ratio of metal elements Fe, Co, Ni, Mn and Cu is 1: 1: 1: 1: 1; the catalyst FeCoNiMnCuBO has an amorphous structure_xThe particle size is 5-30 nm.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuBO_xThe preparation method comprises the following steps:

step 1, solution preparation:

(1) preparation of metal salt precursor solution: weighing 0.5mmol of metal salt precursor of ferrous chloride tetrahydrate (0.0201g), cobalt chloride hexahydrate (0.0243g), nickel chloride hexahydrate (0.0243g), manganese chloride tetrahydrate (0.0200g) and copper chloride dihydrate (0.0170g), completely dissolving the weighed metal salt in 5mL of diethylene glycol, sealing the diethylene glycol with a preservative film, and stirring for 10 hours by using a magnetic stirrer until the solution is completely clarified and uniform to obtain a solution A;

(2) preparation of reducing agent solution: 0.555g of polyethyleneDissolving vinylpyrrolidone in 20mL diethylene glycol solution, sonicating for 100 minutes until a clear and transparent solution is obtained, freezing the solution in an ice water bath for 20 minutes, and adding 0.0965g NaBH₄Stirring at low speed to obtain clear solution, and recording the clear solution as solution B;

and 2, reduction reaction:

under air conditions, solution A was pumped through a peristaltic pump at 3.5 mL. min^-1Dropping the solution into the reducing agent solution B which is rapidly stirred drop by drop to carry out reduction reaction for 30 minutes to obtain a solution C;

step 3, centrifugal washing:

pouring the solution C into a centrifuge tube, adding absolute ethyl alcohol and deionized water for centrifugal washing, and thoroughly washing off residual organic solvent and impurities in the solution C to obtain a solid D;

and 4, drying:

drying the solid D in an oven at 40 ℃ for 10 hours to obtain a high-efficiency oxygen-separated high-entropy amorphous oxide nano catalyst FeCoNiMnCuBO_xThe molar ratio of the metal elements in the prepared high-entropy amorphous oxide nano catalyst is basically consistent with that of the metal elements in the material weighing.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuBO_xThe application method of the working electrode in catalyzing oxygen evolution reaction under alkaline conditions specifically comprises the following steps:

(1) separating out high-entropy amorphous oxide nano catalyst FeCoNiMnCuBO by 5mg of high-efficiency oxygen_xAfter uniformly mixing with 1.5mg of carbon black treated with nitric acid at 90 ℃ for 4 hours, and grinding, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution were added and mixed.

(2) Subjecting the solution to ultrasonic treatment for 60 min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm²The catalyst loading on the carbon paper electrode of (1.1 mg cm)^-2And drying the electrode to be used as a working electrode. The Hg/HgO electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, a three-electrode system is established, 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。

From the SEM result of FIG. 1(e), the high-entropy amorphous oxide nano-catalyst FeCoNiMnCuBO_xThe dispersion is uniform, the particle size is uniform, the particle surface is rough, more active sites can be exposed, and the activity of the catalyst is improved. XRD results of FIG. 5(e) demonstrate that the catalyst FeCoNiMnCuBO_xThe amorphous structure is beneficial to the activity and stability of the catalyst. The nano-scale rough surface can provide rich active sites, and FeCoNiMnCuBO is measured under the alkaline condition_xThe high-entropy amorphous oxide nano-catalyst catalyzes the oxygen evolution reaction, and FIG. 6 shows that the current is 10mA cm^-2The overpotential was measured to be 284mV, with good activity.

