CN115896810A - Noble metal monatomic catalyst based on high entropy effect and preparation method thereof - Google Patents

Noble metal monatomic catalyst based on high entropy effect and preparation method thereof Download PDF

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CN115896810A
CN115896810A CN202211479510.2A CN202211479510A CN115896810A CN 115896810 A CN115896810 A CN 115896810A CN 202211479510 A CN202211479510 A CN 202211479510A CN 115896810 A CN115896810 A CN 115896810A
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CN115896810B (en
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许海涛
边筱扉
邱华军
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Dongguan University of Technology
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Abstract

The invention relates to the technical field of electrochemical catalysis, in particular to a noble metal monatomic catalyst based on a high-entropy effect and a preparation method thereof 3‑x V 2 M x (OH) 2 O 7 ·2H 2 And O, wherein M is an optional metal and is three or more of Ni, co, fe, cu, al and Mn, and the noble metal monoatomic species is one or more of Au, ru, in and Pt. Book (I)The noble metal monatomic composite catalyst prepared by the method has the advantages of regular shape, good crystallinity and adjustable types and proportions of metal elements of the high-entropy hydroxide substrate, can be used for preparing various noble metal monatomic catalysts, and has wide application prospect in the field of catalysis.

Description

Noble metal monatomic catalyst based on high entropy effect and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemical catalysis, in particular to a noble metal monatomic catalyst based on a high entropy effect and a preparation method thereof.
Background
The energy is a foundation stone existing and developing in human society, is a basic restriction condition for economic development and civilization progress, and is an important basis for national economy and national security and realization of sustainable development. Under the guidance of the targets of 'carbon peak reaching and carbon neutralization', hydrogen energy is emerging as a recognized zero-carbon energy source after new energy sources such as solar energy, wind energy and the like are developed rapidly. The preparation technology of the hydrogen mainly comprises hydrogen production by fossil fuel, hydrogen production by water electrolysis, hydrogen production by water photolysis and biological hydrogen production.
The hydrogen production process by water electrolysis is simple, the product purity is high, and the high-efficiency, clean and large-scale preparation of hydrogen can be realized by adopting renewable energy as an energy source. However, water electrolysis is a complex redox reaction process involving multi-electron transfer between the positive electrode and the negative electrode, and therefore, the water electrolysis catalyst is one of the key factors for determining the cost of hydrogen production from water electrolysis.
Currently, the most widely used in industry is alkaline water electrolysis technology, under the current technical conditions, noble metals platinum and yttrium oxide/ruthenium oxide are respectively cathode and anode catalysts with higher catalytic efficiency, but the expensive price and poor stability severely limit the industrial application of the noble metals. Therefore, the electrolytic water catalyst for improving the utilization rate and the catalytic stability of the noble metal catalyst is the key of the competitive power of the technical core for large-scale popularization.
The high-entropy oxyhydroxide is a novel functional material which is derived and developed on the basis of high-entropy alloy, consists of oxygen ions, hydroxyl ions and five or more than five metal elements and has unique structure and function adjustable characteristic. In a highly disordered multicomponent system, the high-entropy oxyhydroxide has a series of unique characteristics, such as lattice distortion effect, high-entropy effect, delayed diffusion effect and cocktail effect, due to the larger mixing entropy.
In recent years, the monatomic composite material is used as a novel catalyst, noble metal atoms are anchored on a substrate, the atom utilization rate and the stability of the noble metal can be greatly improved, and the monatomic composite material has a unique electronic structure and excellent catalytic performance, and is a research hotspot in the field of catalysis. However, the noble metal monoatomic has very high surface free energy, so that it is easy to agglomerate to form clusters and nanoparticles, and thus the preparation of the monoatomic catalyst is a challenge; meanwhile, a large doping amount is easy to agglomerate to form clusters, but too low doping amount cannot ensure the number of catalytic active sites, which affects the activity of the monatomic catalyst to a certain extent. Therefore, the preparation method of noble metal monatomic catalyst with uniform size and rich catalytic active sites is still in the research and development stage.
