Search

CN-122013221-A - Electrolytic water catalyst, preparation method and application thereof

CN122013221ACN 122013221 ACN122013221 ACN 122013221ACN-122013221-A

Abstract

The invention discloses an electrolytic water catalyst, a preparation method and application thereof, wherein the electrolytic water catalyst comprises iridium oxide (IrOx) and/or ruthenium oxide (RuOx), wherein 0< x <2, the catalyst has stable lattice structure and nano-scale particle diameter, the preparation method comprises the steps of introducing fuel gas and oxidant into a flame burner, igniting and burning, controlling the volume flow ratio of the fuel gas and the oxidant to form a reducing atmosphere in the combustion chamber, introducing an iridium-containing or ruthenium-containing compound solution into the combustion chamber in a spraying manner to carry out combustion reaction, generating iridium oxide (IrOx) or ruthenium oxide (RuOx), and collecting products after the combustion reaction to obtain the electrolytic water catalyst. Through the mode, the water electrolysis catalyst provided by the invention realizes high activity and excellent stability, the preparation process is simple in process, good in repeatability, efficient, environment-friendly and high in product quality, and the water electrolysis film electrode applying the catalyst realizes perfect combination of high-efficiency hydrogen production and ultra-long service life.

Inventors

  • GUAN CHUNHONG
  • ZHANG YUN
  • Kang Tianping
  • LI JINGXIN
  • WU XINGHUA
  • MEI YIFAN
  • XIE CHAO
  • DING RONGHUA

Assignees

  • 江苏泛亚微透科技股份有限公司

Dates

Publication Date
20260512
Application Date
20260121

Claims (10)

  1. 1. An electrolyzed water catalyst, characterized in that the catalyst comprises iridium oxide (IrOx) and/or ruthenium oxide (RuOx), wherein 0 < x < 2, the catalyst having a stable lattice structure and a nano-scale particle size.
  2. 2. The electrolyzed water catalyst according to claim 1, wherein the catalyst further comprises a mixture of one or more of titanium oxide (TiOx), cerium oxide (CeOx), manganese oxide (MnOx), zirconium oxide (ZrOx) as a conductive support, wherein 0 < x < 2.
  3. 3. The electrolyzed water catalyst of claim 2 wherein the TiOx, ceOx, mnOx or ZrOx is derived from a titanium-, cerium-, manganese-, or zirconium-containing compound comprising one or more of titanium isopropoxide, titanium tetrachloride, cerium nitrate, cerium acetate, cerium chloride, manganese nitrate, manganese tetrachloride, zirconium n-butoxide, or zirconium chloride.
  4. 4. The electrolyzed water catalyst according to claim 1, wherein x ranges from 0.5< x <1.9 and the average particle size of the nanoscale particle size is between 3 and 8 nanometers.
  5. 5. A method for preparing an electrolyzed water catalyst, which is characterized by comprising the following steps: (1) Introducing fuel gas and oxidant into the flame burner, and igniting and burning; (2) Controlling the volumetric flow ratio of the fuel gas and the oxidant to form a reducing atmosphere in the combustion chamber sufficient to produce an oxide of the metal compound having oxygen vacancies upon combustion at elevated temperatures but insufficient to reduce it to elemental metal; (3) Introducing iridium-containing or ruthenium-containing compound solution into a combustion chamber in a spray mode to carry out combustion reaction to generate iridium oxide (IrOx) or ruthenium oxide (RuOx), wherein 0 < x < 2; (4) And collecting the products after the combustion reaction to obtain the electrolyzed water catalyst.
  6. 6. The method for preparing an electrolyzed water catalyst according to claim 5, wherein the fuel gas is methane, the volume flow ratio of methane to oxygen is controlled to be between 1.05:2 and 20:1 when the oxidant is oxygen, and the flow is converted into an equivalent oxygen flow according to the oxygen content of 21% when the oxidant is air.
  7. 7. The method for preparing an electrolyzed water catalyst according to claim 5, wherein the fuel gas is acetylene, the volume flow ratio of acetylene to oxygen is controlled to be between 2.05:5 and 20:1 when the oxidant is oxygen, and the flow is converted into an equivalent oxygen flow according to the oxygen content of 21% when the oxidant is air.
  8. 8. The method for preparing an electrolyzed water catalyst according to claim 5, wherein when the fuel gas is hydrogen and the oxidant is oxygen, the volume flow ratio of the hydrogen to the oxygen is controlled to be between 2.05:1 and 10:1, and when the oxidant is air, the flow is converted into equivalent oxygen flow according to the oxygen content of 21%.
  9. 9. The method for preparing an electrolytic water catalyst according to claim 5, wherein in the step (3), the iridium-containing compound is chloroiridic acid, the ruthenium-containing compound is ruthenium trichloride, the solution is an aqueous solution, an ethanol solution or an isopropanol solution, and the spraying mode is one selected from pressure spraying, air flow spraying, electrostatic spraying, rotary disk spraying or ultrasonic spraying.
  10. 10. An electrolytic water hydrogen production membrane electrode comprising a proton exchange membrane, an anode catalytic layer coated on one side of the proton exchange membrane, a cathode catalytic layer coated on the other side of the proton exchange membrane, and a gas diffusion layer respectively arranged on the outer surfaces of the cathode catalytic layer and the anode catalytic layer, wherein the anode catalytic layer comprises the electrolytic water catalyst as claimed in any one of claims 1 to 4, the cathode catalytic layer comprises a platinum-based catalyst, and the total loading amount of iridium and ruthenium in the anode catalytic layer is 0.1 mg/cm 2 to 2.0 mg/cm 2 .