Example 6

High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnBO_xThe catalyst consists of Fe, Co, Ni, Mn, Cu, Sn, B and O, wherein the molar ratio of metal elements Fe, Co, Ni, Mn, Cu and Sn is 1: 1: 1: 1: 1: 1; the catalyst FeCoNiMnCuSnBO has an amorphous structure_xThe particle size is 5-30 nm.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnBO_xThe preparation method comprises the following steps:

step 1, solution preparation:

(1) preparation of metal salt precursor solution: weighing 0.5mmol of metal salt precursor of ferrous chloride tetrahydrate (0.0167g), cobalt chloride hexahydrate (0.0202g), nickel chloride hexahydrate (0.0202g), manganese chloride tetrahydrate (0.0167g), copper chloride dihydrate (0.0142g) and tin chloride dihydrate (0.0188g), completely dissolving the weighed metal salt in 5mL of diethylene glycol, sealing the diethylene glycol with a preservative film, and stirring for 3 hours with a magnetic stirrer until the solution is completely clear and uniform to obtain a solution A;

(2) preparation of reducing agent solution: 0.222g of polyvinylpyrrolidone is dissolved in 20mL of diethylene glycol solution, sonicated for 110 minutes until a clear and transparent solution is obtained, which is frozen in an ice water bath for 30 minutes, after which 0.0965g of NaBH is added₄Stirring at low speed to obtain clear solution, and recording the clear solution as solution B;

and 2, reduction reaction:

under air conditions, solution A was pumped through a peristaltic pump at 2 mL. min^-1Dropping the solution into the reducing agent solution B which is rapidly stirred drop by drop to carry out reduction reaction for 30 minutes to obtain a solution C;

step 3, centrifugal washing:

pouring the solution C into a centrifuge tube, adding absolute ethyl alcohol and deionized water for centrifugal washing, and thoroughly washing off residual organic solvent and impurities in the solution C to obtain a solid D;

and 4, drying:

drying the solid D in an oven at 50 ℃ for 10 hours to obtain a high-efficiency oxygen-separated high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnBO_xThe molar ratio of the metal elements in the prepared high-entropy amorphous oxide nano catalyst is basically consistent with that of the metal elements in the material weighing.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnBO_xThe application method of the working electrode in catalyzing oxygen evolution reaction under alkaline conditions specifically comprises the following steps:

(1) separating out high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnBO from 5mg of high-efficiency oxygen_xAfter uniformly mixing with 1.5mg of carbon black treated with nitric acid at 90 ℃ for 5 hours, and grinding, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution were added and mixed.

(2) Subjecting the solution to ultrasonic treatment for 60 min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm²The catalyst loading on the carbon paper electrode of (1.1 mg cm)^-2After drying, 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, a three-electrode system is established, and the electrolyte is 1M KOH; on the Shanghai Chenhua CHI760E electrochemical workstation, electrochemical performance tests were performed: the LSV sweep rate is 10mV s^-1。

From the SEM result of FIG. 1(f), the high-entropy amorphous oxide nano-catalyst FeCoNiMnCuSnBO_xThe dispersion is uniform, the particle size is uniform, the particle surface is rough, more active sites can be exposed, and the activity of the catalyst is improved. As a result of the distribution of the metal elements in FIG. 4(a), all the metal elements are separated in the catalystUniform in distribution and uniform in particle size. XRD results of FIG. 5(f) demonstrate that the catalyst FeCoNiMnCuSnBO_xThe amorphous structure is beneficial to the activity and stability of the catalyst. The nano-scale rough surface can provide rich active sites, and FeCoNiMnCuSnBO is measured under the alkaline condition_xThe high-entropy amorphous oxide nano-catalyst catalyzes the oxygen evolution reaction, and FIG. 6 shows that the current is 10mA cm^-2The overpotential was measured to be 360mV, with good activity.

Example 7

High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbBO_xThe catalyst consists of Fe, Co, Ni, Mn, Cu, Sn, Sb, B and O, wherein the molar ratio of metal elements Fe, Co, Ni, Mn, Cu, Sn and Sb is 1: 1: 1: 1: 1: 1: 1; the catalyst FeCoNiMnCuSnSbBO has an amorphous structure_xThe particle size is 5-30 nm.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbBO_xThe preparation method comprises the following steps:

step 1, solution preparation:

