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CN-119500137-B - Flower-like structure copper cobalt oxide Cu0.92Co2.08O4Preparation method and application of (C)

CN119500137BCN 119500137 BCN119500137 BCN 119500137BCN-119500137-B

Abstract

The invention discloses a preparation method and application of a flower-shaped copper cobalt oxide Cu 0.92 Co 2.08 O 4 , and belongs to the technical field of catalysts. The preparation method comprises the steps of weighing a cobalt source and a copper source according to a molar ratio of 3:1, dissolving the cobalt source and the copper source in water, adding a cationic surfactant into the obtained mixture, adding a reducing agent into the mixture for reduction reaction, filtering, collecting precipitate, washing with water to neutrality to obtain a precursor, and calcining the precursor to obtain the precursor, wherein the cationic surfactant is one or a combination of more than two selected from CTAB, DODMAC, HTAC, DDAB, benzalkonium chloride and stearammonium chloride, and the dosage of the cationic surfactant is 0.59-0.75 times of the molar quantity of the cobalt source. The copper cobalt oxide prepared by the method of the invention is used as a catalyst to show good catalytic performance on NaBH 4 hydrolysis.

Inventors

  • YAN PUXUAN
  • CHEN YUANYUAN
  • WANG YUFENG
  • WANG MENGYI
  • LI WENZHUO
  • SUN LIXIAN
  • LIN WANTING

Assignees

  • 桂林电子科技大学

Dates

Publication Date
20260505
Application Date
20241120

Claims (9)

  1. 1. A preparation method of a flower-like structure copper cobalt oxide Cu 0.92 Co 2.08 O 4 used for hydrogen evolution catalysis is characterized by taking a cobalt source and a copper source to dissolve in water, adding a cationic surfactant, stirring and dissolving to obtain a mixture, adding a reducing agent into the obtained mixture for reduction reaction, filtering after the reaction is completed, collecting a precipitate, washing with water to be neutral to obtain a precursor, calcining the obtained precursor to obtain the flower-like structure copper cobalt oxide Cu 0.92 Co 2.08 O 4 , The molar ratio of the cobalt source to the copper source is 3:1; the cationic surfactant is CTAB; The dosage of the cationic surfactant is 0.59-0.75 times of the molar quantity of the cobalt source.
  2. 2. The method according to claim 1, wherein the cobalt source is one or a combination of two or more selected from cobalt chloride, cobalt chloride hydrate, cobalt nitrate and cobalt nitrate hydrate.
  3. 3. The method according to claim 1, wherein the copper source is one or a combination of two or more selected from copper chloride, a hydrate of copper chloride, copper nitrate and a hydrate of copper nitrate.
  4. 4. The preparation method according to claim 1, wherein the reducing agent is one or a combination of two or more selected from sodium borohydride, lithium aluminum hydride and sodium bisulphite.
  5. 5. The production method according to any one of claims 1 to 4, wherein the reduction reaction is carried out under ice water bath conditions.
  6. 6. The method according to any one of claims 1 to 4, wherein the calcination is performed at 300 to 500 ℃.
  7. 7. The method according to any one of claims 1 to 4, wherein the cationic surfactant is used in an amount of 0.64 to 0.72 times the molar amount of the cobalt source.
  8. 8. The application of the copper cobalt oxide Cu 0.92 Co 2.08 O 4 prepared by the method according to any one of claims 1-7 in preparation of hydrogen evolution catalysts.
  9. 9. The method according to claim 8, wherein the catalyst is used for preparing hydrogen evolution catalyst from metal hydride.

