CN110947374A - Hydroxyl metal oxide nano catalyst and preparation method thereof - Google Patents

Hydroxyl metal oxide nano catalyst and preparation method thereof Download PDF

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CN110947374A
CN110947374A CN201911294089.6A CN201911294089A CN110947374A CN 110947374 A CN110947374 A CN 110947374A CN 201911294089 A CN201911294089 A CN 201911294089A CN 110947374 A CN110947374 A CN 110947374A
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acid
metal oxide
deionized water
acetate
sulfate
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严亮
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Foshan Polytechnic
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
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Abstract

The invention discloses a hydroxyl metal oxide nano catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: 1) ultrasonically cleaning a conductive substrate by using acid, ethanol, acetone and deionized water in sequence to obtain a conductive substrate with a clean surface and rich defects; 2) adding metal salt and urea into deionized water and an organic solvent for dissolving, transferring the solution into a liner of a reaction kettle, then adding a conductive substrate with a clean surface and rich defects, carrying out hydrothermal reaction under a certain condition, washing and drying a product to obtain a reactant 1; 3) adding the reactant 1 into deionized water and an alkaline solution, then adding an oxidant, carrying out magnetic stirring reaction under the oil bath condition, washing and drying a product to obtain the hydroxyl metal oxide nano catalyst. The invention solves the problems of complex synthesis, low activity and poor stability of the oxygen evolution reaction catalyst prepared by the prior art.

