CN116607168A - Metal monoatomic load S-Ni (OH) for electrolysis of water at high current density 2 Universal preparation method of catalyst - Google Patents

Metal monoatomic load S-Ni (OH) for electrolysis of water at high current density 2 Universal preparation method of catalyst Download PDF

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Publication number
CN116607168A
CN116607168A CN202310803195.2A CN202310803195A CN116607168A CN 116607168 A CN116607168 A CN 116607168A CN 202310803195 A CN202310803195 A CN 202310803195A CN 116607168 A CN116607168 A CN 116607168A
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salt
metal
catalyst
nano
electrolyzed water
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赵红
方文荟
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Binzhou Weiqiao National Institute Of Advanced Technology
University of Chinese Academy of Sciences
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Binzhou Weiqiao National Institute Of Advanced Technology
University of Chinese Academy of Sciences
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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
    • C25B11/04—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a metal monoatomic load S-Ni (OH) for electrolyzing water 2 The universal preparation method of the catalyst comprises the following steps: growing Ni (OH) on foam nickel 2 And respectively carrying out nonmetallic heteroatom treatment and metal monoatomic loading two-step treatment on the nano-sheet array to obtain the nano-array catalyst loaded by different metal monoatoms. The synthesis method is simple and has certain universality. Electrochemical tests show that the synthesized array nano-sheet catalyst loaded by different metal monoatoms has extremely excellent catalytic Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) performances, extremely high current density under lower overpotential, and better stability, and is beneficial to realizing engineeringAnd (5) industrialized electrolysis of water to produce hydrogen. In addition, solar panel driving materials can be used for full hydrolysis to produce hydrogen and oxygen.

