CN-121976232-A - Near-distance nickel oxide cluster and nickel monoatomic synergistic two-electron oxygen reduction electrocatalyst grown on carbon substrate

CN121976232ACN 121976232 ACN121976232 ACN 121976232ACN-121976232-A

Abstract

The invention discloses a near-distance nickel oxide cluster and nickel monoatomic synergistic two-electron oxygen reduction electrocatalyst growing on a carbon substrate and a preparation method thereof, wherein the preparation method comprises the steps of oxidizing the carbon substrate to obtain the carbon substrate with oxygen-enriched functional groups on the surface; dispersing the carbon substrate in a solvent to form a carbon-containing solution, introducing a nickel salt metal precursor into the carbon-containing solution, forming a structure of coexistence of nickel oxide clusters and nickel monoatoms on the surface of the carbon substrate by the nickel precursor under the action of a reducing agent, and separating and drying to obtain the electrocatalyst. The electrocatalyst comprises a carbon substrate, nickel oxide clusters and nickel monoatoms distributed on the surface of the carbon substrate. The electrocatalyst can be applied to the electrocatalytic preparation of hydrogen peroxide in two-electron oxygen reduction reaction.

Inventors

DU HEBAO
PENG MIN
HU WEI
ZHAO XI
HE WEI
PENG LIXIONG
ZHAO YUXUAN

Assignees

上海澳思净科技有限公司

Dates

Publication Date: 20260505
Application Date: 20251230

Claims (10)

1. A method for preparing a two-electron oxygen reduction electrocatalyst by the cooperation of a close-range nickel oxide cluster and a nickel monoatom grown on a carbon substrate, which is characterized by comprising the following steps: S1, oxidizing a carbon substrate, adding a carbon material into concentrated acid heated to 40-100 ℃, adding potassium permanganate, stirring and reacting for 1-10 hours at 25-100 ℃, and obtaining the carbon substrate with the surface rich in oxygen functional groups after termination reaction, acid washing and water washing; S2, mixing the carbon substrate with 0.01-2 parts of the carbon substrate Dispersing the solution in deionized water to form a carbon-containing solution; S3, adding a nickel salt metal precursor into the carbon-containing solution to obtain a carbon solution containing a nickel precursor; s4, adding a metal reducing agent into the carbon solution of the nickel-containing precursor, and reacting under the stirring condition to enable the nickel precursor to form a structure that nickel oxide clusters coexist with nickel monoatoms on the surface of the carbon substrate; And S5, filtering and drying the reacted system to obtain the electrocatalyst.
2. The method for preparing a two-electron oxygen reduction electrocatalyst with the cooperation of a close-range nickel oxide cluster and a nickel monoatom grown on a carbon substrate according to claim 1, wherein the carbon material in step S1 is carbon nanotubes, carbon fibers, carbon spheres, graphene or carbon black, and the concentration of the carbon material in concentrated acid is 0.5-2 The concentration of potassium permanganate is 0.01-1 Preferably, the concentration of the carbon material is 1.39 The concentration of the potassium permanganate is 0.26 。
3. The method for preparing the two-electron oxygen reduction electrocatalyst by combining a close-range nickel oxide cluster and a nickel monoatom grown on a carbon substrate according to claim 1, wherein the oxidation treatment in the step S1 is performed at 25-100 ℃, the reaction time is 1-10 h, and preferably, the reaction is stirred for 4h at 60 ℃.
4. The method of claim 1, wherein in step S3, the nickel salt is a divalent nickel salt such as nickel nitrate hexahydrate or nickel chloride, and the concentration thereof is 0.2-3 Preferably, the concentration of the nickel salt is 1 。
5. The method for preparing a two-electron oxygen reduction electrocatalyst with synergistic nickel monoatoms and close-range nickel oxide clusters grown on a carbon substrate according to claim 1, wherein the metal reducing agent in step S4 is sodium borohydride, hydrazine hydrate or vitamin C, and the concentration of the metal reducing agent is 0.1-20 Stirring reaction time is 10-30 h.
6. The method for preparing a two-electron oxygen reduction electrocatalyst according to claim 5, wherein the metal reducing agent is sodium borohydride, and the concentration thereof is 9.8 The reaction time was stirred for 24h.
7. The method for preparing a two-electron oxygen reduction electrocatalyst according to claim 1, wherein the drying in step S5 is performed at 60 ℃.
8. A two-electron oxygen reduction electrocatalyst according to any one of claims 1 to 7, wherein the electrocatalyst comprises a carbon substrate and nickel oxide clusters and nickel monoatoms distributed on the surface of the carbon substrate.
9. A two-electron oxygen reduction electrocatalyst according to claim 8 wherein the nickel oxide clusters and nickel monoatoms grown on the carbon substrate in close proximity cooperate, preferably wherein the nickel oxide clusters and nickel monoatoms are co-located on or adjacent to the surface of the carbon substrate.
10. A two-electron oxygen reduction electrocatalyst according to claim 8, wherein the electrocatalyst is used for the electrocatalytic production of hydrogen peroxide in a two-electron oxygen reduction reaction.