Description

Hydroxyl metal oxide nano catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a hydroxyl metal oxide nano catalyst and a preparation method thereof.
Background
Hydrogen is a renewable energy source with high energy density, cleanness and no pollution. Proton Exchange Membrane Water Electrolysers (PEMWE) are widely considered as a very promising means of converting intermittent solar or wind energy into sustainable hydrogen energy due to their high energy efficiency, high productivity and high purity of hydrogen gas, compared to conventional steam reforming of methane. Water electrolysis involves two half-reactions: hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). Unfortunately, OER on the anode side is still subject to slow reaction kinetics compared to the minimal energy loss of the HER on the cathode side, and becomes a major bottleneck for practical application of PEMWE, and therefore, an electrocatalyst capable of efficiently evolving oxygen needs to be designed to improve the efficiency of PEMWE. Heretofore, noble metal oxide catalysts (e.g., IrO)2And RuO2) Considered the most advanced OER catalysts, the low reserves of Ir and Ru are the major limitations for their widespread use. Therefore, the search for alternatives to noble metal compound catalysts has attracted considerable attention. Non-noble metals (Fe, Co, Ni, Mn, Cu, etc.) and their compounds have been widely reported as OER catalysts with application prospects, but still require very large overpotentials (at 10mA cm)-2At current density>300mV) was used to drive the reaction. Meanwhile, the problems of low reaction efficiency, poor stability and the like exist in the OER reaction catalyzed by using a non-noble metal catalyst instead of noble metal. Therefore, the development of non-noble metal catalysts with high activity and high stability is urgently required to solve the above problems, but it remains a great challenge.
In recent years, transition metal oxyhydroxides (MOOH, M ═ Co, Fe, Ni, and the like) have been confirmed to have activity to catalyze Oxygen Evolution Reaction (OER) and have been widely noticed and studied. However, the transition metal oxyhydroxide catalysts of the type reported in the literature have the following problems: 1) the synthesis method is complicated; 2) the conductivity is low; 3) catalyst particles are easy to agglomerate in the reaction process, so that the catalytic activity and the stability are reduced. Therefore, there is still a lot of work to be done to address the above problems.
Disclosure of Invention
In view of the above, an object of the present invention is to prepare a metal oxide hydroxide nano-catalyst with high OER activity.
The invention also aims to provide a preparation method of the hydroxyl metal oxide nano-catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme.
The preparation method of the hydroxyl metal oxide nano catalyst is characterized by comprising the following steps of:
1) ultrasonically cleaning a conductive substrate by using acid, ethanol, acetone and deionized water in sequence to obtain a conductive substrate with a clean surface;
2) adding metal salt and urea into deionized water and an organic solvent for dissolving, transferring the solution into a liner of a reaction kettle, then adding a conductive substrate with a clean surface, carrying out hydrothermal reaction under a certain condition, washing and drying a product to obtain a reactant 1;
3) adding the reactant 1 into deionized water and an alkaline solution, then adding an oxidant, carrying out magnetic stirring reaction under the condition of oil bath, washing and drying a product to obtain the hydroxyl metal oxide nano catalyst.
Preferably, in step 1), the acid is selected from one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hypochlorous acid and acetic acid, formic acid, oxalic acid.
Preferably, in step 1), the conductive substrate is one of carbon paper, carbon cloth, carbon nanotube, titanium felt, titanium mesh, cobalt foam, iron foam, nickel foam, copper foil, aluminum foil, graphene, graphite alkyne and MXene.
Preferably, in step 2), the transition metal salt is selected from one or two of iron salt, cobalt salt, nickel salt, vanadium salt, manganese salt or chromium salt; the ferric salt is selected from one of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferric acetate, ferrous acetate and ferric acetylacetonate; the cobalt salt is selected from one of cobalt chloride, cobaltous chloride, cobalt sulfate, cobaltous sulfate, cobalt nitrate, cobaltous nitrate, cobalt acetate, cobaltous acetate and cobalt acetylacetonate; the nickel salt is selected from one of nickel chloride, nickel sulfate, nickel nitrate, nickel acetate and nickel acetylacetonate; the vanadium salt is selected from one of vanadium sulfate, vanadium chloride, vanadium acetylacetonate, vanadyl acetylacetonate and ammonium metavanadate; the manganese salt is selected from one of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate and potassium permanganate; the chromium salt is selected from one of chromium chloride, chromium sulfate, chromium nitrate, chromium acetate, ammonium dichromate and potassium dichromate.
Preferably, in step 2), the organic solvent is one or two of methanol, ethanol, ethylene glycol, isopropanol, acetone, N-methylpyrrolidone and N-hexane.
Preferably, in step 3), the alkaline solution is one or two of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium acetate, potassium acetate and sodium sulfide.
Preferably, in step 3), the oxidant is one or two of ozone, chlorine, bromine water, iodine, potassium permanganate, potassium dichromate, potassium chlorate, concentrated sulfuric acid, concentrated nitric acid, manganese dioxide and hydrogen peroxide.
Preferably, in the step 2), the hydrothermal reaction temperature is 30-200 ℃, more preferably 50-180 ℃, most preferably 80-120 ℃, the reaction time is 1-48 hours, more preferably 3-36 hours, and most preferably 5-24 hours.
Preferably, in the step 3), the oil bath reaction temperature is 30-200 ℃, more preferably 30-150 ℃, most preferably 40-100 ℃, the reaction time is 1-48 hours, more preferably 3-36 hours, and most preferably 5-24 hours.
The invention also provides a hydroxyl metal oxide nano catalyst, which comprises the hydroxyl metal oxide nano catalyst obtained by the preparation method.
Compared with the existing method for preparing the hydroxyl metal oxide, the method introduces the conductive substrate with high conductive property and excellent mechanical stability to stably and uniformly disperse the hydroxyl metal oxide, so that the hydroxyl metal oxide nano catalyst with the three-way catalyst active site is designed and constructed, and the three-dimensional nano catalyst shows self-support and high conductive performance. Therefore, the hydroxyl metal oxide nano-catalyst of the invention shows excellent catalytic activity and good stability for OER.
The hydroxyl metal oxide nano catalyst obtained by the specific preparation method of the invention has high catalytic activity on OER, and solves the problems of complex synthesis method, low conductivity and low OER activity and stability caused by agglomeration easily in the traditional hydroxyl metal oxide synthesis method. The preparation method of the hydroxyl metal oxide nano catalyst has the advantages of simple process, low cost and easy scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Fig. 1 is a scanning electron microscope image of the surface-cleaned carbon paper prepared in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of reactant 1 prepared in example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of CoOOH/CP prepared according to example 1 of the present invention.
FIG. 4 is a scanning electron micrograph of FeOOH/CP prepared in example 5 of the present invention.
FIG. 5 is a scanning electron micrograph of NiOOH/MXene prepared according to example 7 of the present invention.
FIG. 6 is a scanning electron micrograph of VOOH/MXene prepared according to EXAMPLE 8 of the present invention.
FIG. 7 is a scanning electron micrograph of MnOOH/CP prepared according to example 9 of the present invention.
Detailed Description
The invention provides a hydroxyl metal oxide nano catalyst and a preparation method thereof, which can solve the problems of complex synthesis method, low activity and poor stability of an OER catalyst prepared by the prior art.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the following examples are all commercially available or self-made.
Example 1
This example provides a first hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the growth of the subsequent hydrothermal reaction.
