Cobalt-doped cerium oxide composite material and preparation method thereof
By preparing cobalt-doped cerium oxide composite materials, the problem of easy recombination of electron-hole pairs in CeO2 photocatalysts was solved, achieving efficient electron separation and CO2 activation, thus improving the photocatalytic conversion of CO2 into hydrocarbon chemicals.
Patent Information
- Application Number
- CN202511698299.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-19
- Publication Date
- 2026-02-10
AI Technical Summary
Existing CeO2 photocatalysts suffer from problems such as easy recombination of electron-hole pairs and difficulty in electronic excitation, which limits their practical application.
A method for preparing cobalt-doped cerium oxide composite materials includes steps involving cerium nitrate hexahydrate, ethylene glycol, ethanol, and cobalt nitrate hexahydrate. Through processes such as solvothermal reaction, calcination, and centrifugation, a Co/CeO2 material with uniform size structure and high dispersibility is prepared.
It improves electron transport and separation capabilities, provides abundant surface sites, enhances the adsorption and activation of CO2 molecules, and promotes the efficiency of photocatalytic CO2 conversion into hydrocarbon chemicals.
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Figure CN121490771A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of photocatalytic material preparation, and particularly relates to a cobalt-doped cerium oxide composite material and a preparation method thereof. BACKGROUND
[0002] Cerium oxide (CeO2) is an important rare earth oxide, which is non-toxic and has excellent redox performance. In addition, cerium ions have specific valence conversion capability and can easily transfer between the reduced state (Ce3p) and the oxidized state (Ce4p), so that it has good electron transport and transfer capability, and its surface has rich oxygen vacancies, which are all conducive to the photocatalytic CO2 reduction reaction.
[0003] However, the existing CeO2 photocatalyst has the defects of easy recombination of electron-hole pairs and difficult electron excitation in the original components, which greatly limits the practical application of the CeO2 photocatalyst. SUMMARY
[0004] The present application aims to provide a cobalt-doped cerium oxide composite material and a preparation method thereof, and aims to solve the technical problem that the existing CeO2 photocatalyst has the defects of easy recombination of electron-hole pairs and difficult electron excitation in the original components, which greatly limits the practical application of the CeO2 photocatalyst.
[0005] To achieve the above-mentioned purpose, the cobalt-doped cerium oxide composite material used in the present application comprises cerium nitrate hexahydrate, ethylene glycol, ethanol, an aqueous solution and cobalt nitrate hexahydrate.
[0006] The present application also provides a preparation method of the cobalt-doped cerium oxide composite material, comprising the following steps: Weigh the cerium nitrate hexahydrate and dissolve it in ethylene glycol, and stir it with a magnetic stirrer until it is completely dissolved; Transfer the solution to a reaction kettle and place it in an oven for solvothermal reaction; Wash it with ethanol and an aqueous solution respectively, and dry it in a vacuum drying oven overnight to obtain a powder; Calcine it in a muffle furnace to obtain a CeO2 powder; Weigh the cerium oxide and disperse it in an ethanol solution, stir and mix it uniformly at room temperature, and add cobalt nitrate hexahydrate; Put it into an oil bath and continue to heat and stir to react, and obtain a mixed solution after the reaction is completed; Centrifuge, wash and dry the solution after the reaction, and calcine it in air to obtain Co / CeO2.
[0007] In the step of weighing the cerium nitrate hexahydrate and dissolving it in ethylene glycol, and stirring it with a magnetic stirrer until it is completely dissolved: The volume of ethylene glycol is 50 mL.
[0008] wherein, in the step of washing with ethanol and aqueous solution respectively and drying in a vacuum drying oven overnight to obtain powder: The volume of diol is 20 mL.
[0009] wherein, in the step of transferring the solution to a reaction kettle and placing it in an oven for solvothermal reaction: The solvothermal reaction condition is: reaction at 180℃ for 28 h.
