CN-121972188-A - Method for enhancing activity of monoatomic catalyst, fluorinated monoatomic catalyst and hydrogen production method by water splitting

CN121972188ACN 121972188 ACN121972188 ACN 121972188ACN-121972188-A

Abstract

The invention relates to the technical field of contact electro-catalysis and energy materials, in particular to a method for enhancing the activity of a single-atom catalyst, a fluorinated single-atom catalyst and a water splitting hydrogen production method. The method for enhancing the activity of the single-atom catalyst comprises the steps of providing a single-atom catalyst, carrying out fluorination treatment on the surface of the single-atom catalyst through an organic solvent containing fluorine silane to obtain the fluorinated single-atom catalyst, wherein the fluorinated single-atom catalyst enhances the contact electrification capability of a carrier based on a contact electro-catalysis effect and can form an interface electric field around the single-atom active center in the single-atom catalyst, so that the catalytic activity of the single-atom catalyst is enhanced. The method provides a brand new thought for solving the technical problem of weak catalytic activity of the conventional single-atom catalyst, and not only can the technical problem of weak catalytic activity of the single-atom catalyst be solved by the thought, but also the single-atom catalyst with the catalytic activity improved can be applied to the field of hydrogen production to improve the hydrogen production efficiency.

Inventors

WANG ZHONGLIN
WANG ZIMING
YANG XUEYAN
JIANG DONGJIAN

Assignees

北京纳米能源与系统研究所

Dates

Publication Date: 20260505
Application Date: 20260303

Claims (10)

1. A method of enhancing the activity of a monoatomic catalyst comprising: Providing a single-atom catalyst comprising a carrier and a single atom supported on the carrier; The fluorinated monoatomic catalyst is obtained by carrying out fluorination treatment on the surface of the monoatomic catalyst by using an organic solvent containing fluorosilane, the fluorinated monoatomic catalyst enhances the contact electrification capability of a carrier based on contact electro-catalysis effect, and an interface electric field for enhancing the reduction activity of monoatomic sites is formed around the monoatomic active center in the monoatomic catalyst based on charge aggregation caused by contact electrification, so that the catalytic activity of the monoatomic catalyst is enhanced.
2. The method for enhancing the activity of a monoatomic catalyst according to claim 1, wherein the organic solvent of the fluorosilane is a 1h,2 h-perfluorodecyl triethoxysilane/isooctane solution; And/or the single-atom catalyst is Ru/SiO 2 ; and/or the time of the fluorination treatment is 12-48 h.
3. The method for enhancing the activity of a monoatomic catalyst according to claim 2, wherein the concentration of the 1H, 2H-perfluorodecyl triethoxysilane/isooctane solution is 1 mM-20mM.
4. The method of enhancing the activity of a single-atom catalyst as recited in claim 1, wherein the carrier comprises any one of an organic polymer, an inorganic oxide, or a carbon-based material.
5. The method for enhancing the activity of a monoatomic catalyst according to claim 4, wherein when the carrier is an organic polymer, it comprises any one of polytetrafluoroethylene powder, nylon film, and cellulose microspheres; And/or, when the carrier is an inorganic oxide, the carrier comprises any one of mesoporous silica, alumina and titanium dioxide; And/or when the carrier is a carbon-based material, the carrier comprises any one of activated carbon, graphene and nitrogen-doped carbon nanotubes.
6. The method of enhancing the activity of a single-atom catalyst as recited in claim 1, wherein the morphology of the support comprises any one of a powder, a thin film material, or a three-dimensional porous structure.
7. The method for enhancing the activity of a monoatomic catalyst according to claim 6, wherein when the carrier is in a powder form, the particle size of the carrier ranges from 100nm to 10 μm; And/or, when the carrier is in a form of a film material, the thickness of the carrier is 10-200 mu m; And/or when the carrier is in a three-dimensional porous structure, the pore diameter of the carrier is 2 nm-50 nm.
8. A fluorinated monoatomic catalyst obtainable by a method of enhancing the activity of a monoatomic catalyst according to any one of claims 1 to 7, comprising a monoatomic catalyst and an organic solvent for a fluorosilane, wherein the mass to volume ratio of the monoatomic catalyst to the organic solvent for a fluorosilane is 5g:1l.
9. A method for producing hydrogen by water splitting, comprising: Providing a fluorinated monoatomic catalyst according to claim 8; And adding the fluorinated monoatomic catalyst and water into a sealed reactor according to the mass volume ratio of 0.1 g-1.0 g:1L, and performing ultrasonic treatment under the protection of inert atmosphere to enable the fluorinated monoatomic catalyst and the water to alternately contact and separate so as to accumulate electrons on the surface of the fluorinated monoatomic catalyst, and transferring the accumulated electrons to hydrogen ions in the subsequent contact and separation process of the fluorinated monoatomic catalyst and the water, so that the hydrogen ions are reduced into hydrogen.
10. The hydrogen production method by water pyrolysis according to claim 9, wherein the frequency of the ultrasonic treatment is 20 khz-200 khz; and/or the water includes any one of pure water or seawater.