Description

Metal monoatomic load S-Ni (OH) for electrolysis of water at high current density 2 Universal preparation method of catalyst
Technical Field
The invention belongs to the field of hydrogen production by electrochemical catalytic water decomposition, and particularly relates to a method for synthesizing a plurality of metal monoatomic catalysts in a universal way.
Background
The use of solar energy, wind energy, tidal energy, or the like as an energy source for the electrolysis of water is considered as a strategy for the efficient, economical and sustainable production of hydrogen. The electrolyzed water mainly comprises an anodic Oxygen Evolution Reaction (OER) and a cathodic Hydrogen Evolution Reaction (HER). However, the kinetics of both half reactions are slow, so that it is necessary to accelerate the reaction by means of a catalyst. The advanced HER and OER catalysts are Pt-based materials and Ru or Ir oxides respectively at present, and the required overpotential is still high to achieve the high current density required for practical large-scale electrolysis of water; second, the scarcity and high cost of noble metals also limit their widespread use.
Although most catalysts have low overpotential at low current density, the current density of the catalyst is further increased to 500 mA cm when the catalyst is used for industrial hydrogen production -2 Above, there is therefore still a further need to explore HER catalysts useful at high current densities. In general, an ideal electrolyzed water catalyst with high catalytic activity needs to meet the following requirements: (1) high conductivity to achieve efficient electron transfer; (2) sufficient H/OH adsorption active sites; (3) a highly potent intrinsic active center; (4) rapid escape of gaseous products from the active surface; (5) good stability, long service life, etc. Therefore, it is important to rationally design and synthesize a catalyst with high activity and low cost, which can be used for a large current density, in terms of an electronic structure, a surface/interface state, a three-dimensional structure, and the like.
Based on this, we disclose a continuous hydrothermal synthesis of active metal supported, heteroatom (S) -doped nickel hydroxide (Ni (OH) 2 ) Nano array catalyst (M) 9 @S-Ni(OH) 2 ) Is a method of (2). A large number of signs show that the metal loaded by us is in monoatomic dispersion, and electrochemical tests show that M 9 @S-Ni(OH) 2 The series of catalysts have good hydrogen evolution reaction and oxygen evolution reaction performance, and can reach 700 mA cm under low overpotential -2 Is favorable for realizing industrialization.
Disclosure of Invention
The invention discloses a preparation method of an electrolyzed water catalyst, which can realize high-efficiency electrolysis of water to produce hydrogen and oxygen.
The invention adopts the following technical proposal for solving the technical problems, and is characterized in that the specific process is as follows:
step 1): nickel hydroxidePreparing a nano-sheet precursor: immersing the substrate in an aqueous solution containing nickel salt, urea and the like, and heating at 100-200 ℃ for reaction 2-48 h. Then washing and drying to obtain Ni (OH) 2 An array nanoplatelet precursor;
step 2): vulcanization treatment of metal hydroxide: ni (OH) to be synthesized 2 The array nano-sheet precursor is immersed in an aqueous solution containing sulfur element and reacts at 30-150 ℃ for 1-20 h. Washing the generated product with water and drying;
step 3): preparation of a metal monoatomic supported catalyst: ni (OH) doped with synthetic sulfur atoms 2 The array nano-sheets are placed in aqueous solution containing different metal salts and react at 30-150 ℃ for 1-10 h.
Further defined, the reaction temperature in step 1 is 160 ℃, and the reaction time is 6;
further defined, the reaction temperature in step 2 is 80 ℃ and the reaction time is 8 h;
further defined, the reaction temperature in step 3 is 70 ℃ and the reaction time is 2 h.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a cheap, efficient and universal method for synthesizing various metal single-atom supported catalysts, which has simple preparation process and is expected to be used for large-scale production. Ni (OH) 2 The nano-sheet array structure provides a super-hydrophobic surface for catalytic reaction, and can greatly reduce the adhesive force of bubbles, thereby promoting the release and escape of gas and ensuring the exposure of active sites; the X-ray absorption near-edge structure and the spherical aberration electron microscope prove that the metal monoatoms are successfully synthesized, and the introduction of the active metal monoatoms maximizes the number of catalytic sites in the material; doping of the heteroatom S adjusts Ni (OH) 2 The electronic structure of the catalyst improves the conductivity of the catalyst, and is beneficial to water electrolysis of the material under high current density; metal monoatoms and support S-Ni (OH) 2 The Ni and O (S) form a bond, the electronic structure of the whole catalyst is adjusted, and the catalytic activity of the catalyst is enhanced.
Drawings
FIG. 1 shows the S-Ni (OH) obtained in example 1) 2 Scanning electron microscope pictures of the catalytic materials are in a nano array structure;
FIG. 2 is a graph of Pt@S-Ni (OH) obtained in example 1 2 A spherical aberration electron microscope image of the catalytic material;
FIG. 3 is a graph of Pt@S-Ni (OH) obtained in example 1 2 Catalytic Material, fe@S-Ni (OH) prepared in example 2 2 Catalytic Material, mn@S-Ni (OH) prepared in example 3 2 Catalytic material and Cu@S-Ni (OH) prepared in example 4 2 Cathode polarization curve of hydrogen evolution reaction of catalytic material;
FIG. 4 shows Pt@S-Ni (OH) obtained in example 1 2 Catalytic Material, fe@S-Ni (OH) prepared in example 2 2 Catalytic Material, mn@S-Ni (OH) prepared in example 3 2 Catalytic material and Cu@S-Ni (OH) prepared in example 4 2 Anodic polarization curve of oxygen evolution reaction of catalytic material.
Description of the embodiments
Example 1
1. Synthetic Ni (OH) 2 The precursor comprises the following specific steps:
1) 0.5-1.0 mmol Ni(NO 3 ) 2 ·6H 2 dissolving O and 2.0-4.0 mmol urea in 30 mL ultrapure water, uniformly dispersing by ultrasonic, and stirring for 10 min at room temperature;
2) Transfer it to a containing a piece of 2X 3 cm 2 A 50 mL autoclave of nickel foam;
3) Transferring the reaction kettle into an oven to react at 160 ℃ for 6 h;
4) After the reaction, the mixture was washed with water and ethanol, and finally dried at 40℃for 6 h.
2. With Ni (OH) 2 S-Ni (OH) is synthesized as a precursor 2 The specific method comprises the following steps:
1) One piece of Ni (OH) 2 Precursor material (2×3 cm) 2 ) Placing the mixture in a reaction kettle;
2) Adding Na with the concentration of 0.5-1.0 mM into the reaction kettle, wherein the concentration of the Na is 30 mL 2 S·9H 2 An aqueous O solution;
3) Transferring the reaction kettle into an oven to react at 80 ℃ for 8 h;
4) After the reaction, the mixture was washed with water and ethanol, and finally dried at 40℃for 6 h.
3. By S-Ni (OH) 2 Synthesis of Pt@S-Ni (OH) as precursor 2 The specific method comprises the following steps:
1) One piece of S-Ni (OH) 2 Precursor material (2×3 cm) 2 ) Placing the mixture in a reaction kettle;
2) Adding 5-10 mu mol of H containing 30 mL water into a reaction kettle 2 PtCl 6 ·6H 2 An aqueous O solution;
3) Transferring the reaction kettle into an oven to react at 70 ℃ for 2 h;
4) After the reaction, the mixture was washed with water and ethanol, and finally dried at 40℃for 6 h.
Example 2
1. Synthesis of Fe@S-Ni (OH) 2 The specific method comprises the following steps:
1) One piece of S-Ni (OH) 2 Precursor material (2×3 cm) 2 ) Placed in a reaction kettle (method same: example 1);
2) Adding 5-10 mu mol of Fe (NO) containing 30 mL water into a reaction kettle 3 ) 3 ·9H 2 An aqueous O solution;
3) Transferring the reaction kettle into an oven to react at 70 ℃ for 2 h;
4) After the reaction, the mixture was washed with water and ethanol. Finally, it was dried at 40℃for 6 h.
Example 3
1. Synthesis of Mn@S-Ni (OH) 2 The specific method comprises the following steps:
1) One piece of S-Ni (OH) 2 Precursor material (2×3 cm) 2 ) Placed in a reaction kettle (method same: example 1);
2) Adding 5-10 mu mol of MnSO containing 30 mL water into a reaction kettle 4 ·H 2 An aqueous O solution;
3) Transferring the reaction kettle into an oven to react at 70 ℃ for 2 h;
4) After the reaction, the mixture was washed with water and ethanol, and finally dried at 40℃for 6 h.
Example 4
1. Synthesis of Cu@S-Ni (OH) 2 The specific method comprises the following steps:
1) One piece of S-Ni (OH) 2 Precursor material (2×3 cm) 2 ) Placed in a reaction kettle (method same: example 1);
2) Adding 5-10 mu mol of CuSO containing 30 mL water into a reaction kettle 4 ·5H 2 An aqueous O solution;
3) Transferring the reaction kettle into an oven to react at 70 ℃ for 2 h;
4) After the reaction, the mixture was washed with water and ethanol, and finally dried at 40℃for 6 h.
The preferred embodiments and examples of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above-described embodiments and examples, and various changes may be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (9)