Disclosure of Invention
The invention provides a noble metal monatomic catalyst based on a high entropy effect and a preparation method thereof, which can solve the problems of low loading capacity and uneven fraction of the monatomic catalyst in the prior art.
A noble metal monatomic catalyst based on high-entropy effect is a noble metal monatomic supported high-entropy oxyhydroxide catalyst, and the molecular formula of the high-entropy oxyhydroxide is Zn 3-x V 2 M x (OH) 2 O 7 ·2H 2 And O, wherein M is an optional metal and is three or more of Ni, co, fe, cu, al and Mn, and the single atom species of the noble metal is one or more of Au, ru, in and Pt.
Preferably, each optional metal element is present in an atomic percentage of 0.05 to 0.3 of all non-noble metal elements.
A preparation method of a noble metal monatomic catalyst based on a high entropy effect specifically comprises the following steps:
step S1, adding vanadium pentoxide and inorganic non-noble metal salt into distilled water serving as a solvent, and performing ultrasonic mixing to obtain a mixed metal salt solution;
s2, under the condition of magnetic stirring, sequentially adding a mixed metal salt solution, a noble metal monoatomic metal salt, urotropine and anhydrous sodium sulfate, and fully and uniformly mixing to obtain a precursor solution;
and S3, transferring the precursor solution in the step S2 into a reaction kettle for hydrothermal reaction, cooling, collecting the grey brown powder on the upper layer in the reaction kettle, centrifugally washing, and drying in vacuum to obtain the noble metal monatomic catalyst.
Preferably, the inorganic non-noble metal salt in step S1 is a nitrate, sulfate and/or hydrochloride.
Preferably, the noble metal monoatomic metal salt in step S2 is chloroauric acid, ruthenium chloride, chloroplatinic acid, indium chloride/indium nitrate/indium sulfate.
Preferably, the ultrasonic treatment time of the mixed metal salt solution in step S1 is 30-60min.
Preferably, the reaction temperature of the hydrothermal reaction in the step S3 is 110-130 ℃ and the reaction time is 24-36h.
Preferably, the vanadium ion concentration in the precursor solution in step S2 is 0.14 to 0.17 mol.L -1 The concentration of zinc ions is 0.03-0.05 mol.L -1 Sodium sulfate is 0.10-0.14 mol.L -1 The concentration of urotropin is 0.06-0.11 mol.L -1 The concentration of inorganic non-noble metal salt is 0.01-0.02 mol.L -1 The concentration of the noble metal monoatomic metal salt is 0.001-0.005 mol.L -1 。
Due to the adoption of the technical scheme, the invention has the remarkable technical effects that:
(1) The noble metal monatomic catalyst is a noble metal monatomic supported high-entropy oxyhydroxide catalyst, the substrate of the noble metal monatomic supported high-entropy oxyhydroxide catalyst is high-entropy oxyhydroxide, and based on the unique property of the high-entropy oxyhydroxide, the noble metal monatomic catalyst is an excellent electrolytic water catalyst on one hand, the activity of the catalyst can be improved to a certain extent, and meanwhile, the noble metal monatomic supported high-entropy oxyhydroxide catalyst can be used as an excellent carrier to anchor noble metal monatomic, so that the loading amount and the stability of the monatomic are improved.
(2) The substrate high-entropy hydroxide oxide has good crystallinity and regular shape, the types and the proportions of metal elements are adjustable, and the coordination environment of the monatomic catalyst can be changed by the cocktail effect of the high-entropy compound, so that the electronic structure of the monatomic catalyst is regulated, the electronic structure of the noble metal monatomic catalyst is regulated, the coordination environment of the catalyst is optimized, and the monatomic catalyst with multifunctional catalytic property is prepared.
(3) The types and the proportion of metal elements in the high-entropy oxyhydroxide are adjustable, and the special high-entropy effect can provide coordination environment and bonding action for anchoring different types of noble metal monoatomic atoms. Therefore, the invention provides a general monatomic catalyst synthesis strategy, and provides a new idea for the controllable preparation of the monatomic catalyst.