[0010] wherein, in the step of calcining in a muffle furnace to obtain CeO2 powder: The calcination condition in the muffle furnace is: calcination at 450℃ with a heating rate of 5℃ / min for 4 h.
[0011] wherein, in the step of weighing cerium oxide, dispersing it in an ethanol solution, stirring and mixing uniformly at room temperature, and adding cobalt nitrate hexahydrate: The heating temperature for adding cobalt nitrate hexahydrate is 70℃, and the heating and stirring reaction is 2 h.
[0012] wherein, in the step of centrifuging, washing and drying the solution after the reaction, and calcining under air to obtain Co / CeO2: The calcination is carried out in a tube furnace: heating temperature is 300℃, and the heating and stirring reaction is 1 h.
[0013] The cobalt-doped ceria composite material and its preparation method of the present application adopt cerium nitrate hexahydrate, ethylene glycol, ethanol, aqueous solution and cobalt nitrate hexahydrate to perform the following steps: weigh cerium nitrate hexahydrate, dissolve it in ethylene glycol, and stir with a magnetic stirrer until it is completely dissolved; transfer the solution to a reaction kettle, and place it in an oven for solvothermal reaction; wash with ethanol and aqueous solution respectively, and dry in a vacuum drying oven overnight to obtain powder; calcine in a muffle furnace to obtain CeO2 powder; weigh cerium oxide, disperse it in an ethanol solution, stir and mix uniformly at room temperature, and add cobalt nitrate hexahydrate; put it into an oil bath and continue to heat and stir to react, and obtain a mixed solution after the reaction; centrifuge, wash and dry the solution after the reaction, and calcine under air to obtain Co / CeO2. The obtained cobalt ceria has uniform size structure and high dispersity, and the introduction of cobalt provides rich surface sites for the adsorption and activation of CO2 molecules, greatly accelerates the separation of charge carriers and the transmission of electrons in the catalytic system, provides guarantee for the enrichment of electrons, and has broad application prospects in the photocatalytic conversion of CO2 to prepare carbon-hydrogen chemicals. BRIEF DESCRIPTION OF DRAWINGS
[0014] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description only represent some of the embodiments of the present application, and for those skilled in the art, other drawings can also be obtained without creative labor based on these drawings.
[0015] Figure 1 is a step flow chart of the preparation method of the cobalt-doped ceria composite material of the present application. DETAILED DESCRIPTION
[0016] The exemplary embodiments will be described in detail herein with reference to the accompanying drawings. Unless otherwise indicated, the same numbers in different drawings indicate the same or similar elements. The embodiments described in the following exemplary embodiments do not represent all the embodiments consistent with the present application.
[0017] The terms used in the present application are merely for the purpose of describing specific embodiments and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the present application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise. It should also be understood that the term "and / or" used herein means and includes any or all possible combinations of one or more associated listed items.
[0018] It should be understood that although the terms first, second, third, etc. can be used in the present application to describe various information, these information should not be limited to these terms. These terms are only used to distinguish information of the same type from each other. For example, without departing from the scope of the present application, the first information can also be referred to as the second information, and similarly, the second information can also be referred to as the first information. Depending on the context, the word "if" as used herein can be interpreted as "when" or "upon determining" or "in response to determining".
[0019] The present application provides a cobalt-doped ceria composite material, comprising cerium nitrate hexahydrate, ethylene glycol, ethanol, aqueous solution and cobalt nitrate hexahydrate.
