CN116356368A - Method and apparatus for preparing amorphous nano-catalyst - Google Patents
Method and apparatus for preparing amorphous nano-catalyst Download PDFInfo
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- CN116356368A CN116356368A CN202310637700.0A CN202310637700A CN116356368A CN 116356368 A CN116356368 A CN 116356368A CN 202310637700 A CN202310637700 A CN 202310637700A CN 116356368 A CN116356368 A CN 116356368A
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- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 139
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000006260 foam Substances 0.000 claims abstract description 106
- 239000003054 catalyst Substances 0.000 claims abstract description 98
- 229910052751 metal Inorganic materials 0.000 claims abstract description 87
- 239000002184 metal Substances 0.000 claims abstract description 87
- 239000007788 liquid Substances 0.000 claims abstract description 58
- 238000002360 preparation method Methods 0.000 claims abstract description 56
- 239000006262 metallic foam Substances 0.000 claims abstract description 47
- 238000004140 cleaning Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- NNJPGOLRFBJNIW-HNNXBMFYSA-N (-)-demecolcine Chemical compound C1=C(OC)C(=O)C=C2[C@@H](NC)CCC3=CC(OC)=C(OC)C(OC)=C3C2=C1 NNJPGOLRFBJNIW-HNNXBMFYSA-N 0.000 claims description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000840 electrochemical analysis Methods 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000012535 impurity Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
Abstract
The invention relates to a preparation method and a preparation device of an amorphous nano catalyst. Relates to the technical field of hydrogen production by water electrolysis, and the method comprises the following steps: preparing a catalyst growth solution; removing an oxide layer on the surface of the foam metal; placing the foam metal with the surface oxide layer removed in a catalyst growth liquid to generate a load type foam metal; cleaning the supported metal foam to produceAmorphous nanocatalyst is produced. The preparation method has the advantages of simpler preparation conditions, no need of other complicated steps, simplified process, reduced production cost, higher application prospect, higher catalytic activity of the amorphous nano-catalyst prepared by the preparation method, and good OER performance of the amorphous nano-catalyst prepared by the method in electrochemical test, and current density of 100mA/cm 2 The overpotential is not higher than 250mV. HER performance is also better at a current density of 100mA/cm 2 The overpotential is not higher than 350mV.
Description
Technical Field
The invention relates to the technical field of hydrogen production by water electrolysis, in particular to a preparation method and a preparation device of an amorphous nano catalyst.
Background
The traditional water electrolysis catalyst such as noble metals of platinum, palladium and the like has high price, thus not only increasing the production cost, but also having influence on the environment. Therefore, the development of a novel low-cost and high-efficiency water electrolysis catalyst has important significance, can promote the development of sustainable energy, promote the popularization of clean energy automobiles, promote the development of energy conversion and storage technologies, and realize the sustainable development of energy. The characteristics of the micro-nano metal material determine that the micro-nano metal material has excellent catalytic performance, so that the micro-nano metal material is a focus of researchers. Meanwhile, compared with a crystal catalyst, the amorphous catalyst has higher catalytic activity site density and more flexible components, and can adjust the components in a larger range, but the preparation conditions generally required for preparing a large amount of amorphous catalysts are more severe, the production cost is high, and the industrial application prospect is poor.
Disclosure of Invention
In view of the above, one of the purposes of the present invention is to solve the problems of high production cost, complex process and poor industrial application prospect of the amorphous catalyst, and to solve the above problems, the present invention provides a method for preparing an amorphous nano catalyst.
Specifically, the invention is realized by the following technical scheme:
according to a first aspect of the present invention, there is provided a method of preparing an amorphous nanocatalyst, the method comprising: preparing a catalyst growth solution; removing an oxide layer on the surface of the foam metal; placing the foam metal with the surface oxide layer removed in a catalyst growth liquid to generate a load type foam metal; the supported metal foam is washed to prepare the amorphous nano-catalyst.
According to the preparation method of the amorphous nano-catalyst, the amorphous nano-catalyst can be prepared by foam metal and catalyst growth liquid. The oxide layer on the surface of the foam metal needs to be removed during the preparation so as to facilitate the contact and reaction of the foam metal and the catalyst growth liquid. And placing the foam metal with the surface oxide layer removed in a catalyst growth liquid to react to generate load-type foam metal, and cleaning the load-type foam metal at the moment to obtain the required amorphous nano-catalyst. It will be appreciated that the supported metal foam comprises amorphous nanocatalysts and some other impurities, and that washing the supported metal foam washes away other impurities to provide amorphous nanocatalysts. The preparation method of the amorphous nano catalyst has the advantages of simpler preparation conditions, no need of other complicated steps, simplified process, reduced production cost and higher application prospect, and the amorphous nano catalyst prepared by the preparation method has higher catalytic activity, and in electrochemical test, the amorphous nano catalyst prepared by the preparation method shows good OER (Oxygen Evolution Reaction ) performance and has the current density of 100mA/cm 2 Under the condition of no overpotentialAbove 250mV. Its HER (hydrogen evolution reaction ) performance is also good, at a current density of 100mA/cm 2 The overpotential is not higher than 350mV.