Drawings
FIG. 1 is a scanning electron micrograph of a monoatomic Ru-Au-Pt-in supported Zn-V-Al-Ni-Co-Fe-Cu-Mn oxyhydroxide prepared in example 1;
FIG. 2 is an X-ray powder diffraction pattern of a monoatomic Ru-Au-Pt-in-supported Zn-V-Al-Ni-Co-Fe-Cu-Mn-OH oxide prepared in example 1;
FIG. 3 is an X-ray energy spectrum of the monoatomic Ru-Au-Pt-in supported Zn-V-Al-Ni-Co-Fe-Cu-Mn oxyhydroxide prepared in example 1;
FIG. 4 is a high angle annular dark field transmission and energy spectrum profile of a single atom Ru-Au-Pt-in supported Zn-V-Al-Ni-Co-Fe-Cu-Mn-OH oxide prepared in example 1;
FIG. 5 is a transmission electron micrograph of single atom Ru-Au-Pt-in supported Zn-V-Al-Ni-Co-Fe-Cu-Mn-OH oxide prepared in example 1 corrected by spherical aberration;
FIG. 6 is an electrolytic water polarization curve for a monatomic Ru-Au-Pt-in supported Zn-V-Al-Ni-Co-Fe-Cu-Mn-OH oxide working electrode prepared in example 1;
FIG. 7 is an X-ray powder diffraction pattern of the monoatomic ruthenium indium supported zinc vanadium aluminum nickel cobalt iron oxyhydroxide prepared in example 2;
FIG. 8 is a transmission electron micrograph of the monoatomic platinum supported Zn-V-Al-Ni-Co-Fe-oxyhydroxide prepared in example 2 corrected for spherical aberration;
FIG. 9 is an X-ray powder diffraction pattern of a monatomic platinum-supported zinc vanadium nickel copper manganese oxyhydroxide prepared in example 3;
FIG. 10 is a transmission electron micrograph of the spherical aberration corrected zinc vanadium nickel copper manganese oxyhydroxide supported on monoatomic platinum prepared in example 3.
Detailed Description
For a further understanding of the present invention, reference is made to the following detailed description taken in conjunction with the accompanying drawings and examples. It is to be understood that the examples are illustrative of the invention and not limiting.
Example 1
The embodiment 1 of the invention relates to a noble metal monatomic catalyst based on a high-entropy stabilizing effect, in particular to a zinc-vanadium-aluminum-nickel-cobalt-iron-copper-manganese hydroxide catalyst loaded by monatomic ruthenium-gold-platinum-indium, and a preparation method of the catalyst comprises the following steps:
(1) Adding a proper amount of distilled water as a solvent into a container, sequentially adding reagents of vanadium pentoxide, zinc nitrate, aluminum nitrate, nickel nitrate, cobalt nitrate, ferric nitrate, copper nitrate and manganese nitrate, and controlling the concentration of vanadium ions in the solution to be 0.14 mol.L -1 The zinc ion concentration is 0.03 mol.L -1 And the concentration of aluminum ions is 0.01 mol.L -1 And the concentration of nickel ions is 0.01 mol.L -1 And the cobalt ion concentration is 0.01 mol.L -1 And the iron ion concentration is 0.01 mol.L -1 The copper ion concentration is 0.01 mol.L -1 The concentration of manganese ions was 0.01 mol.L -1 Carrying out ultrasonic treatment on the mixed solution for 30 minutes to ensure that the solution is uniformly mixed;
(2) On the basis of magnetic stirring, adding the mixed solution, chloroauric acid, ruthenium chloride, indium nitrate, chloroplatinic acid, urotropine and sodium sulfate reagents in the step (1) in sequence, wherein the adding time interval of each reagent is 5 minutes, after mixing, carrying out magnetic stirring for 30 minutes, and controlling the gold ion concentration in the precursor solution to be 0.001 mol.L -1 The concentration of ruthenium ions was 0.001 mol. L -1 And the indium ion concentration is 0.001 mol.L -1 The platinum ion concentration was 0.001 mol. L -1 The concentration of urotropin is 0.06 mol.L -1 Sodium sulfate concentration of 0.10 mol. L -1 Finally, ultrasonically treating the mixed solution stirred by the magnetic force for 60 minutes to ensure that the solution is uniformly mixed;
(3) And (3) transferring the mixed solution obtained in the step (2) into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction at 110 ℃ for 24 hours, cooling, collecting the grey brown powder on the upper layer in the reaction kettle, centrifugally washing, and drying to obtain the product, namely the monoatomic ruthenium-gold-platinum-indium loaded zinc-vanadium-aluminum-nickel-cobalt-iron-copper-manganese oxyhydroxide.
