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CN-121988392-A - Preparation method of piezoelectric-mechanical oxidation reduction hydrogen peroxide catalyst with oxygen defects connected in series

CN121988392ACN 121988392 ACN121988392 ACN 121988392ACN-121988392-A

Abstract

The invention discloses a preparation method of a piezoelectric-mechanical oxidation reduction hydrogen peroxide catalyst with oxygen defects connected in series, which comprises the following steps of firstly constructing a zinc oxide substrate with a litchi-shaped structure through water phase thermal induction self-assembly reaction; the catalyst can be used for preparing hydrogen peroxide efficiently and selectively under pure water and normal temperature conditions by ultrasonic excitation, has the advantages of mild reaction conditions, high generation rate, good stability, environmental protection and the like, and is suitable for application scenes of in-situ preparation of distributed hydrogen peroxide.

Inventors

  • YE FEI
  • LI LONGFEI
  • LI CHANG
  • TANG CHONGJUN
  • LI WANLU
  • ZHANG QINGRUI

Assignees

  • 燕山大学

Dates

Publication Date
20260508
Application Date
20260202

Claims (8)

  1. 1. The preparation method of the piezoelectric-mechanical oxidation reduction hydrogen peroxide catalyst with oxygen defects connected in series is characterized by sequentially performing the following steps: S1, placing zinc acetate dihydrate in ethanolamine, stirring for 1-3 h to obtain a mixed solution, transferring the mixed solution into a polytetrafluoroethylene lining autoclave, performing solvothermal reaction, cooling to room temperature after the reaction is finished, washing, suction filtering and drying the obtained product, and grinding the product to 800-1500 meshes to obtain zinc oxide powder; s2, dispersing zinc oxide powder in ultrapure water, ultrasonically treating the mixture for 20 to 60 min hours, dropwise adding sodium borohydride aqueous solution into the mixture under the protection of inert gas and stirring conditions, stirring the mixture to react for 0.5 to 6 h times, washing the product for 3 to 5 times after the reaction is finished, filtering the product, drying the product at 40 to 70 ℃ for 8 to 14 h hours, and grinding the product to 800 to 1500 meshes to obtain zinc oxide materials with oxygen defects; S3, placing the zinc oxide material with oxygen defects into a buffer solution, adding dopamine hydrochloride after ultrasonic dispersion, stirring and reacting 24h under a light-shielding condition, washing the product for 3-5 times after the reaction is finished, filtering, drying 8-14 h at 40-70 ℃, and grinding to 800-1500 meshes to obtain the piezoelectric-mechanical oxidation reduction hydrogen peroxide catalyst with oxygen defects connected in series.
  2. 2. The method for preparing the piezoelectric-mechanical oxidation-reduction hydrogen peroxide catalyst with oxygen defects connected in series according to claim 1, wherein in the step S1, the mass-volume ratio of the zinc acetate dihydrate to the ethanolamine is (3-3.5) (120-170) g/mL.
  3. 3. The method for preparing a catalyst for producing hydrogen peroxide by piezo-mechanical oxidation and reduction of oxygen deficiency series according to claim 1, wherein in the step S1, the temperature of the solvothermal reaction is 160-200 ℃ and the time is 7-9 h.
  4. 4. The method for preparing a catalyst for producing hydrogen peroxide by piezo-mechanical oxidation and reduction of oxygen deficiency according to claim 1, wherein in step S1, the temperature is 40-70 ℃ and the time is 8-14 h.
  5. 5. The method for preparing the piezoelectric-mechanical oxidation-reduction hydrogen peroxide catalyst with oxygen defects connected in series according to claim 1, wherein in the step S2, the mass-volume ratio of the zinc oxide powder to the ultrapure water is (0.3-0.5): (80-120) g/mL, the concentration of the sodium borohydride aqueous solution is 0.26 g/mL, and the mass-volume ratio of the zinc oxide powder to the sodium borohydride aqueous solution is (0.3-0.5): 25 g/mL.
  6. 6. The method for preparing a catalyst for producing hydrogen peroxide by piezo-mechanical oxidation and reduction of oxygen deficiency series according to claim 1, wherein in step S2, the dropping rate of the sodium borohydride aqueous solution is 8-10 mL/min.
  7. 7. The method for preparing the piezoelectric-mechanical oxidation-reduction hydrogen peroxide catalyst with oxygen defects connected in series according to claim 1, wherein in the step S3, the buffer solution is Tris-HCl, the concentration of the buffer solution is 45-55 mM, the pH value is 8-9, and the mass-volume ratio of the zinc oxide material with oxygen defects to Tris-HCl is (0.25-0.35) to (80-120) g/mL.
  8. 8. The method for preparing the piezoelectric-mechanical oxidation-reduction hydrogen peroxide catalyst with oxygen defects connected in series according to claim 1, wherein in the step S3, the mass ratio of the zinc oxide material containing the oxygen defects to the dopamine hydrochloride is (0.25-0.35): 0.015-0.06.