(1) preparation of metal salt precursor solution: weighing 0.5mmol of metal salt precursor of ferrous chloride tetrahydrate (0.0143g), cobalt chloride hexahydrate (0.0173g), nickel chloride hexahydrate (0.0173g), manganese chloride tetrahydrate (0.0143g), copper chloride dihydrate (0.0122g), tin chloride dihydrate (0.0161g) and antimony trichloride (0.0165g), completely dissolving the weighed metal salt in 5mL of diethylene glycol, sealing the diethylene glycol with a preservative film, and stirring for 3 hours by using a magnetic stirrer until the solution is completely clear and uniform to obtain a solution A;

(2) preparation of reducing agent solution: 0.2775g of polyvinylpyrrolidone was dissolved in 20mL of diethylene glycol solution, sonicated for 130 minutes until a clear and transparent solution was obtained, which was frozen in an ice water bath for 20 minutes, and 0.0965g of NaBH was added₄Stirring at low speed to obtain clear solution, and recording the clear solution as solution B;

and 2, reduction reaction:

under air conditions, solution A was pumped through a peristaltic pump at 1 mL. min^-1At a rapid rate of dripping dropwiseCarrying out reduction reaction in the rapidly stirred reducing agent solution B for 30 minutes to obtain a solution C;

step 3, centrifugal washing:

pouring the solution C into a centrifuge tube, adding absolute ethyl alcohol and deionized water for centrifugal washing, and thoroughly washing off residual organic solvent and impurities in the solution C to obtain a solid D;

and 4, drying:

drying the solid D in an oven at 60 ℃ for 10 hours to obtain the high-efficiency oxygen-precipitated high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbBO_xThe molar ratio of the metal elements in the prepared high-entropy amorphous oxide nano catalyst is basically consistent with that of the metal elements in the material weighing.

The catalyst prepared by the synthesis strategy of the high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst is used as a working electrode in a catalytic oxygen precipitation reaction under an alkaline condition, and the specific method comprises the following steps:

(1) separating out high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbBO from 5mg of high-efficiency oxygen_xAfter uniformly mixing with 1.5mg of carbon black treated with nitric acid at 80 ℃ for 8 hours, and grinding, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution were added and mixed.

(2) Subjecting the solution to ultrasonic treatment for 60 min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm²The catalyst loading on the carbon paper electrode of (1.1 mg cm)^-2After drying, 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, a three-electrode system is established, and the electrolyte is 1M KOH; on the Shanghai Chenhua CHI760E electrochemical workstation, electrochemical performance tests were performed: the LSV sweep rate is 10mV s^-1。

From the SEM result of FIG. 1(g), the high-entropy amorphous oxide nano-catalyst FeCoNiMnCuSnSbBO_xThe dispersion is uniform, the particle size is uniform, the particle surface is rough, more active sites can be exposed, and the activity of the catalyst is improved. As a result of the distribution of the metal elements in fig. 4(b), all the metal elements are uniformly distributed in the catalyst and have uniform particle diameters. XRD results of FIG. 5(g) demonstrate that the catalyst FeCoNiMnCuSnSbBO_xAmorphous structure, beneficial to catalystActivity and stability of (c). The nano-scale rough surface can provide rich active sites, and FeCoNiMnCuSnSbBO is measured under the alkaline condition_xThe high-entropy amorphous oxide nano-catalyst catalyzes the oxygen evolution reaction, and FIG. 6 shows that the current is 10mA cm^-2The measured overpotential was 332mV, with good activity.

Example 8

High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuBO_xThe catalyst consists of Fe, Co, Ni, Mn, Cu, Sn, Sb, Ru, B and O, wherein the molar ratio of metal elements Fe, Co, Ni, Mn, Cu, Sn, Sb and Ru is 1: 1: 1: 1: 1: 1: 1: 1; the catalyst FeCoNiMnCuSnSbRuBO has an amorphous structure_xThe particle size is 5-30 nm.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuBO_xThe preparation method comprises the following steps:

step 1, solution preparation:

(1) preparation of metal salt precursor solution: weighing 0.5mmol of metal salt precursor of ferrous chloride tetrahydrate (0.0126g), cobalt chloride hexahydrate (0.0152g), nickel chloride hexahydrate (0.0152g), manganese chloride tetrahydrate (0.0125g), copper chloride dihydrate (0.0107g), stannic chloride dihydrate (0.0141g), antimony trichloride (0.0144g) and ruthenium chloride hydrate (0.0130g), completely dissolving the weighed metal salt in 5mL of diethylene glycol, sealing the diethylene glycol with a preservative film, and stirring for 3 hours by using a magnetic stirrer until the solution is completely clear and uniform to obtain a solution A;