Referring to the attached drawings, fig. 1 is a scanning electron microscope image of the monatomic ruthenium gold platinum indium-loaded zinc vanadium aluminum nickel cobalt iron copper manganese oxyhydroxide prepared in the embodiment, and it can be known that the monatomic catalyst prepared in the embodiment has a nanosheet structure and a regular morphology, and no attachments such as obvious nanoparticles and the like are present on the surface of the nanosheet.
Fig. 2 and fig. 3 are an X-ray powder diffraction pattern and an X-ray energy spectrum of the monatomic ru-au-pt-in supported zn-v-al-ni-co-fe-cu-mn oxyhydroxide prepared in this example, all diffraction peaks in the X-ray powder diffraction pattern have a significant left shift relative to the standard card JCPDF NO #50-0750, and NO diffraction peaks of other impurities, respectively, and the X-ray energy spectrum proves that the prepared catalyst contains metallic elements of zn, v, al, ni, co, fe, cu, mn, ru, au, pt, and in. The ICP test is combined to prove that the noble metal single-atom catalyst synthesized by the embodiment is RuAuPtIn @ Zn 2.7 V 2 Al 0.05 Ni 0.05 Co 0.05 Fe 0.05 Cu 0.05 Mn 0.05 (OH) 2 O 7 ·2H 2 O。
Fig. 4 is a high-angle annular dark field diagram and an energy spectrum scan of the monatomic ru-au-pt-in supported zinc-vanadium-aluminum-nickel-cobalt-iron-copper-manganese-oxyhydroxide prepared in this example, and the metal elements on the data surface are uniformly distributed on the nanosheets without obvious element aggregation and enrichment.
Fig. 5 is a transmission electron microscope image of spherical aberration correction of zinc vanadium aluminum nickel cobalt iron copper manganese oxyhydroxide loaded by monoatomic ruthenium gold platinum indium prepared in this example, and heavy metal elements ruthenium, gold, platinum, and indium on the data surface are dispersed on the zinc vanadium aluminum nickel cobalt iron copper manganese high-entropy oxyhydroxide nanosheets in a monoatomic manner.
Therefore, as can be seen from fig. 1, fig. 2, fig. 3, fig. 4 and fig. 5, we successfully prepared the monatomic ru-au-pt-in supported zinc-vanadium-aluminum-nickel-cobalt-iron-copper-manganese oxyhydroxide nanosheet material.
The prepared high-entropy oxyhydroxide is prepared into an oxygen evolution reaction working electrode, the polarization curve test result is shown in figure 5, and the test result in figure 5 shows that the catalytic activity of the crystal porous high-entropy zinc-vanadium-aluminum-nickel-cobalt-iron-ruthenium oxyhydroxide catalyst product is greatly improved compared with that of commercial ruthenium oxide, because the prepared high-entropy oxyhydroxide has higher specific surface area and abundant catalytic activity sites, and the electronic structure of the catalyst can be regulated and controlled by the cocktail effect of the high-entropy compound, so that the activity of the catalyst is finally improved.