[0020] Please refer to Figure 1 The present application also provides a preparation method of a cobalt-doped ceria composite material, comprising the following steps: S100: weigh cerium nitrate hexahydrate and dissolve it in ethylene glycol, and stir with a magnetic stirrer until completely dissolved; S200: transfer the solution to a reaction kettle and place it in an oven for solvothermal reaction; S300: wash with ethanol and aqueous solution respectively, and place in a vacuum drying oven to dry overnight to obtain a powder; S400: Calcination in a muffle furnace to obtain CeO2 powder; S500: Weigh cerium oxide and disperse it in an ethanol solution, stir and mix uniformly at room temperature, and add cobalt nitrate hexahydrate; S600: Put into an oil bath and continue to heat and stir to react, and obtain a mixed solution after the reaction is completed; S700: Perform centrifugation, washing and drying processes on the solution after the reaction is completed, and calcine under air to obtain Co / CeO2.
[0021] In this embodiment, 6.0 g of cerium nitrate hexahydrate is dissolved in 50 mL of ethylene glycol, stirred with a magnetic stirrer until completely dissolved, and then transferred to a 100 mL reaction kettle. Heat at 180℃ for 28h, wash with water and ethanol solution several times, and dry in a 60℃ oven overnight. Calcine in a muffle furnace at 450℃ with a temperature rise rate of 5℃ / min for 4h to obtain yellow CeO2 powder. Then, 100 mg of CeO2 is dispersed in an ethanol solution and stirred and mixed uniformly at room temperature. Add 12.06 mg of cobalt nitrate hexahydrate to the above solution, and then put it into an oil bath and continue to heat and stir to react. After the reaction is completed, a mixed solution is obtained. Centrifuge, wash, and dry the solution after the reaction is completed, and finally calcine at 300℃ under air for 1h to obtain Co / CeO2, which is named as 3%Co / CeO2.
[0022] Example One Weigh 6.0 g of cerium nitrate hexahydrate and dissolve it in 50 mL of ethylene glycol, stir with a magnetic stirrer until completely dissolved, and then transfer the solution to a 100 mL reaction kettle. Heat at 180℃ for 28h, wash with water and ethanol solution several times, and dry in a 60℃ oven overnight. Calcine in a muffle furnace at 450℃ with a temperature rise rate of 5℃ / min for 4h to obtain yellow CeO2 powder. Then, 100 mg of CeO2 is dispersed in an ethanol solution and stirred and mixed uniformly at room temperature. Add 12.06 mg of cobalt nitrate hexahydrate to the above solution, and then put it into an oil bath and continue to heat and stir to react. After the reaction is completed, a mixed solution is obtained. Centrifuge, wash, and dry the solution after the reaction is completed, and finally calcine at 300℃ under air for 1h to obtain Co / CeO2, which is named as 3%Co / CeO2.
[0023] Example Two Take 6.0 g of cerium nitrate hexahydrate and dissolve it in 50 mL of ethylene glycol. Stir with a magnetic stirrer until completely dissolved, then move the solution into a 100 mL reaction kettle. Heat at 180°C for 28 h, wash with water and ethanol solution several times, and dry in a 60°C oven overnight. Calcine at 450°C with a temperature rise rate of 5°C / min in a muffle furnace for 4 h to obtain yellow CeO2 powder. Then take 100 mg of CeO2 and disperse it in an ethanol solution, stir and mix uniformly at room temperature. Add 40.20 mg of cobalt nitrate hexahydrate to the above solution, then place it in an oil bath and continue to heat and stir to react. After the reaction is completed, a mixed solution is obtained. Centrifuge, wash, and dry the solution after the reaction to obtain Co / CeO2. Finally, calcine at 300°C in air for 1 h to obtain 10% CoCeO2.
[0024] Among them, the material of Example 2 has more excellent photocatalytic CO2 reduction performance compared with Example 1, the main reason is that different Co component loadings affect the photocatalytic activity.