Description

Near-distance nickel oxide cluster and nickel monoatomic synergistic two-electron oxygen reduction electrocatalyst grown on carbon substrate Technical Field The invention relates to the technical field of electrocatalytic materials, in particular to a two-electron oxygen reduction electrocatalyst with the cooperation of a nickel oxide cluster and a nickel monoatom growing on a carbon substrate at a short distance. Background Hydrogen peroxide is an important green oxidant and has wide application in the fields of chemical synthesis, environmental management, medical disinfection, energy systems and the like. The existing industrial hydrogen peroxide preparation method mainly adopts an anthraquinone method, has complex process flow and higher energy consumption, relies on centralized production and transportation, has certain potential safety hazard and environmental burden, and is difficult to meet the requirements of the distributed and on-site hydrogen peroxide preparation. In recent years, electrochemical two-electron oxygen reduction (2ORR) methods for preparing hydrogen peroxide have received considerable attention because of the advantages of mild reaction conditions, coupling with renewable energy sources, and the like. In this process, the performance of the electrocatalyst has an important influence on the reaction pathway selectivity, hydrogen peroxide yield and reaction stability. Therefore, the development of efficient and stable two-electron oxygen reduction electrocatalysts is one of the important research points in this field. The existing research shows that the single-atom electrocatalyst has good application potential in oxygen reduction reaction due to high dispersion of metal atoms and high atom utilization rate. Among them, nickel-based monoatomic catalysts are attracting attention because of their relatively low cost and good chemical stability. However, only a single metal monoatomic active site is relied on, so that the reaction activity and the selectivity are difficult to be simultaneously achieved in the reaction process, and the problems of performance decay and the like are easy to occur under the condition of higher current density. On the other hand, the metal oxide cluster catalytic material has certain activity in the oxygen reduction reaction, but the active sites of the metal oxide cluster catalytic material are unevenly distributed, the atom utilization rate is lower, and agglomeration or structural evolution is easy to occur in part of the system, so that the stability of the catalytic performance is influenced. Therefore, how to reasonably construct a catalytic structure with coexistence of metal monoatoms and metal oxide clusters on a carbon-based carrier and realize effective control of a material structure and a preparation process is still a technical problem to be solved in the field. For the above reasons, it is necessary to provide an electrocatalytic material with controllable structure and definite preparation method and a preparation method thereof, so as to meet the application requirement of electrochemically preparing hydrogen peroxide under the condition of two-electron oxygen reduction reaction. Disclosure of Invention The invention aims to provide a two-electron oxygen reduction electrocatalyst with the cooperation of nickel oxide clusters and nickel monoatoms grown on a carbon substrate at a short distance, so as to solve the problems in the prior art. In order to solve the technical problems, the invention provides a preparation method of a near-distance nickel oxide cluster and nickel monoatomic synergistic two-electron oxygen reduction electrocatalyst growing on a carbon substrate, which comprises the following steps of S1, oxidizing the carbon substrate, adding a carbon material into concentrated acid heated to 40-100 ℃, adding potassium permanganate, stirring and reacting for 1-10 h at 25-100 ℃, terminating the reaction, pickling and washing to obtain the carbon substrate with oxygen-enriched functional groups on the surface, S2, adding the carbon substrate into concentrated acid heated to 0.01-2The method comprises the steps of dispersing the nickel salt metal precursor into deionized water to form a carbon-containing solution, S3, adding the nickel salt metal precursor into the carbon-containing solution to obtain a nickel-containing precursor carbon solution, S4, adding a metal reducing agent into the nickel-containing precursor carbon solution, reacting under the stirring condition to enable the nickel precursor to form a structure with nickel oxide clusters coexisting with nickel monoatoms on the surface of a carbon substrate, and S5, filtering and drying the reacted system to obtain the electrocatalyst. According to the technical scheme, in the step S1, the carbon material is carbon nano tube, carbon fiber, carbon sphere, graphene or carbon black, and the concentration of the carbon material in the concentrated acid is 0.5-2The concentration