Description

Method for enhancing activity of monoatomic catalyst, fluorinated monoatomic catalyst and hydrogen production method by water splitting Technical Field The invention relates to the technical field of contact electro-catalysis and energy materials, in particular to a method for enhancing the activity of a single-atom catalyst, a fluorinated single-atom catalyst and a water splitting hydrogen production method. Background Single-atom catalysts (SACs) are a great breakthrough in the field of heterogeneous catalysis, and have great potential in the fields of energy conversion, chemical synthesis and the like by virtue of the maximum atom utilization efficiency and unique electronic structure characteristics. In the research process of the existing single-atom catalyst, the carrier material is generally regarded as an inert support body simply, so that the improvement of the catalytic performance of the single-atom catalyst is limited. Furthermore, existing catalytic systems based on monoatomic catalysts often rely on external light fields, electric fields or chemical sacrificial agents, which not only increase the complexity and running costs of the system, but also limit the practical application range thereof. Furthermore, the hydrogen production efficiency of existing single-atom catalysts in pure water systems is often limited by slow water dissociation kinetics and proton starvation issues. Conventional solutions typically promote the water dissociation process by alkalizing the electrolyte or using sacrificial agents, which not only increase the complexity of the overall system but may introduce side reactions. Disclosure of Invention In order to solve the technical problem of weak catalytic activity of the monoatomic catalyst in the prior art, the invention provides a method for enhancing the activity of the monoatomic catalyst, a fluorinated monoatomic catalyst and a water-splitting hydrogen production method. The invention adopts the following technical scheme that the method for enhancing the activity of the monoatomic catalyst comprises the step of providing the monoatomic catalyst which comprises a carrier and monoatomic atoms loaded on the carrier. The fluorinated monoatomic catalyst is obtained by carrying out fluorination treatment on the surface of the monoatomic catalyst by using an organic solvent containing fluorosilane, the fluorinated monoatomic catalyst enhances the contact electrification capability of a carrier based on contact electro-catalysis effect, and an interface electric field for enhancing the reduction activity of monoatomic sites is formed around the monoatomic active center in the monoatomic catalyst based on charge aggregation caused by contact electrification, so that the catalytic activity of the monoatomic catalyst is enhanced. As a further improvement of the present invention, the organic solvent for the fluorosilane is a 1H, 2H-perfluorodecyl triethoxysilane/isooctane solution. As a further improvement of the invention, the monoatomic catalyst is Ru/SiO 2. As a further improvement of the invention, the fluorination treatment time is 12-48 h. As a further improvement of the invention, the concentration of the 1H, 2H-perfluoro decyl triethoxysilane/isooctane solution is 1 mM-20 mM. As a further improvement of the present invention, the carrier includes any one of an organic polymer, an inorganic oxide, or a carbon-based material. As a further improvement of the invention, when the carrier is an organic polymer, it includes any one of polytetrafluoroethylene powder, nylon film, and cellulose microspheres. As a further improvement of the invention, when the carrier is an inorganic oxide, the carrier comprises any one of mesoporous silica, alumina and titanium dioxide. As a further improvement of the invention, when the carrier is a carbon-based material, the carrier comprises any one of active carbon, graphene and nitrogen-doped carbon nanotubes. As a further improvement of the present invention, the morphology of the support includes any of a powder state, a thin film material, or a three-dimensional porous structure. As a further improvement of the invention, when the carrier is in a powder state, the particle size range is 100 nm-10 mu m. As a further improvement of the invention, when the carrier is in the form of a film material, the thickness of the carrier is 10-200 mu m. As a further improvement of the invention, when the carrier is in a three-dimensional porous structure, the pore diameter is 2 nm-50 nm. The invention also includes a fluorinated monoatomic catalyst obtainable by a method of enhancing monoatomic catalyst activity as described above. The fluorinated monoatomic catalyst comprises a monoatomic catalyst and an organic solvent of fluorine-containing silane, wherein the mass volume ratio of the monoatomic catalyst to the organic solvent of fluorine-containing silane is 5g to 1L. The invention also includes a method for producing hydrogen by water splittin