2) Dissolving cobalt sulfate and urea in deionized water and ethylene glycol to obtain a solution a, adding the carbon paper obtained by the treatment in the step 1) into the solution a, carrying out hydrothermal reaction at 100 ℃ for 5 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding potassium permanganate, and carrying out oil bath at 45 ℃ for 18 hours to obtain the Carbon Paper (CP) supported cobalt oxyhydroxide nano catalyst (CoOOH/CP).
From the change from fig. 1 to fig. 3, it can be seen that: after the carbon paper is introduced, the hydroxyl metal oxide can uniformly grow on the carbon paper; and after the hydroxyl metal oxide uniformly grown on the carbon paper is subjected to a specific oxidation treatment process, a three-dimensional self-supporting nano catalyst with rich catalytic active sites can be designed and constructed, almost no agglomeration exists, and the catalytic activity is excellent.
Example 2
This example provides a second hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) Dissolving cobalt nitrate and urea in deionized water and ethylene glycol to obtain a solution a, then adding the carbon paper obtained by the treatment in the step 1) into the solution a, carrying out hydrothermal reaction at 80 ℃ for 10 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding potassium permanganate, and carrying out oil bath at 40 ℃ for 24 hours to obtain the Carbon Paper (CP) supported cobalt oxyhydroxide nano catalyst (CoOOH/CP).
Example 3
This example provides a third hydroxy metal oxide nanocatalyst prepared as follows:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) Dissolving cobalt chloride and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding the carbon paper obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 120 ℃ for 8 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding potassium permanganate, and carrying out oil bath at 100 ℃ for 5 hours to obtain the Carbon Paper (CP) supported cobalt oxyhydroxide nano catalyst (CoOOH/CP).
Example 4
This example provides a fourth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) Dissolving cobalt acetate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding the carbon paper obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 200 ℃ for 1 hour, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 200 ℃ for 1 hour to obtain the Carbon Paper (CP) supported cobalt oxyhydroxide nano catalyst (CoOOH/CP).
Example 5
This example provides a fifth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) And (2) dissolving ferric sulfate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding the carbon paper obtained by the treatment in the step (1) into the solution a, carrying out hydrothermal reaction at 100 ℃ for 5 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 60 ℃ for 24 hours to obtain the Carbon Paper (CP) supported iron oxyhydroxide nano catalyst (FeOOH/CP).
As can be seen from fig. 4: the FeOOH/CP prepared by the embodiment has almost no agglomeration, and the three-dimensional self-supporting nano-catalyst with rich catalytic active sites is constructed, so that the catalytic activity is excellent.
Example 6
This example provides a sixth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the foamed nickel is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the foamed nickel with a clean surface and rich defects, and attachment sites are added for the growth of the subsequent hydrothermal reaction.
2) Dissolving cobalt sulfate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding the foamed nickel obtained by the step 1 into the solution a, carrying out hydrothermal reaction at 30 ℃ for 48 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 30 ℃ for 48 hours to obtain the foam Nickel (NF) supported cobalt oxyhydroxide nano catalyst (CoOOH/NF).
Example 7
This example provides a seventh hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the MXene is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the MXene with a clean surface and rich defects, and attachment sites are added for the growth of the subsequent hydrothermal reaction.
2) Dissolving nickel sulfate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding MXene obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 180 ℃ for 3 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 150 ℃ for 3 hours to obtain the MXene supported nickel oxyhydroxide nano catalyst (NiOOH/MXene).
As can be seen from fig. 5: the NiOOH/MXene prepared by the embodiment is almost free of agglomeration, the three-dimensional self-supporting nano-catalyst with rich catalytic active sites is constructed, and the catalytic activity is excellent.
Example 8
This example provides an eighth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the MXene is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the MXene with a clean surface and rich defects, and attachment sites are added for the growth of the subsequent hydrothermal reaction.
2) Dissolving ammonium metavanadate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, adding MXene obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 160 ℃ for 8 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 50 ℃ for 36 hours to obtain the MXene supported hydroxyl vanadium oxide nano catalyst (VOOH/MXene).
As can be seen from fig. 6: the VOOH/MXene prepared by the embodiment is almost free of agglomeration, the three-dimensional self-supporting nano-catalyst with rich catalytic active sites is constructed, and the catalytic activity is excellent.
Example 9
This example provides a ninth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) Dissolving manganese acetate and urea in deionized water and N-methyl pyrrolidone to obtain a solution a, adding the carbon paper obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 140 ℃ for 24 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 60 ℃ for 24 hours to obtain the Carbon Paper (CP) supported manganese oxyhydroxide nano catalyst (MnOOH/CP).
As can be seen from fig. 7: the MnOOH/CP prepared by the embodiment has almost no agglomeration, and the three-dimensional self-supporting nano-catalyst with abundant catalytic active sites is constructed, so that the catalytic activity is excellent.
Example 10
This example provides a tenth hydroxy metal oxide nanocatalyst, which is prepared by the following steps:
1) and ultrasonically cleaning the titanium mesh by using nitric acid, ethanol, acetone and deionized water in sequence to obtain the titanium mesh with a clean surface and rich defects, so that attachment sites are increased for the growth of the subsequent hydrothermal reaction.
2) And (2) dissolving ammonium dichromate and urea in deionized water and N-methylpyrrolidone to obtain a solution a, then adding the titanium mesh obtained by the treatment in the step (1) into the solution a, carrying out hydrothermal reaction at 50 ℃ for 48 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and a sodium hydroxide solution, then adding hydrogen peroxide, and carrying out oil bath at 150 ℃ for 12 hours to obtain the titanium mesh (Ti) supported cobalt oxyhydroxide nano catalyst (CrOOH/Ti).
Comparative example 1
This example provides a comparative example, which was prepared as follows:
1) the carbon paper is sequentially ultrasonically cleaned by nitric acid, ethanol, acetone and deionized water to obtain the carbon paper with a clean surface and rich defects, and attachment sites are added for the subsequent hydrothermal reaction growth.
2) Dissolving cobalt sulfate and urea in deionized water and ethylene glycol to obtain a solution a, adding the carbon paper obtained by the treatment in the step 1 into the solution a, carrying out hydrothermal reaction at 100 ℃ for 5 hours, and sequentially filtering and drying the product to obtain a reactant 1.
3) Adding the reactant 1 obtained by the treatment in the step 2) into deionized water and sodium hydroxide solution, and then adding concentrated H2SO4Oil bath was carried out at 45 ℃ for 18 hours.
The Carbon Paper (CP) supported cobalt oxyhydroxide nanocatalyst (CoOOH/CP) could not be obtained with the method of the comparative example.
It will be appreciated by those skilled in the art from the foregoing description of construction and principles that the invention is not limited to the specific embodiments described above, and that modifications and substitutions based on the teachings of the art may be made without departing from the scope of the invention as defined by the appended claims and their equivalents. The details not described in the detailed description are prior art or common general knowledge.