In the above technical solution, the catalyst growth solution includes: ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 F and CH 4 N 2 O。
In this technical scheme, the catalyst growth liquid includes: ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 F and CH 4 N 2 O, thereby being capable of reacting with the metal foam to produce the amorphous nanocatalyst.
In the technical proposal, ni (NO 3 ) 2 ·6H 2 The concentration of O substance is 0.02mol/L or more and 0.08mol/L or less.
In this technical scheme, ni (NO 3 ) 2 ·6H 2 The concentration of the O substance is more than or equal to 0.02mol/L and less than or equal to 0.08mol/L, so that the catalytic performance of the prepared catalyst can be ensured.
In the above technical scheme, co (NO 3 ) 2 ·6H 2 The concentration of O substance is 0.02mol/L or more and 0.08mol/L or less.
In this technical scheme, co (NO 3 ) 2 ·6H 2 The concentration of the O substance is more than or equal to 0.02mol/L and less than or equal to 0.08mol/L, so that the catalytic performance of the prepared catalyst can be ensured.
In the technical proposal, na in the catalyst growth liquid 2 MoO 4 ·2H 2 The concentration of O substance is 0.01mol/L or more and 0.03mol/L or less.
In the technical proposal, na in the catalyst growth liquid 2 MoO 4 ·2H 2 Amount of O substanceThe concentration is more than or equal to 0.01mol/L and less than or equal to 0.03mol/L, so that the catalytic performance of the prepared catalyst can be ensured.
In the technical proposal, NH in the catalyst growth liquid 4 The concentration of the substance F is not less than 0.01mol/L and not more than 0.2mol/L.
In the technical proposal, NH in the catalyst growth liquid 4 The concentration of the F substance is more than or equal to 0.01mol/L and less than or equal to 0.2mol/L, so that the catalytic performance of the prepared catalyst can be ensured.
In the technical proposal, CH in the catalyst growth liquid 4 N 2 The concentration of O substance is 0.1mol/L or more and 0.3mol/L or less.
In the technical proposal, CH in the catalyst growth liquid 4 N 2 The concentration of the O substance is more than or equal to 0.1mol/L and less than or equal to 0.3mol/L, so that the catalytic performance of the prepared catalyst can be ensured.
In the above technical solution, the step of preparing the catalyst growth solution specifically includes: ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 F and CH 4 N 2 O is mixed in deionized water and stirred to prepare a catalyst growth liquid.
In this embodiment, ni (NO 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 F and CH 4 N 2 O is mixed together in deionized water and stirred so that the components are thoroughly mixed to form a catalyst growth solution.
In the technical scheme, the stirring time is greater than or equal to 30 minutes.
In the technical scheme, the quality of the formed catalyst growth liquid can be ensured by stirring for at least 30 minutes, so that the performance of the finally prepared catalyst is ensured.
In the above technical solution, the step of placing the metal foam with the surface oxide layer removed in a catalyst growth solution to generate a supported metal foam specifically includes: placing the foam metal with the surface oxide layer removed in a catalyst growth solution to form a mixture; the mixture is baked to produce a supported metal foam.
In this technical scheme, the foam metal from which the surface oxide layer is removed may be placed in a catalyst growth liquid and reacted with the catalyst growth liquid to form a mixture, and then the mixture is baked to produce the supported foam metal.
In the above technical scheme, the baking time of the baking mixture is greater than or equal to 6 hours.
In this solution, the mixture can be baked for at least 6 hours to ensure smooth formation of the supported metal foam.
In the above technical scheme, the baking temperature of the baking mixture is more than or equal to 100 ℃.
In the technical scheme, the baking temperature is limited to be more than or equal to 100 ℃, so that the baking quality can be ensured, and the baking time is reduced.
In any of the above technical solutions, the step of removing the oxide layer on the surface of the metal foam specifically includes: the metal foam is placed in sulfuric acid solution to remove the oxide layer on the surface of the metal foam.
In the technical scheme, the sulfuric acid solution can be used for removing the oxide layer on the surface of the foam metal, and the oxide layer on the surface of the foam metal can be effectively removed. Other substances can of course be used to remove the oxide layer from the foam metal surface.
Further, the concentration of the sulfuric acid solution is 1mol/L or more.