Description

Electrolytic water catalyst, preparation method and application thereof Technical Field The invention relates to the field of catalyst preparation, in particular to a high-activity high-stability electrolyzed water catalyst for a proton exchange membrane electrolyzed water anode oxygen evolution reaction and a preparation method thereof. Background The hydrogen is used as a green energy source, the used product only contains water, the hydrogen belongs to a clean renewable energy source in the new era, and the hydrogen production by water electrolysis becomes one of the most effective hydrogen production methods due to the efficient energy conversion. However, commercial application of this technology is severely limited by the slow kinetics of the anodic oxygen evolution reaction. The oxygen evolution reaction involves four sequential proton-coupled electron transfer processes, the inherent high energy barrier of which results in low reaction rates and large overpotential, which directly limits the efficiency of the overall water electrolysis hydrogen production process. Oxygen evolution reactions are carried out under acidic conditions, which can achieve higher energy efficiency and lower ohmic losses, but place very high demands on the activity and stability of the catalyst. Currently, commonly used oxygen evolution reaction catalysts are iridium oxide (IrOx) and ruthenium oxide (RuOx), which are generally prepared by wet chemical reduction. The method has the obvious defects that firstly, the process is complex and lengthy, a plurality of procedures such as stirring reaction, filtering, drying, calcining and crushing are needed, secondly, a large amount of water or solvent is needed to be consumed during mass production, filtrate to be treated is produced, and environmental pressure is brought, and most importantly, the catalyst particles prepared by the method are generally of an amorphous structure, have larger particle size and uneven distribution, so that the catalyst particles have poor catalytic activity and poor durability, and are difficult to meet the requirements of high-efficiency stable electrolytic hydrogen production. Disclosure of Invention The invention mainly solves the technical problem of providing the electrolyzed water catalyst which has simple process, is environment-friendly and can realize high activity and excellent stability at the same time, and the preparation method thereof. In order to solve the technical problems, the invention adopts a technical scheme that an electrolytic water catalyst is provided, the catalyst comprises iridium oxide (IrOx) and/or ruthenium oxide (RuOx), wherein 0 < x < 2, and the catalyst has a stable lattice structure and nano-scale particle size. The sub-stoichiometric bit property of 0 < x < 2 means that abundant oxygen vacancies are successfully introduced into the catalyst crystal lattice, which not only improves the catalytic intrinsic activity, but also improves the electronic conductivity remarkably, thereby reducing the ohmic internal resistance, and being suitable for electrolytic water Oxygen Evolution Reaction (OER). Meanwhile, the stable lattice structure and the nanoscale particle size ensure that the catalyst has long service life and high specific surface area under a severe anode environment, and active sites are fully exposed. In a preferred embodiment of the present invention, the catalyst further comprises a mixture of one or more of titanium oxide (TiOx), cerium oxide (CeOx), manganese oxide (MnOx), zirconium oxide (ZrOx) as a conductive carrier, wherein 0 < x < 2, and the carrier is used for dispersing IrOx or RuOx, and increasing active sites. The invention can also contain carriers with oxygen vacancies, not only can effectively disperse and anchor active components, prevent agglomeration, increase the number of active sites, but also can form a synergistic effect by utilizing the conductivity of the carriers, thereby reducing the loading of expensive Ir and Ru and achieving the effects of cost reduction and synergy while ensuring excellent performance. In a preferred embodiment of the present invention, the TiOx, ceOx, mnOx or ZrOx is derived from a titanium, cerium, manganese or zirconium containing compound, including one or more of titanium isopropoxide, titanium tetrachloride, cerium nitrate, cerium acetate, cerium chloride, manganese nitrate, manganese tetrachloride, zirconium n-butoxide or zirconium chloride. In a preferred embodiment of the invention, x is in the range of 0.5< x <1.9, and the average particle size of the nanoscale particle size is between 3 and 8 nanometers. The preferred range of 0.5< x <1.9 allows the concentration of oxygen vacancies to be in the optimum interval to obtain optimum catalytic activity and conductivity, and the average particle size of 3-8 nm ensures extremely large specific surface area and uniform physical properties. The invention adopts another technical scheme that the preparation