Example 2
The same as example 1, except that the monatomic ruthenium indium supported zinc vanadium aluminum nickel cobalt iron oxyhydroxide catalyst material was prepared in this example as follows:
(1) Adding a proper amount of distilled water as a solvent into a container, sequentially adding vanadium pentoxide, zinc sulfate, aluminum sulfate, nickel sulfate, cobalt sulfate and ferric sulfate reagents, and controlling the concentration of vanadium ions in the solution to be 0.17 mol.L -1 The zinc ion concentration is 0.05 mol.L -1 And the aluminum ion concentration is 0.02 mol.L -1 The concentration of nickel ions is 0.02 mol.L -1 And the cobalt ion concentration is 0.02 mol.L -1 And the concentration of iron ions is 0.02 mol.L -1 Carrying out ultrasonic treatment on the mixed solution for 60 minutes to ensure that the solution is uniformly mixed;
(2) On the basis of magnetic stirring, the mixed solution in the step (1), ruthenium chloride, indium chloride, urotropine and sodium sulfate reagent are added in sequence, the adding time interval of each reagent is 5 minutes, the magnetic stirring is carried out for 30 minutes after the mixing is finished, and the concentration of ruthenium ions in the precursor solution is controlled to be 0.005 mol.L -1 And the indium ion concentration is 0.005 mol.L -1 The concentration of urotropin is 0.11 mol.L -1 The sodium sulfate concentration was 0.14 mol. L -1 Finally, ultrasonically treating the mixed solution stirred by the magnetic force for 60 minutes to ensure that the solution is uniformly mixed;
(3) And (3) transferring the mixed solution obtained in the step (2) into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction at 130 ℃ for 36 hours, cooling, collecting the grey brown powder on the upper layer in the reaction kettle, centrifugally washing, and drying to obtain the product, namely the monoatomic ruthenium-indium-loaded zinc-vanadium-aluminum-nickel-cobalt-iron oxyhydroxide.
Referring to the drawings, FIGS. 7 and 8 are respectively a monoatomic ruthenium-indium-supported zinc vanadium prepared in the present exampleThe X-ray powder diffraction pattern and the spherical aberration correction transmission electron micrograph of the aluminum-nickel-cobalt-iron oxyhydroxide show that all diffraction peaks in the X-ray powder diffraction pattern have obvious left shift relative to a standard card JCPDF NO #50-0750 and do not have diffraction peaks of other impurities. The ICP test and the spherical aberration correction transmission electron microscope image are combined at the same time, so that the precious metal monoatomic catalyst synthesized by the embodiment is RuIn @ Zn 1.8 V 2 Al 0.3 Ni 0.3 Co 0.3 Fe 0.3 (OH) 2 O 7 ·2H 2 O。
Example 3
The same as example 1, except that the monatomic platinum-supported zinc vanadium aluminum nickel copper manganese hydroxide catalyst material was prepared as follows in this example:
(1) Adding a proper amount of distilled water as a solvent into a container, sequentially adding vanadium pentoxide, zinc chloride, ferric sulfate, copper chloride and manganese sulfate reagents, and controlling the concentration of vanadium ions in the solution to be 0.15 mol.L -1 And the zinc ion concentration is 0.04 mol.L -1 And an aluminum ion concentration of 0.018 mol. L -1 (iii) a nickel ion concentration of 0.018 mol. L -1 The copper ion concentration was 0.018 mol. L -1 Manganese ion concentration of 0.018 mol. L -1 Carrying out ultrasonic treatment on the mixed solution for 40 minutes to ensure that the solution is uniformly mixed;
(2) On the basis of magnetic stirring, the mixed solution in the step (1), chloroplatinic acid, urotropine and sodium sulfate reagent are added in sequence, the adding time interval of each reagent is 5 minutes, magnetic stirring is carried out for 30 minutes after mixing is finished, and the concentration of platinum ions in the precursor solution is controlled to be 0.004 mol.L -1 The concentration of urotropin is 0.1 mol.L -1 The sodium sulfate concentration was 0.13 mol. L -1 Finally, ultrasonically treating the mixed solution stirred by the magnetic force for 60 minutes to ensure that the solution is uniformly mixed;
(3) And (3) transferring the mixed solution obtained in the step (2) into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 30 hours, cooling, collecting the grey brown powder on the upper layer in the reaction kettle, centrifugally washing, and drying to obtain the product, namely the monatomic platinum-loaded zinc-vanadium-aluminum-nickel-copper-manganese oxyhydroxide.