In the technical scheme, the concentration of substances in the sulfuric acid solution is limited to be more than or equal to 1mol/L, so that the oxide layer on the surface of the foam metal can be removed more thoroughly, and the reaction efficiency is improved.
In any of the above embodiments, the step of placing the metal foam with the surface oxide layer removed in a catalyst growth solution to generate a supported metal foam includes: the foam metal with the surface oxide layer removed is washed at least three times with a washing liquid.
In the technical scheme, after the oxide layer on the surface of the foam metal is removed, the foam metal is further required to be washed with a washing liquid at least three times, so that the foam metal is prevented from being accompanied with sulfuric acid solution and the like to influence the preparation of the catalyst.
Further, the cleaning solution comprises ethanol and deionized water.
In the technical scheme, the ethanol and the deionized water are used for cleaning, and the cleaning effect is good.
In any of the above embodiments, the metal foam comprises nickel foam, iron foam, or nickel foam.
In any of the above embodiments, the supported metal foam comprises NiMoO 4 And CoMoO 4 The step of cleaning the supported metal foam to prepare the amorphous nano-catalyst specifically comprises the following steps: niMoO in supported foam metal 4 And/or CoMoO 4 Washing with deionized water; cleaning NiMoO 4 And/or CoMoO 4 Drying is performed to prepare the amorphous nano-catalyst.
In this technical solution, the supported metal foam comprises NiMoO 4 And CoMoO 4 Thereby NiMoO in the supported foam metal can be reduced 4 And/or CoMoO 4 Washing with deionized water, and washing with NiMoO 4 And/or CoMoO 4 Drying is performed to prepare the amorphous nano-catalyst. It will be appreciated that the metal foam comprises NiMoO 4 、CoMoO 4 Other impurities, and NiMoO 4 And/or CoMoO 4 Namely, the amorphous nano catalyst.
In the technical proposal, the cleaned NiMoO 4 And/or CoMoO 4 The drying time for drying is 12 hours or longer.
In the technical proposal, cleaned NiMoO 4 And/or CoMoO 4 Drying time of drying is more than or equal to 12 hours, so that the catalytic effect of the prepared catalyst is ensured.
In any of the above technical solutions, the cleaned NiMoO 4 And/or CoMoO 4 The drying temperature is 60 ℃ or higher.
In the technical proposal, cleaned NiMoO 4 And/or CoMoO 4 The drying temperature of the catalyst is more than or equal to 60 ℃, so that the drying effect can be improved, the drying time is shortened, and the catalyst preparation efficiency is improved.
According to a second aspect of the present invention, there is provided an apparatus for preparing an amorphous nanocatalyst, for implementing the method for preparing an amorphous nanocatalyst according to any one of the first aspect.
According to the preparation device of the amorphous nano-catalyst, provided by the invention, the preparation method of the amorphous nano-catalyst in any one of the technical schemes in the first aspect is realized. Since the apparatus for producing an amorphous nanocatalyst is for realizing the method for producing an amorphous nanocatalyst as in any one of the aspects of the first aspect. Therefore, the apparatus for preparing amorphous nanocatalyst provided by the present invention further has all the advantages of the method for preparing amorphous nanocatalyst according to any one of the first aspect, and will not be described herein.
The technical scheme of the third aspect of the invention provides an amorphous nano-catalyst, which is prepared by adopting the preparation method of the amorphous nano-catalyst in any one of the technical schemes of the first aspect.
According to the amorphous nano-catalyst provided by the invention, the amorphous nano-catalyst preparation method in any one of the technical schemes in the first aspect is adopted. Since the amorphous nanocatalyst is prepared using the method of preparing an amorphous nanocatalyst according to any of the first aspects. Therefore, the amorphous nanocatalyst provided by the invention has all the advantages of the preparation method of the amorphous nanocatalyst in any one of the technical schemes of the first aspect, and is not repeated herein.
The fourth aspect of the present invention provides an electrode prepared using the amorphous nanocatalyst according to any of the third aspects.
According to the electrode provided by the invention, the amorphous nano-catalyst in any one of the technical schemes of the third aspect is adopted for preparation. Since the electrode is prepared using the amorphous nanocatalyst according to any of the embodiments of the third aspect. Therefore, the electrode provided by the invention also has all the beneficial effects of the amorphous nano-catalyst in any one of the technical schemes of the third aspect, and is not described herein.
In a fifth aspect of the invention there is provided an electrolysis apparatus comprising an electrode according to any of the fourth aspects.