(2) preparation of reducing agent solution: 0.2775g of polyvinylpyrrolidone was dissolved in 20mL of diethylene glycol solution, sonicated for 150 minutes until a clear and transparent solution was obtained, which was frozen in an ice water bath for 20 minutes, and 0.0772g of NaBH was added₄Stirring at low speed to obtain clear solution, and recording the clear solution as solution B;

and 2, reduction reaction:

under air conditions, solution A was pumped through a peristaltic pump at 4 mL. min^-1Dropping into the reducing agent solution B with rapid stirring at a certain speed for reduction reaction for 30 min to obtain solutionLiquid C;

step 3, centrifugal washing:

pouring the solution C into a centrifuge tube, adding absolute ethyl alcohol and deionized water for centrifugal washing, and thoroughly washing off residual organic solvent and impurities in the solution C to obtain a solid D;

and 4, drying:

drying the solid D in an oven at 40 ℃ for 12 hours to obtain the high-efficiency oxygen-precipitated high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuBO_xThe molar ratio of the metal elements in the prepared high-entropy amorphous oxide nano catalyst is basically consistent with that of the metal elements in the material weighing.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuBO_xThe application method of the working electrode in catalyzing oxygen evolution reaction under alkaline conditions specifically comprises the following steps:

(1) separating out high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuBO by 5mg of high-efficiency oxygen_xAfter uniformly mixing with 1.5mg of carbon black treated with nitric acid at 80 ℃ for 4 hours, and grinding, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution were added and mixed.

(2) Subjecting the solution to ultrasonic treatment for 30 min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm²The catalyst loading on the carbon paper electrode of (1.1 mg cm)^-2After drying, 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, a three-electrode system is established, and the electrolyte is 1M KOH; on the Shanghai Chenhua CHI760E electrochemical workstation, electrochemical performance tests were performed: the LSV sweep rate is 10mV s^-1。

From the SEM result of FIG. 1(h), the high-entropy amorphous oxide nano-catalyst FeCoNiMnCuSnSbRuBO_xThe dispersion is uniform, the particle size is uniform, the particle surface is rough, more active sites can be exposed, and the activity of the catalyst is improved. The elemental metal ratios of fig. 3(c) demonstrate that the elemental metal ratios of the catalyst are close to the design molar ratios, demonstrating that the non-equilibrium chemical reduction strategy of the present invention achieves precise adjustment of the catalyst component ratios. FIG. 4(c) shows the distribution of metal elements in the catalystThe medium distribution is uniform, and the particle size is uniform. XRD results of FIG. 5(h) demonstrate that the catalyst FeCoNiMnCuSnSbRuBO_xThe amorphous structure is beneficial to the activity and stability of the catalyst. The nano-scale rough surface can provide rich active sites, and FeCoNiMnCuSnSbRuBO is measured under the alkaline condition_xThe high-entropy amorphous oxide nano-catalyst catalyzes the oxygen evolution reaction, and FIG. 6 shows that the current is 10mA cm^-2The measured overpotential was 308mV, with good activity.

Example 9

High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuCrBO_xThe catalyst consists of Fe, Co, Ni, Mn, Cu, Sn, Sb, Ru, Cr, B and O, wherein the molar ratio of metal elements Fe, Co, Ni, Mn, Cu, Sn, Sb, Ru and Cr is 1: 1: 1: 1: 1: 1: 1: 1: 1; the catalyst FeCoNiMnCuSnSbRuCrBO has an amorphous structure_xThe particle size is 5-30 nm.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuCrBO_xThe preparation method comprises the following steps:

step 1, solution preparation:

(1) preparation of metal salt precursor solution: weighing 0.5mmol of metal salt precursor of ferrous chloride tetrahydrate (0.0112g), cobalt chloride hexahydrate (0.0135g), nickel chloride hexahydrate (0.0135g), manganese chloride tetrahydrate (0.0111g), copper chloride dihydrate (0.0095g), stannic chloride dihydrate (0.0125g), antimony trichloride (0.0128g), ruthenium chloride hydrate (0.0115g) and chromium chloride hexahydrate (0.0150g), completely dissolving the weighed metal salt in 5mL of diethylene glycol, sealing the metal salt with a preservative film, and stirring for 3 hours by using a magnetic stirrer until the solution is completely clarified and uniform to obtain a solution A;

(2) preparation of reducing agent solution: 0.2775g of polyvinylpyrrolidone was dissolved in 20mL of diethylene glycol solution, sonicated for 100 minutes until a clear and transparent solution was obtained, which was frozen in an ice water bath for 20 minutes, and 0.1158g of NaBH was added₄Stirring at low speed to obtain clear solution, and recording the clear solution as solution B;

and 2, reduction reaction:

under air conditions, solution A was pumped through a peristaltic pump at 5 mL. min^-1Dropping the solution into the reducing agent solution B which is rapidly stirred drop by drop to carry out reduction reaction for 30 minutes to obtain a solution C;

step 3, centrifugal washing:

pouring the solution C into a centrifuge tube, adding absolute ethyl alcohol and deionized water for centrifugal washing, and thoroughly washing off residual organic solvent and impurities in the solution C to obtain a solid D;

and 4, drying:

drying the solid D in an oven at 50 ℃ for 12 hours to obtain the high-efficiency oxygen-precipitated high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuCrBO_xThe molar ratio of the metal elements in the prepared high-entropy amorphous oxide nano catalyst is basically consistent with that of the metal elements in the material weighing.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuCrBO_xThe application method of the working electrode in catalyzing oxygen evolution reaction under alkaline conditions specifically comprises the following steps:

(1) separating out high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuCrBO by 5mg of high-efficiency oxygen_xAfter uniformly mixing with 1.5mg of carbon black treated with nitric acid at 90 ℃ for 4 hours, and grinding, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution were added and mixed.

(2) Subjecting the solution to ultrasonic treatment for 80 min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm²The catalyst loading on the carbon paper electrode of (1.1 mg cm)^-2After drying, 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, a three-electrode system is established, and the electrolyte is 1M KOH; on the Shanghai Chenhua CHI760E electrochemical workstation, electrochemical performance tests were performed: the LSV sweep rate is 10mV s^-1。

From the SEM result of FIG. 1(i), the high-entropy amorphous oxide nano-catalyst FeCoNiMnCuSnSbRuCrBO_xThe dispersion is uniform, the particle size is uniform, the particle surface is rough, more active sites can be exposed, and the activity of the catalyst is improved. The metal element ratio of FIG. 3(d) confirms that the metal element ratio of the catalyst is close to that of the catalystThe timing molar ratio proves that the non-equilibrium chemical reduction strategy of the invention realizes the precise adjustment of the ratio of the catalyst components. As a result of the distribution of the metal elements in fig. 4(d), all the metal elements are uniformly distributed in the catalyst and have uniform particle diameters. XRD results of FIG. 5(i) demonstrate that the catalyst FeCoNiMnCuSnSbRuCrBO_xThe amorphous structure is beneficial to the activity and stability of the catalyst. The nano-scale rough surface can provide rich active sites, and FeCoNiMnCuSnSbRuCrBO is measured under the alkaline condition_xThe high-entropy amorphous oxide nano-catalyst catalyzes the oxygen evolution reaction, and FIG. 6 shows that the current is 10mA cm^-2The overpotential was found to be 369mV, with good activity.