1. The electrolytic water catalyst is characterized by being prepared by the following process:
step 1): preparing nickel hydroxide nano-sheet precursor: immersing the substrate in an aqueous solution containing nickel salt, urea and the like, and heating at 100-200 ℃ for reaction 2-48 h. Then washing and drying to obtain Ni (OH) 2 An array nanoplatelet precursor;
step 2): vulcanization treatment of metal hydroxide: ni (OH) to be synthesized 2 The array nano-sheet precursor is immersed in an aqueous solution containing sulfur element and reacts at 30-150 ℃ for 1-20 h. The generated product is dried after being washed by water;
step 3): preparation of a metal monoatomic supported catalyst: ni (OH) doped with synthetic sulfur atoms 2 The array nano-sheets are placed in aqueous solution containing different metal salts and react at 30-150 ℃ for 1-10 h.
2. The full water splitting catalyst of claim 1, wherein the substrate is selected from the group consisting of carbon paper, nickel foam, carbon cloth, and conductive glass.
3. The electrolyzed water catalyst according to claim 1, wherein the nickel salt in step 1 comprises one or more metal salts selected from the group consisting of chloride, sulfate, nitrate, and the like.
4. The electrolyzed water catalyst according to claim 1, wherein the content ratio of nickel salt to urea in step 1 is in the range of 0.01 to 10.
5. The electrolyzed water catalyst according to claim 1, wherein the sulfur source in step 2 comprises one or more of thioacetamide, sodium sulfide, and thiourea.
6. The electrolyzed water catalyst according to claim 1, wherein the metal salt in step 3 comprises one or more of manganese salt, iron salt, cobalt salt, copper salt, gold salt, silver salt, platinum salt, palladium salt, molybdenum salt, etc.
7. The electrolyzed water catalyst of claim 1 wherein the metal salt in step 3 comprises one or both of a chloride salt, a sulfate salt, and a nitrate salt.
8. The electrolyzed water catalyst according to claim 1, wherein,
the amount of nickel salt material in step 1) is 0.1-20 mmol;
the urea content of step 1) is 1.0-100 mmol;
step 2) an aqueous solution having a sulfur source concentration of 0.1 to 20 mM;
step 3) an aqueous solution having a concentration of metal salt of 0.001. Mu.M-5 mM.
9. An electrolyzed water catalyst obtainable by the process according to any of claims 1 to 8.
CN202310803195.2A 2023-07-03 2023-07-03 Metal monoatomic load S-Ni (OH) for electrolysis of water at high current density 2 Universal preparation method of catalyst Pending CN116607168A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117374302A (en) * 2023-12-08 2024-01-09 华北电力大学 Nickel/nickel hydroxide electrode catalyst, preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117374302A (en) * 2023-12-08 2024-01-09 华北电力大学 Nickel/nickel hydroxide electrode catalyst, preparation method and application
CN117374302B (en) * 2023-12-08 2024-02-27 华北电力大学 Nickel/nickel hydroxide electrode catalyst, preparation method and application

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