According to the present invention there is provided an electrolysis device comprising an electrode according to any one of the fourth aspects. Since the electrolysis apparatus comprises an electrode according to any of the fourth aspects. Therefore, the electrolysis device provided by the invention has all the beneficial effects of the electrode in any one of the technical schemes of the fourth aspect, and the description is omitted here.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the related art will be briefly described below, and it will be apparent to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a flow chart of a method for preparing an amorphous nanocatalyst according to a first embodiment of the invention;
FIG. 2 is a flow chart of a method for preparing an amorphous nanocatalyst according to a second embodiment of the invention;
FIG. 3 is a flow chart of a method for preparing an amorphous nanocatalyst according to a third embodiment of the invention;
FIG. 4 is a flow chart of a method for preparing an amorphous nanocatalyst according to a fourth embodiment of the invention;
FIG. 5 is an X-ray diffraction (XRD) pattern provided by one embodiment of the invention;
FIG. 6 is a SEM (scanning electron microscope) image provided by one embodiment of the present invention;
fig. 7 is another SEM (scanning electron microscope) electron microscope image provided in an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing an amorphous nano-catalyst, which may include the steps of:
s101, preparing a catalyst growth liquid.
S102, removing an oxide layer on the surface of the foam metal.
And S103, placing the foam metal with the surface oxide layer removed in a catalyst growth liquid to generate the supported foam metal.
S104, cleaning the supported foam metal to prepare the amorphous nano-catalyst.
According to the preparation method of the amorphous nano-catalyst, the amorphous nano-catalyst can be prepared by foam metal and catalyst growth liquid. The oxide layer on the surface of the foam metal needs to be removed during the preparation so as to facilitate the contact and reaction of the foam metal and the catalyst growth liquid. And placing the foam metal with the surface oxide layer removed in a catalyst growth liquid to react to generate load-type foam metal, and cleaning the load-type foam metal at the moment to obtain the required amorphous nano-catalyst. It will be appreciated that the supported metal foam includes amorphous nanocatalysts and some other impurities, and that cleaning the supported metal foam will drive it outHis impurities were washed away to obtain amorphous nanocatalyst. The preparation method of the amorphous nano catalyst has the advantages of simpler preparation conditions, no need of other complicated steps, simplified process, reduced production cost and higher application prospect, and the amorphous nano catalyst prepared by the preparation method has higher catalytic activity, and in electrochemical test, the amorphous nano catalyst prepared by the preparation method shows good OER (Oxygen Evolution Reaction ) performance and has the current density of 100mA/cm 2 The overpotential is not higher than 250mV. Its HER (hydrogen evolution reaction ) performance is also good, at a current density of 100mA/cm 2 The overpotential is not higher than 350mV.
In the above embodiment, the catalyst growth liquid includes: ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 F and CH 4 N 2 O。
In this embodiment, the catalyst growth liquid includes: ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 F and CH 4 N 2 O, thereby being capable of reacting with the metal foam to produce the amorphous nanocatalyst.
In the above embodiment, ni (NO 3 ) 2 ·6H 2 The concentration of O substance is 0.02mol/L or more and 0.08mol/L or less.
In this example, ni (NO 3 ) 2 ·6H 2 The concentration of the O substance is more than or equal to 0.02mol/L and less than or equal to 0.08mol/L, so that the catalytic performance of the prepared catalyst can be ensured.
In the above examples, co (NO 3 ) 2 ·6H 2 The concentration of O substance is 0.02mol/L or more and 0.08mol/L or less.
In this example, catalysisCo (NO) in the growth solution 3 ) 2 ·6H 2 The concentration of the O substance is more than or equal to 0.02mol/L and less than or equal to 0.08mol/L, so that the catalytic performance of the prepared catalyst can be ensured.
In the above examples, na in the catalyst growth liquid 2 MoO 4 ·2H 2 The concentration of O substance is 0.01mol/L or more and 0.03mol/L or less.
In this example, na in the catalyst growth solution 2 MoO 4 ·2H 2 The concentration of the O substance is more than or equal to 0.01mol/L and less than or equal to 0.03mol/L, so that the catalytic performance of the prepared catalyst can be ensured.
In the above embodiment, NH in the catalyst growth liquid 4 The concentration of the substance F is not less than 0.01mol/L and not more than 0.2mol/L.
In this example, NH in the catalyst growth fluid 4 The concentration of the F substance is more than or equal to 0.01mol/L and less than or equal to 0.2mol/L, so that the catalytic performance of the prepared catalyst can be ensured.
In the above examples, CH in the catalyst growth liquid 4 N 2 The concentration of O substance is 0.1mol/L or more and 0.3mol/L or less.
In this example, CH in the catalyst growth fluid 4 N 2 The concentration of the O substance is more than or equal to 0.1mol/L and less than or equal to 0.3mol/L, so that the catalytic performance of the prepared catalyst can be ensured.
As shown in fig. 2, the embodiment of the present invention provides a method for preparing an amorphous nano-catalyst, which may include the following steps:
s201, ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 F and CH 4 N 2 O is mixed in deionized water and stirred to prepare a catalyst growth liquid.