[0025] Example Three Take 6.0 g of cerium nitrate hexahydrate and dissolve it in 50 mL of ethylene glycol. Stir with a magnetic stirrer until completely dissolved, then move the solution into a 100 mL reaction kettle. Heat at 180°C for 28 h, wash with water and ethanol solution several times, and dry in a 60°C oven overnight. Calcine at 450°C with a temperature rise rate of 5°C / min in a muffle furnace for 4 h to obtain yellow CeO2 powder. Then take 100 mg of CeO2 and disperse it in an ethanol solution, stir and mix uniformly at room temperature. Add 40.20 mg of cobalt nitrate hexahydrate to the above solution, then place it in an oil bath and continue to heat and stir to react. After the reaction is completed, a mixed solution is obtained. Centrifuge, wash, and dry the solution after the reaction to obtain Co / CeO2. Finally, calcine at 300°C in air for 1 h to obtain 10% CoCeO2.
[0026] Among them, the material of Example 3 has poorer photocatalytic CO2 reduction performance compared with Example 2, the main reason is that different Co component loadings affect the photocatalytic activity. The material in Example 2 is the best ratio material.
[0027] Other embodiments of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope of the application being indicated by the following claims.
[0028] It is to be understood that the application is not limited to the precise construction already described above and shown in the drawings, and that various modifications and changes can be made by those skilled in the art without departing from the scope thereof.
Claims
1. A cobalt-doped cerium oxide composite material, characterized in that, Including cerium nitrate hexahydrate, ethylene glycol, ethanol, aqueous solution, and cobalt nitrate hexahydrate.
2. A method for preparing a cobalt-doped cerium oxide composite material, as described in claim 1, characterized in that, Includes the following steps: Weigh out cerium nitrate hexahydrate and dissolve it in ethylene glycol. Stir with a magnetic stirrer until completely dissolved. The solution was transferred to a reaction vessel and placed in an oven for a solvothermal reaction. The powder was washed separately with ethanol and aqueous solution and then dried overnight in a vacuum drying oven to obtain the powder. Calcination in a muffle furnace yields CeO2 powder; Weigh out cerium oxide and disperse it in an ethanol solution. Stir and mix it evenly at room temperature, and then add cobalt nitrate hexahydrate. Place the mixture in an oil bath and heat and stir continuously to carry out the reaction. After the reaction is complete, a mixed solution is obtained. After the reaction was completed, the solution was centrifuged, washed, and dried, and then calcined in air to obtain Co / CeO2.
3. The method for preparing the cobalt-doped cerium oxide composite material as described in claim 2, characterized in that, In the step of weighing out cerium nitrate hexahydrate and dissolving it in ethylene glycol, and stirring with a magnetic stirrer until completely dissolved: The volume of ethylene glycol is 50 mL.
4. The method for preparing the cobalt-doped cerium oxide composite material as described in claim 3, characterized in that, In the steps of washing with ethanol and aqueous solution respectively, and drying in a vacuum drying oven overnight to obtain powder: The volume of the diol is 20 mL.
5. The method for preparing the cobalt-doped cerium oxide composite material as described in claim 4, characterized in that, In the step of transferring the solution to the reaction vessel and placing it in an oven for a solvothermal reaction: The conditions for the solvothermal reaction were: reaction at 180℃ for 28 h.
6. The method for preparing the cobalt-doped cerium oxide composite material as described in claim 5, characterized in that, In the step of calcining in a muffle furnace to obtain CeO2 powder: The calcination conditions in the muffle furnace were: calcination at 450℃ for 4 h at a heating rate of 5℃ / min.
7. The method for preparing the cobalt-doped cerium oxide composite material as described in claim 6, characterized in that, In the step of weighing cerium oxide, dispersing it in an ethanol solution, stirring and mixing it evenly at room temperature, and then adding cobalt nitrate hexahydrate: Add cobalt nitrate hexahydrate, heat to 70°C, and stir for 2 hours.
8. The method for preparing the cobalt-doped cerium oxide composite material as described in claim 7, characterized in that, In the steps of centrifuging, washing, and drying the solution after the reaction, and then calcining it in air to obtain Co / CeO2: Calcination was carried out in a tube furnace: the heating temperature was 300℃, and the reaction was stirred for 1 h.