Example 10

High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuCrIrBO_xThe catalyst consists of Fe, Co, Ni, Mn, Cu, Sn, Sb, Ru, Cr, Ir, B and O, wherein the molar ratio of metal elements Fe, Co, Ni, Mn, Cu, Sn, Sb, Ru, Cr and Ir is 1: 1: 1: 1: 1: 1: 1: 1: 1: 1; the catalyst FeCoNiMnCuSnSbRuCrIrBO has an amorphous structure_xThe particle size is 5-30 nm.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuCrIrBO_xThe preparation method comprises the following steps:

step 1, solution preparation:

(1) preparation of metal salt precursor solution: weighing 0.5mmol of metal salt precursors of ferrous chloride tetrahydrate (0.0100g), cobalt chloride hexahydrate (0.0121g), nickel chloride hexahydrate (0.0121g), manganese chloride tetrahydrate (0.0100g), copper chloride dihydrate (0.0085g), stannic chloride dihydrate (0.0113g), antimony trichloride (0.0115g), ruthenium chloride hydrate (0.0104g), chromium chloride hexahydrate (0.0135g) and iridium chloride hydrate (0.0149g), completely dissolving the weighed metal salts in 5mL of diethylene glycol, sealing the diethylene glycol with a preservative film, and stirring for 3 hours with a magnetic stirrer until the solution is completely clarified and uniform to obtain a solution A;

(2) preparation of reducing agent solution: 0.2775g of polyvinylpyrrolidone was dissolved in 20mL of diethylene glycol solution and sonicated for 100 minutesTo give a clear and transparent solution, the solution was frozen in an ice-water bath for 20 minutes and 0.193g of NaBH was added₄Stirring at low speed to obtain clear solution, and recording the clear solution as solution B;

and 2, reduction reaction:

under air conditions, solution A was pumped through a peristaltic pump at 3.5 mL. min^-1Dropping the solution into the reducing agent solution B which is rapidly stirred drop by drop to carry out reduction reaction for 30 minutes to obtain a solution C;

step 3, centrifugal washing:

pouring the solution C into a centrifuge tube, adding absolute ethyl alcohol and deionized water for centrifugal washing, and thoroughly washing off residual organic solvent and impurities in the solution C to obtain a solid D;

and 4, drying:

drying the solid D in an oven at the temperature of 60 ℃ for 12 hours to obtain the high-efficiency oxygen-precipitated high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuCrIrBO_xThe molar ratio of the metal elements in the prepared high-entropy amorphous oxide nano catalyst is basically consistent with that of the metal elements in the material weighing.

The high-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuCrIrBO_xThe application method of the working electrode in catalyzing oxygen evolution reaction under alkaline conditions specifically comprises the following steps:

(1) separating out high-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuCrIrBO by 5mg of high-efficiency oxygen_xAfter uniformly mixing with 1.5mg of carbon black treated with nitric acid at 90 ℃ for 8 hours, and grinding, 0.5mL of N, N-Dimethylformamide (DMF) and 10. mu.L of Nafion solution were added and mixed.

(2) Subjecting the solution to ultrasonic treatment for 100 min to obtain suspension, and dripping 20 μ L of suspension into 0.18cm²The catalyst loading on the carbon paper electrode of (1.1 mg cm)^-2After drying, 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, a three-electrode system is established, and the electrolyte is 1M KOH; on the Shanghai Chenhua CHI760E electrochemical workstation, electrochemical performance tests were performed: the LSV sweep rate is 10mV s^-1。

From the SEM result of FIG. 1(j), theHigh-entropy amorphous oxide nano catalyst FeCoNiMnCuSnSbRuCrBO_xThe dispersion is uniform, the particle size is uniform, the particle surface is rough, more active sites can be exposed, and the activity of the catalyst is improved. As a result of the distribution of the metal elements in fig. 4(e), all the metal elements are uniformly distributed in the catalyst and have uniform particle diameters. XRD results of FIG. 5(j) demonstrate that the catalyst FeCoNiMnCuSnSbRuCrIrBO_xThe amorphous structure is beneficial to the activity and stability of the catalyst. The nano-scale rough surface can provide rich active sites, and FeCoNiMnCuSnSbRuCrIrBO is measured under the alkaline condition_xThe high-entropy amorphous oxide nano-catalyst catalyzes the oxygen evolution reaction, and FIG. 6 shows that the current is 10mA cm^-2The overpotential was found to be 279mV, with good activity.