Referring to the drawings, fig. 9 and 10 are an X-ray powder diffractogram and a spherical aberration correction transmission electron micrograph of the monoatomic platinum-supported zinc-vanadium-nickel-iron-manganese oxyhydroxide prepared in this example, respectively, in which all diffraction peaks in the X-ray powder diffractogram are significantly shifted to the left relative to standard card JCPDF NO #50-0750, and there are NO diffraction peaks of other impurities. The ICP test and the spherical aberration correction transmission electron microscope image are combined at the same time, so that the precious metal monoatomic catalyst synthesized by the embodiment is Pt @ Zn 2.24 V 2 Al 0.19 Ni 0.19 Cu 0.19 Mn 0.19 (OH) 2 O 7 ·2H 2 O。
Example 4
The same as example 1, except that the monatomic indium-platinum supported zinc vanadium iron copper manganese oxyhydroxide catalyst material was prepared in this example as follows:
(1) Adding a proper amount of distilled water as a solvent into a container, sequentially adding vanadium pentoxide, zinc chloride, ferric chloride, copper chloride and manganese chloride reagents, and controlling the concentration of vanadium ions in the solution to be 0.15 mol.L -1 The zinc ion concentration is 0.04 mol.L -1 The cobalt ion concentration was 0.015 mol. L -1 And the iron ion concentration is 0.015 mol.L -1 The copper ion concentration was 0.015 mol. L -1 The manganese ion concentration was 0.015 mol. L -1 Carrying out ultrasonic treatment on the mixed solution for 40 minutes to ensure that the solution is uniformly mixed;
(2) On the basis of magnetic stirring, adding the mixed solution in the step (1), indium sulfate, chloroplatinic acid, urotropine and sodium sulfate reagent in sequence, wherein the adding time interval of each reagent is 5 minutes, and after the mixing is finished, carrying out magnetic stirring for 30 minutes, and controlling the concentration of indium ions in the precursor solution to be 0.003 mol.L -1 And the platinum ion concentration is 0.003 mol.L -1 The concentration of urotropin is 0.09 mol.L -1 The sodium sulfate concentration was 0.12 mol. L -1 Finally, ultrasonically treating the mixed solution stirred by the magnetic force for 60 minutes to ensure that the solution is uniformly mixed;
(3) Transferring the mixed solution obtained in the step (2) into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction for 30 hours at 120 ℃, cooling and collecting the grey brown color of the upper layer in the reaction kettleAnd (3) centrifuging and washing the powder, and drying to obtain a product, namely the zinc vanadium iron copper manganese hydroxide loaded by the monatomic indium platinum. The combination of XRD and ICP tests can prove that the noble metal monatomic catalyst synthesized by the embodiment is InPt @ Zn 2.49 V 2 Fe 0.17 Cu 0.17 Mn 0.17 (OH) 2 O 7 ·2H 2 O。
Example 5
The same as example 1, except that the preparation of the monatomic platinum-indium supported zinc vanadium aluminum nickel cobalt iron manganese oxyhydroxide catalyst material in this example was as follows:
(1) Adding a proper amount of distilled water as a solvent into a container, sequentially adding vanadium pentoxide, zinc nitrate, aluminum chloride, nickel nitrate, cobalt chloride, ferric nitrate and manganese sulfate reagents, and controlling the concentration of vanadium ions in the solution to be 0.16 mol.L -1 The zinc ion concentration is 0.04 mol.L -1 And the aluminum ion concentration is 0.013 mol.L -1 The nickel ion concentration was 0.013 mol. L -1 The cobalt ion concentration was 0.013 mol. L -1 And the iron ion concentration is 0.013 mol.L -1 The manganese ion concentration was 0.013 mol. L -1 Carrying out ultrasonic treatment on the mixed solution for 30 minutes to ensure that the solution is uniformly mixed;
(2) On the basis of magnetic stirring, adding the mixed solution, chloroauric acid, indium sulfate, chloroplatinic acid, urotropine and sodium sulfate reagent in the step (1) in sequence, wherein the adding time interval of each reagent is 5 minutes, and after mixing, carrying out magnetic stirring for 30 minutes, and controlling the gold ion concentration in the precursor solution to be 0.002 mol.L -1 And the indium ion concentration is 0.002 mol.L -1 The platinum ion concentration was 0.002 mol. L -1 The concentration of urotropin is 0.1 mol.L -1 The sodium sulfate concentration was 0.12 mol. L -1 Finally, ultrasonically treating the mixed solution stirred by the magnetic force for 60 minutes to ensure that the solution is uniformly mixed;
(3) Transferring the mixed solution obtained in the step (2) into a reaction kettle, sealing the reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 28 hours, cooling, collecting the grayish brown powder on the upper layer in the reaction kettle, centrifugally washing, and drying to obtain a product, namely the monoatomic gold-platinum-indium-loaded zinc-vanadium-aluminum-nickel-cobalt-iron-manganese oxyhydroxide. The combination of XRD and ICP tests proves that the noble metal monatomic catalyst synthesized by the example is PtAuIn @ Zn 2.25 V 2 Al 0.15 Ni 0.15 Co 0.15 Fe 0.15 Mn 0.15 (OH) 2 O 7 ·2H 2 O。
The present invention and its embodiments have been described above schematically, and the description is not intended to be limiting, and what is shown in the drawings is only one of the embodiments of the present invention, and the actual structure is not limited thereto. Therefore, without departing from the spirit of the present invention, a person of ordinary skill in the art should understand that the present invention shall not be limited to the embodiments and the similar structural modes without creative design.