Description

Preparation method and application of flower-like structure copper cobalt oxide Cu 0.92Co2.08O4 Technical Field The invention relates to the technical field of catalysts, in particular to a preparation method and application of copper cobalt oxide Cu 0.92Co2.08O4 with a flower-shaped structure. Background With the exhaustion of fossil energy and the increase of carbon dioxide emissions, the problem of greenhouse effect becomes more serious. In order to mitigate the impact on the global environment, hydrogen energy is considered as an ideal choice for future energy sources due to its high combustion heating value and zero carbon dioxide emissions. Therefore, it becomes particularly important to develop efficient, safe hydrogen storage materials. Sodium borohydride (NaBH 4) is the focus of research because of its hydrogen storage capacity of up to 10.57 wt%, stability in alkaline solutions, and non-toxicity and recyclability of the hydrolysis products. However, naBH 4 reacts very slowly at room temperature with autohydrolysis. The use of the catalyst can reduce the kinetic energy barrier of NaBH 4 hydrolysis, thereby improving the hydrogen generation rate and reaction efficiency and enabling the application to be more controllable. At present, noble metal catalysts (such as Pd and Ru) show good catalytic performance, but the industrial application thereof is limited due to the scarcity and high cost. Therefore, the search for inexpensive, resource-rich non-noble metal catalysts is an important direction to replace noble metal catalysts. Among the transition metal compounds, cobalt-based phosphides, borides and oxides show good catalytic performance for NaBH 4 hydrolysis. In particular to a composite bimetallic catalyst, and the bimetallic oxide catalyst prepared by methods such as in-situ reduction, high-temperature calcination and the like shows higher hydrogen gas precipitation rate due to the electron transfer and bimetallic synergistic effect. Therefore, the application of the non-noble metal bimetallic catalyst in the NaBH 4 hydrolysis hydrogen production is studied in depth, and the development of industrial application of the non-noble metal bimetallic catalyst is promoted. Mingzhen Hu et al provide a general template-free method, and 6 mesoporous transitional oxides such as Co3O4、CoO、Cu0.92Co2.0804、MnCo2O4.5、ZnCo2O4 and CuO are successfully synthesized, wherein Cu 0.92Co2.0804、MnCo2O4.5 and ZnCo 2O4 have a two-dimensional lamellar structure, and Co 3O4 and the like can catalyze hydrogen peroxide to decompose to generate oxygen (Hu et al., Template-free Synthesis of Mesoporous and Crystalline Transition Metal Oxide Nanoplates with Abundant Surface Defects, Matter 2,1-16,May6, 2020.)., but related reports of application of Cu 0.92Co2.08O4 cobalt oxide as a catalyst in catalyzing metal hydride (such as NaBH 4) hydrolysis to generate hydrogen are not found in the prior art. Disclosure of Invention The technical problem to be solved by the invention is to provide a preparation method and application of a novel flower-like structure copper cobalt oxide Cu 0.92Co2.08O4, and the copper cobalt oxide Cu 0.92Co2.08O4 prepared by the method provided by the invention shows good catalytic performance on NaBH 4 hydrolysis as a catalyst. In order to solve the technical problems, the invention adopts the following technical scheme: A preparation method of copper cobalt oxide Cu 0.92Co2.08O4 with flower-like structure comprises dissolving cobalt source and copper source in water, adding cationic surfactant, stirring to dissolve to obtain mixture, adding reducer into the mixture for reduction reaction, filtering, collecting precipitate, washing with water to neutrality to obtain precursor, calcining the precursor to obtain copper cobalt oxide Cu 0.92Co2.08O4 with flower-like structure, The molar ratio of the cobalt source to the copper source is 3:1; The cationic surfactant is one or more than two selected from CTAB (cetyltrimethylammonium bromide), DODMAC (behenyl dimethyl ammonium chloride), HTAC (cetyltrimethylammonium chloride), DDAB (behenyl dimethyl benzotrichlor), benzalkonium chloride (Benzalkonium Chloride) and stearylammonium chloride (Stearalkonium Chloride); The dosage of the cationic surfactant is 0.59-0.75 times of the molar quantity of the cobalt source. In the above technical solution, the cobalt source may be one or more selected from cobalt chloride, a hydrate of cobalt chloride (such as hexahydrate of cobalt chloride, etc.), cobalt nitrate and a hydrate of cobalt nitrate (such as hexahydrate of cobalt nitrate), preferably cobalt chloride or hexahydrate of cobalt chloride. In the above technical solution, the copper source may be one or a combination of two or more selected from copper chloride, copper chloride hydrate (such as copper chloride monohydrate, copper chloride dihydrate, copper chloride trihydrate or copper chloride tetrahydrate, etc.), copper nitrate, and copper nitrate hydrate (such as co