S202, removing an oxide layer on the surface of the foam metal.
And S203, placing the foam metal with the surface oxide layer removed in a catalyst growth liquid to generate the supported foam metal.
S204, cleaning the supported foam metal to prepare the amorphous nano-catalyst.
According to the preparation method of the amorphous nano-catalyst, the amorphous nano-catalyst can be prepared by foam metal and catalyst growth liquid. The oxide layer on the surface of the foam metal needs to be removed during the preparation so as to facilitate the contact and reaction of the foam metal and the catalyst growth liquid. And placing the foam metal with the surface oxide layer removed in a catalyst growth liquid to react to generate load-type foam metal, and cleaning the load-type foam metal at the moment to obtain the required amorphous nano-catalyst. It will be appreciated that the supported metal foam comprises amorphous nanocatalysts and some other impurities, and that washing the supported metal foam washes away other impurities to provide amorphous nanocatalysts. Specifically, ni (NO 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 F and CH 4 N 2 O is mixed together in deionized water and stirred so that the components are thoroughly mixed to form a catalyst growth solution. The preparation method of the amorphous nano catalyst has the advantages of simpler preparation conditions, no need of other complicated steps, simplified process, reduced production cost and higher application prospect, and the amorphous nano catalyst prepared by the preparation method has higher catalytic activity, and in electrochemical test, the amorphous nano catalyst prepared by the preparation method shows good OER (Oxygen Evolution Reaction ) performance and has the current density of 100mA/cm 2 The overpotential is not higher than 250mV. Its HER (hydrogen evolution reaction ) performance is also good, at a current density of 100mA/cm 2 The overpotential is not higher than 350mV.
In the above examples, the stirring time period was 30 minutes or longer.
In this example, by stirring for at least 30 minutes, the quality of the catalyst growth liquid formed can be ensured, thereby ensuring the performance of the finally prepared catalyst.
As shown in fig. 3, the embodiment of the present invention provides a method for preparing an amorphous nano-catalyst, which may include the following steps:
s301, preparing a catalyst growth liquid.
S302, placing the foam metal in sulfuric acid solution to remove an oxide layer on the surface of the foam metal.
S303, placing the foam metal with the surface oxide layer removed in a catalyst growth liquid to form a mixture.
And S304, baking the mixture to generate the load type foam metal.
S305, cleaning the supported foam metal to prepare the amorphous nano-catalyst.
According to the preparation method of the amorphous nano-catalyst, the amorphous nano-catalyst can be prepared by foam metal and catalyst growth liquid. The oxide layer on the surface of the foam metal needs to be removed during the preparation so as to facilitate the contact and reaction of the foam metal and the catalyst growth liquid. And placing the foam metal with the surface oxide layer removed in a catalyst growth liquid to react to generate load-type foam metal, and cleaning the load-type foam metal at the moment to obtain the required amorphous nano-catalyst. It will be appreciated that the supported metal foam comprises amorphous nanocatalysts and some other impurities, and that washing the supported metal foam washes away other impurities to provide amorphous nanocatalysts. The preparation method of the amorphous nano catalyst has the advantages of simpler preparation conditions, no need of other complicated steps, simplified process, reduced production cost and higher application prospect, and the amorphous nano catalyst prepared by the preparation method has higher catalytic activity, and in electrochemical test, the amorphous nano catalyst prepared by the preparation method shows good OER (Oxygen Evolution Reaction ) performance and has the current density of 100mA/cm 2 Under the condition that the overpotential is not higher than 250mV is provided. Its HER (hydrogen evolution reaction ) performance is also good, at a current density of 100mA/cm 2 The overpotential is not higher than 350mV.
Wherein the metal foam with the surface oxide layer removed can be placed in a catalyst growth liquid and reacted with the catalyst growth liquid to form a mixture, and then the mixture is baked to generate the supported metal foam. The sulfuric acid solution can be used for removing the oxide layer on the surface of the foam metal, so that the oxide layer on the surface of the foam metal can be effectively removed. Other substances can of course be used to remove the oxide layer from the foam metal surface.
In the above embodiment, the baking time period of the baking mixture was 6 hours or longer.
In this example, the mixture may be baked for at least 6 hours to ensure smooth formation of the supported metal foam.
In the above embodiment, the baking temperature of the baked mixture is 100 ℃ or higher.
In this embodiment, by limiting the baking temperature to 100 ℃ or higher, the baking quality can be ensured and the baking time can be reduced.
Further, the concentration of the sulfuric acid solution is 1mol/L or more.
In this embodiment, by limiting the concentration of the substance in the sulfuric acid solution to 1mol/L or more, more thorough removal of the oxidized layer on the surface of the metal foam can be ensured to improve the reaction efficiency.