Claims (8)

1. A noble metal monatomic catalyst based on the high entropy effect is characterized in that: the catalyst is a noble metal monoatomic supported high-entropy oxyhydroxide catalyst, and the molecular formula of the high-entropy oxyhydroxide is Zn 3-x V 2 M x (OH) 2 O 7 ·2H 2 And O, wherein M is an optional metal and is three or more of Ni, co, fe, cu, al and Mn, and the noble metal monoatomic species is one or more of Au, ru, in and Pt.
2. A noble metal monatomic catalyst based on the high entropy effect according to claim 1, characterized in that: each optional metal element accounts for 0.05-0.3 atomic percent of all non-noble metal elements.
3. A preparation method of a noble metal monatomic catalyst based on a high entropy effect is characterized by comprising the following steps:
s1, adding vanadium pentoxide and inorganic non-noble metal salt into distilled water serving as a solvent, and ultrasonically mixing to obtain a mixed metal salt solution;
s2, under the condition of magnetic stirring, sequentially adding a mixed metal salt solution, a noble metal monoatomic metal source, urotropine and anhydrous sodium sulfate, and fully and uniformly mixing to obtain a precursor solution;
and S3, transferring the precursor solution in the step S2 into a reaction kettle for hydrothermal reaction, cooling, collecting the grey brown powder on the upper layer in the reaction kettle, centrifugally washing, and drying in vacuum to obtain the noble metal monatomic catalyst.
4. A process for the preparation of a noble metal monatomic catalyst based on a high entropy effect according to claim 3, characterized in that: in the step S1, the inorganic non-noble metal salt is nitrate, sulfate and/or hydrochloride.
5. A process for the preparation of a noble metal monatomic catalyst based on a high entropy effect according to claim 3, characterized in that: in the step S2, the noble metal monoatomic metal source is one or more of chloroauric acid, ruthenium chloride, chloroplatinic acid, indium chloride, indium nitrate or indium sulfate.
6. The preparation method of the noble metal monatomic catalyst based on the high entropy effect according to claim 3, characterized in that: the ultrasonic treatment time of the mixed metal salt solution in the step S1 is 30-60min.
7. The preparation method of the noble metal monatomic catalyst based on the high entropy effect according to claim 3, characterized in that: the reaction temperature of the hydrothermal reaction in the step S3 is 110-130 ℃, and the reaction time is 24-36h.
8. The preparation method of the noble metal monatomic catalyst based on the high entropy effect according to claim 3, characterized in that: the concentration of vanadium ions in the precursor solution in the step S2 is 0.14-0.17 mol.L -1 The concentration of zinc ions is 0.03-0.05 mol.L -1 Sodium sulfate is 0.10-0.14 mol.L -1 The concentration of urotropin is 0.06-0.11 mol.L -1 The concentration of inorganic non-noble metal salt is 0.01-0.02 mol.L -1 The concentration of the noble metal monoatomic metal source is 0.001-0.005 mol.L -1 。
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