Claims (10)

1. The preparation method of the hydroxyl metal oxide nano catalyst is characterized by comprising the following steps of:
1) ultrasonically cleaning a conductive substrate by using acid, ethanol, acetone and deionized water in sequence to obtain a conductive substrate with a clean surface;
2) adding metal salt and urea into deionized water and an organic solvent for dissolving, transferring the solution into a liner of a reaction kettle, then adding a conductive substrate with a clean surface, carrying out hydrothermal reaction under a certain condition, washing and drying a product to obtain a reactant 1;
3) adding the reactant 1 into deionized water and an alkaline solution, then adding an oxidant, carrying out magnetic stirring reaction under the condition of oil bath, washing and drying a product to obtain the hydroxyl metal oxide nano catalyst.
2. The method according to claim 1, wherein in step 1), the acid is one selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hypochlorous acid, acetic acid, formic acid, and oxalic acid.
3. The method according to claim 1, wherein in step 1), the conductive substrate is one of carbon paper, carbon cloth, carbon nanotube, titanium felt, titanium mesh, cobalt foam, iron foam, nickel foam, copper foil, aluminum foil, graphene, graphite alkyne, and MXene.
4. The method according to claim 1, wherein in step 2), the metal salt is selected from one or two of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferric acetate, ferrous acetate, ferric acetylacetonate, cobalt chloride, cobaltous chloride, cobalt sulfate, cobaltous sulfate, cobalt nitrate, cobaltous nitrate, cobalt acetate, cobalt acetylacetonate, nickel chloride, nickel sulfate, nickel nitrate, nickel acetate, nickel acetylacetonate, vanadium sulfate, vanadium chloride, vanadium acetylacetonate, vanadyl acetylacetonate, ammonium metavanadate, manganese sulfate, manganese chloride, manganese nitrate, manganese acetate, potassium permanganate, chromium chloride, chromium sulfate, chromium nitrate, chromium acetate, ammonium dichromate, and potassium dichromate.
5. The method according to claim 1, wherein in step 2), the organic solvent is one or two selected from methanol, ethanol, ethylene glycol, isopropanol, diethyl ether, acetone, N-methylpyrrolidone, ethyl acetate, dichloromethane, N-hexane, and chloroform.
6. The method according to claim 1, wherein in the step 2), the hydrothermal reaction temperature is 30 to 200 ℃ and the reaction time is 1 to 48 hours.
7. The method according to claim 1, wherein in step 3), the alkaline solution is one or two of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium acetate, potassium acetate, and sodium sulfide.
8. The preparation method according to claim 1, wherein in step 3), the oxidant is one or two of ozone, chlorine, bromine water, iodine, potassium permanganate, potassium dichromate, potassium chlorate, concentrated sulfuric acid, concentrated nitric acid, manganese dioxide and hydrogen peroxide.
9. The production method according to claim 1, wherein in the step 3), the oil bath condition is performed at a reaction temperature of 30 to 200 ℃ for 1 to 48 hours.
10. A hydroxy metal oxide nanocatalyst, comprising the hydroxy metal oxide nanocatalyst obtained by the preparation method according to any one of claims 1 to 9.
CN201911294089.6A 2019-12-16 2019-12-16 Hydroxyl metal oxide nano catalyst and preparation method thereof Pending CN110947374A (en)

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