As shown in fig. 4, an embodiment of the present invention provides a method for preparing an amorphous nano-catalyst, which may include the steps of:
s401, ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 F and CH 4 N 2 O is mixed in deionized water and stirred to prepare a catalyst growth liquid.
S402, placing the foam metal in sulfuric acid solution to remove an oxide layer on the surface of the foam metal.
S403, cleaning the foam metal with the surface oxide layer removed by using a cleaning liquid at least three times.
S404, placing the foam metal with the surface oxide layer removed in a catalyst growth liquid to form a mixture.
And S405, baking the mixture to generate the load type foam metal.
S406, niMoO in the load type foam metal 4 And/or CoMoO 4 Washing with deionized water.
S407, cleaning the NiMoO 4 And/or CoMoO 4 Drying is performed to prepare the amorphous nano-catalyst.
According to the preparation method of the amorphous nano-catalyst, the amorphous nano-catalyst can be prepared by foam metal and catalyst growth liquid. The oxide layer on the surface of the foam metal needs to be removed during the preparation so as to facilitate the contact and reaction of the foam metal and the catalyst growth liquid. And placing the foam metal with the surface oxide layer removed in a catalyst growth liquid to react to generate load-type foam metal, and cleaning the load-type foam metal at the moment to obtain the required amorphous nano-catalyst. It will be appreciated that the supported metal foam comprises amorphous nanocatalysts and some other impurities, and that washing the supported metal foam washes away other impurities to provide amorphous nanocatalysts. Specifically, ni (NO 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 F and CH 4 N 2 O is mixed together in deionized water and stirred so that the components are thoroughly mixed to form a catalyst growth solution. The preparation method of the amorphous nano catalyst has the advantages of simpler preparation conditions, no need of other complicated steps, simplified process, reduced production cost and higher application prospect, and the amorphous nano catalyst prepared by the preparation method has higher catalytic activity and shows good OER (Oxyg in electrochemical test)en Evolution Reaction, oxygen evolution reaction) at a current density of 100mA/cm 2 The overpotential is not higher than 250mV. Its HER (hydrogen evolution reaction ) performance is also good, at a current density of 100mA/cm 2 The overpotential is not higher than 350mV.
Wherein the metal foam with the surface oxide layer removed can be placed in a catalyst growth liquid and reacted with the catalyst growth liquid to form a mixture, and then the mixture is baked to generate the supported metal foam. The sulfuric acid solution can be used for removing the oxide layer on the surface of the foam metal, so that the oxide layer on the surface of the foam metal can be effectively removed. Other substances can of course be used to remove the oxide layer from the foam metal surface. After the oxide layer on the surface of the foam metal is removed, the foam metal is further required to be washed for at least three times by a washing liquid, so that the foam metal is prevented from being accompanied by sulfuric acid solution and the like to influence the preparation of the catalyst. The supported foam metal comprises NiMoO 4 And CoMoO 4 Thereby NiMoO in the supported foam metal can be reduced 4 And/or CoMoO 4 Washing with deionized water, and washing with NiMoO 4 And/or CoMoO 4 Drying is performed to prepare the amorphous nano-catalyst. It will be appreciated that the metal foam comprises NiMoO 4 、CoMoO 4 Other impurities, and NiMoO 4 And/or CoMoO 4 Namely, the amorphous nano catalyst.
Further, the cleaning solution comprises ethanol and deionized water.
In this example, the cleaning is performed with ethanol and deionized water, and the cleaning effect is good.
In the above examples, cleaned NiMoO was used 4 And/or CoMoO 4 The drying time for drying is 12 hours or longer.
In this example, cleaned NiMoO was used 4 And/or CoMoO 4 Drying time of drying is more than or equal to 12 hours, so that the catalytic effect of the prepared catalyst is ensured.
In any of the above embodiments, the metal foam comprises nickel foam, iron foam, or nickel foam.
In any of the above embodiments, the cleaned NiMoO is subjected to 4 And/or CoMoO 4 The drying temperature is 60 ℃ or higher.
In this example, cleaned NiMoO was used 4 And/or CoMoO 4 The drying temperature of the catalyst is more than or equal to 60 ℃, so that the drying effect can be improved, the drying time is shortened, and the catalyst preparation efficiency is improved.
In one embodiment, a method for preparing an amorphous nanocatalyst is provided, using 1M H 2 SO 4 The nickel foam or the Fe foam or the NiFe foam is cleaned to remove the surface oxide layer. The foam was then thoroughly washed three times with ethanol and deionized water.