Description

Preparation method of piezoelectric-mechanical oxidation reduction hydrogen peroxide catalyst with oxygen defects connected in series Technical Field The invention belongs to the technical field of hydrogen peroxide production by mechanocatalysis, and relates to a preparation method of a piezoelectric-mechanical oxidation reduction hydrogen peroxide catalyst with oxygen defects connected in series. Background Hydrogen peroxide is not only an environment-friendly green oxidant, but also an energy carrier with potential application value, and has wide application prospect in the fields of environmental pollution control, chemical synthesis, fuel cell power generation and the like. The existing industrial hydrogen peroxide preparation method mainly adopts an anthraquinone method, the method has the advantages of complex process flow, high requirements on equipment and operation conditions, high energy consumption, and capability of generating a large amount of refractory pollutants, and bringing no small pressure to the subsequent waste treatment links. Therefore, development of an energy-saving, environment-friendly and efficient potential hydrogen peroxide synthesis technology to replace the traditional anthraquinone method is always a research direction focused in the field. In recent years, strategies for driving the synthesis of hydrogen peroxide by using water and oxygen as raw materials and utilizing inexhaustible mechanical energy (such as ultrasonic waves, water flow and the like) widely existing in the environment are increasingly paid attention to. Mechanocatalysis generally refers to the process of collecting and regulating charges from a bulk material or a reaction environment under mechanical force stimulation through internal polarization effects or interfacial charge transfer behaviors of the material, so as to drive redox reactions, and common forms of the processes include piezoelectric effects, contact electrification effects and the like. Taking common piezoelectric semiconductor material zinc oxide as an example, the inorganic crystal generally has higher piezoelectric response coefficient, larger forbidden bandwidth and stronger redox driving force, and can effectively generate polarized electric field and participate in reaction under the stimulation of mechanical force. However, the existing researches show that the inorganic piezoelectric material still has a plurality of problems in the hydrogen peroxide synthesis process, namely, on one hand, the surface of the inorganic piezoelectric material lacks a definite oxidation-reduction site, the adsorption and activation capability of oxygen molecules are limited, and effective regulation and control of two electron paths in the oxygen reduction reaction are difficult, and on the other hand, the electron and proton transfer behaviors in the reaction process lack fine control, so that carrier recombination or side reaction is easy to occur, and even further decomposition of generated hydrogen peroxide is caused. Therefore, how to cooperatively regulate and control the characteristics of charge generation, separation and reaction sites in a mechanocatalytic system, so as to realize the precise control of a hydrogen peroxide generation path is still a key technical problem to be solved in the field. The present invention has been made in order to solve the above-described conventional problems. Disclosure of Invention Aiming at the technical problems, the invention aims to provide a preparation method of a piezoelectric-mechanical oxidation reduction hydrogen peroxide catalyst with oxygen defects connected in series, which comprises the steps of firstly constructing a zinc oxide substrate with a litchi-shaped structure through water phase heat induction self-assembly reaction, then introducing the oxygen defects with controllable content on the surface of the zinc oxide in a liquid phase mediated chemical reduction mode, finally forming a polydopamine coating on the surface of the zinc oxide with the modified defects in situ self-polymerization mode, thus obtaining the target catalyst, and the catalyst can efficiently and selectively prepare hydrogen peroxide under pure water and normal temperature conditions through ultrasonic excitation, has the advantages of mild reaction conditions, high generation rate, good stability, environmental friendliness and the like, and is suitable for application scenes of in-situ preparation of distributed hydrogen peroxide In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: The preparation method of the piezoelectric-mechanical oxidation reduction hydrogen peroxide catalyst with oxygen defects connected in series sequentially comprises the following steps: S1, placing zinc acetate dihydrate in ethanolamine, stirring for 1-3 h to obtain a mixed solution, transferring the mixed solution into a polytetrafluoroethylene lining autoclave, performing solvothermal reac