Then preparing the supported foam nickel NiMoO 4 /CoMoO 4 Composite material and supported foam nickel NiMoO 4 /CoMoO 4 The preparation route of the composite material is simpler, firstly, a growth solution (catalyst growth solution) is prepared from 0.02M to 0.08M
Ni（NO 3 ） 2 ·6H 2 O, co (NO) of 0.02M-0.08M 3 ） 2 ·6H 2 O, na of 0.01M-0.03M 2 MoO 4 ·2H 2 O, NH 0.01M-0.2M 4 F and 0.1M-0.3M CH 4 N 2 O-mix was prepared in 70mL deionized water. And then stirring the growth solution for 30min, and uniformly mixing.
And transferring the cleaned foam nickel or foam iron or foam nickel iron and the growth solution into a 100mL glass bottle, and placing the glass bottle in a hot air oven at 100 ℃ for 6 hours. The foam nickel is vertically placed inside the glass bottle. After the end of the reaction time, the reaction mixture was loaded with NiMoO 4 /CoMoO 4 The metal foam was rinsed with deionized water and dried at 60 ℃ for 12 hours.
Under electrochemical test, the OER performance current density of the catalyst prepared by the method is 100mA/cm 2 The overpotential is not higher than 250mV, and the HER performance current density is 100mA/cm 2 The overpotential is not higher than 350mV.
As shown in fig. 5, an amorphous nanocatalyst (NiMoO 4 And CoMoO 4 ) In the X-ray diffraction pattern of (2), the diffraction angle is shown on the abscissaθThe diffraction angle is expressed in units of/(deg.), the intensity is expressed in ordinate, and (a.u.) is an arbitrary unit.
As shown in fig. 6 and 7, the amorphous nanocatalyst (NiMoO 4 And CoMoO 4 ) SEM electron microscopy images of fig. 6 and 7 were scaled to 50 μm.
Embodiments of the second aspect of the present invention provide a device for preparing an amorphous nanocatalyst, for implementing the method for preparing an amorphous nanocatalyst according to any of the embodiments of the first aspect.
According to the preparation device of the amorphous nano-catalyst provided by the invention, the preparation method of the amorphous nano-catalyst in any one embodiment of the first aspect is realized. Since the apparatus for preparing an amorphous nanocatalyst is for realizing the method for preparing an amorphous nanocatalyst as in any of the embodiments of the first aspect. Therefore, the apparatus for preparing amorphous nanocatalyst provided by the present invention further has all the advantages of the method for preparing amorphous nanocatalyst according to any one of the embodiments of the first aspect, and will not be described herein.
Embodiments of the third aspect of the present invention provide an amorphous nanocatalyst prepared using the method of preparing an amorphous nanocatalyst as in any of the embodiments of the first aspect.
According to the amorphous nanocatalyst provided by the invention, the preparation method of the amorphous nanocatalyst in any one of the embodiments of the first aspect is adopted. Since the amorphous nanocatalyst is prepared using the method of preparation of the amorphous nanocatalyst in any of the embodiments of the first aspect. Therefore, the amorphous nanocatalyst provided by the invention also has all the advantages of the preparation method of the amorphous nanocatalyst in any one of the embodiments of the first aspect, and is not described herein.
Embodiments of the fourth aspect of the present invention provide an electrode prepared using the amorphous nanocatalyst of any of the embodiments of the third aspect.
According to the electrode provided by the invention, the amorphous nano-catalyst in any embodiment of the third aspect is adopted for preparation. Since the electrode is prepared using the amorphous nanocatalyst of any of the embodiments of the third aspect. Therefore, the electrode provided by the invention also has all the beneficial effects of the amorphous nano-catalyst in any one of the embodiments of the third aspect, and is not described herein.
An embodiment of a fifth aspect of the invention provides an electrolysis apparatus comprising an electrode according to any embodiment of the fourth aspect.
According to the present invention there is provided an electrolysis device comprising an electrode according to any one of the embodiments of the fourth aspect. Since the electrolysis device comprises an electrode according to any of the embodiments of the fourth aspect. Therefore, the electrolysis device provided by the invention has all the beneficial effects of the electrode in any embodiment of the fourth aspect, and is not described herein.
While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any invention or of what may be claimed, but rather as descriptions of features of specific embodiments of particular inventions. Certain features that are described in this specification in the context of separate embodiments can also be implemented in combination in a single embodiment. On the other hand, the various features described in the individual embodiments may also be implemented separately in the various embodiments or in any suitable subcombination. Furthermore, although features may be acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination.
Thus, particular embodiments of the subject matter have been described. Other embodiments are within the scope of the following claims. In some cases, the actions recited in the claims can be performed in a different order and still achieve desirable results. Furthermore, the processes depicted in the accompanying drawings are not necessarily required to be in the particular order shown, or sequential order, to achieve desirable results. In some implementations, multitasking and parallel processing may be advantageous.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (24)
1. A method for preparing an amorphous nanocatalyst, comprising:
preparing a catalyst growth solution;
removing an oxide layer on the surface of the foam metal;
placing the foam metal with the surface oxide layer removed in the catalyst growth liquid to generate a load type foam metal;
and cleaning the supported foam metal to prepare the amorphous nano-catalyst.
2. The method for preparing amorphous nanocatalyst according to claim 1, wherein the catalyst growth liquid comprises:
Ni(NO 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 f and CH 4 N 2 O。
3. The method for preparing amorphous nanocatalyst according to claim 2, wherein Ni (NO 3 ) 2 ·6H 2 The concentration of O substance is 0.02mol/L or more and 0.08mol/L or less.
4. The method for preparing amorphous nanocatalyst according to claim 2, wherein Co (NO 3 ) 2 ·6H 2 The concentration of O substance is 0.02mol/L or more and 0.08mol/L or less.
5. The method for preparing amorphous nanocatalyst according to claim 2, wherein Na in the catalyst growth solution 2 MoO 4 ·2H 2 The concentration of O substance is 0.01mol/L or more and 0.03mol/L or less.
6. The method for preparing amorphous nanocatalyst according to claim 2, wherein NH in the catalyst growth fluid 4 The concentration of the substance F is not less than 0.01mol/L and not more than 0.2mol/L.
7. The method for preparing amorphous nanocatalyst according to claim 2, wherein CH in the catalyst growth liquid 4 N 2 The concentration of O substance is 0.1mol/L or more and 0.3mol/L or less.
8. The method for preparing the amorphous nano-catalyst according to claim 2, wherein the step of preparing the catalyst growth solution specifically comprises:
ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Na 2 MoO 4 ·2H 2 O、NH 4 F and CH 4 N 2 O is mixed in deionized water and stirred to prepare the catalyst growth liquid.
9. The method for preparing an amorphous nanocatalyst according to claim 8, wherein the stirring time is 30 minutes or longer.
10. The method for preparing amorphous nanocatalyst according to claim 1, wherein the step of placing the metal foam with the surface oxide layer removed in the catalyst growth liquid to produce a supported metal foam specifically comprises:
placing the foam metal with the surface oxide layer removed in the catalyst growth liquid to form a mixture;
the mixture is baked to produce the supported metal foam.
11. The method of preparing amorphous nanocatalyst of claim 10, wherein the baking time of baking the mixture is greater than or equal to 6 hours.
12. The method for producing an amorphous nanocatalyst according to claim 10, wherein a baking temperature at which the mixture is baked is 100 ℃ or higher.
13. The method for preparing an amorphous nanocatalyst according to any of claims 1 to 12, characterized in that the step of removing the oxide layer of the metal foam surface comprises:
and placing the foam metal in a sulfuric acid solution to remove an oxide layer on the surface of the foam metal.
14. The method for producing an amorphous nanocatalyst according to claim 13, wherein the concentration of the substance in the sulfuric acid solution is 1mol/L or more.
15. The method of preparing an amorphous nanocatalyst according to any of claims 1 to 12, wherein the step of placing the surface oxide layer removed metal foam in the catalyst growth liquid to produce a supported metal foam is preceded by:
the foam metal with the surface oxide layer removed is washed at least three times with a washing liquid.
16. The method of claim 15, wherein the cleaning fluid comprises ethanol and deionized water.
17. The method of preparing an amorphous nanocatalyst of any of claims 1-12, wherein the metal foam comprises nickel foam, iron foam, or nickel iron foam.
18. The method of preparing amorphous nanocatalyst of any of claims 1-12, wherein the supported metal foam comprises NiMoO 4 And CoMoO 4 The step of washing the supported metal foam to prepare the amorphous nano-catalyst specifically comprises the following steps:
NiMoO in the supported metal foam 4 And/or CoMoO 4 Washing with deionized water;
cleaning NiMoO 4 And/or CoMoO 4 Drying is performed to prepare the amorphous nano-catalyst.
19. The method of preparing amorphous nanocatalyst of claim 18, wherein the NiMoO after washing is performed 4 And/or CoMoO 4 The drying time for drying is 12 hours or longer.
20. The method of preparing amorphous nanocatalyst of claim 18, wherein the NiMoO after washing is performed 4 And/or CoMoO 4 The drying temperature is 60 ℃ or higher.
21. A device for preparing an amorphous nanocatalyst, characterized by being used for realizing the preparation method of an amorphous nanocatalyst according to any one of claims 1 to 20.
22. An amorphous nanocatalyst prepared by the method of preparation of an amorphous nanocatalyst according to any of claims 1 to 20.
23. An electrode prepared using the amorphous nanocatalyst of claim 22.
24. An electrolysis device comprising an electrode according to claim 23.
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