Preparation method of copper-cobalt double-doped octahedral cerium dioxide nano material
阅读说明：本技术 一种铜钴双掺杂八面体二氧化铈纳米材料的制备方法 (Preparation method of copper-cobalt double-doped octahedral cerium dioxide nano material ) 是由 崔康 李旭 周晨曦 于京华 于 2021-01-04 设计创作，主要内容包括：本发明提供了一种铜钴双掺杂八面体二氧化铈纳米材料的制备方法,属于纳米材料制备技术领域。在该发明过程中,以超纯水为溶剂,分别配制硝酸铈和十二水合磷酸三钠的水溶液,室温下将硝酸铈的溶液在不断搅拌下,滴加到磷酸钠溶液中,得到的溶液经过高温高压反应得到八面体二氧化铈纳米颗粒；分别配制氯化铜和氯化钴的水溶液,并将两种溶液在室温搅拌下滴加到八面体二氧化铈的水溶液中,再通过高温高压反应得到铜钴双掺杂八面体二氧化铈纳米颗粒。获得的纳米颗粒形貌规整,尺寸均一,在有机溶剂中具有良好的分散性。制备的铜钴双掺杂八面体二氧化铈纳米颗粒在生物传感分析领域具有较好的应用前景。(The invention provides a preparation method of a copper-cobalt double-doped octahedral cerium dioxide nano material, belonging to the technical field of nano material preparation. In the process, ultrapure water is used as a solvent to respectively prepare aqueous solutions of cerium nitrate and trisodium phosphate dodecahydrate, the solution of cerium nitrate is dropwise added into a sodium phosphate solution at room temperature under the condition of continuous stirring, and the obtained solution is subjected to high-temperature high-pressure reaction to obtain octahedral cerium dioxide nanoparticles; respectively preparing aqueous solutions of copper chloride and cobalt chloride, dropwise adding the two solutions into the aqueous solution of octahedral cerium dioxide under the condition of stirring at room temperature, and then carrying out high-temperature high-pressure reaction to obtain the copper-cobalt double-doped octahedral cerium dioxide nanoparticles. The obtained nano-particles have regular appearance, uniform size and good dispersibility in organic solvents. The prepared copper-cobalt double-doped octahedral cerium dioxide nanoparticles have a good application prospect in the field of biosensing analysis.)
1. A preparation method of a copper-cobalt double-doped octahedral cerium dioxide nano material is characterized by comprising the following steps:
(1) preparation of octahedral cerium dioxide nano material: 0.434 g Ce (NO)3)3·6H2Dissolving O in 5 mL of ultrapure water, stirring to form a clear solution, adding 0.0076 g of Na3PO4·12H2O was dissolved in 35 mL of ultrapure water, and then Ce (NO) was added under stirring3)3The aqueous solution of (A) is poured with Na3PO4Stirring the aqueous solution of (1)Stirring for 10 min, performing ultrasonic treatment for 5 min, transferring the obtained mixed solution into a polytetrafluoroethylene-lined high-pressure kettle with the capacity of 50 mL, putting the high-pressure kettle into an oven for reaction at 190 ℃ for 20 h, after the reaction kettle is naturally cooled to room temperature, centrifuging at 8000 rpm for 10 min, collecting a product, washing the product with ethanol and water for three times respectively, and finally, drying the product at 60 ℃ overnight to obtain the octahedral cerium dioxide nano material;
(2) preparing a copper-cobalt double-doped octahedral cerium dioxide nano material: 800 mg of octahedral CeO2And 200 mg of polyvinylpyrrolidone in 15 mL of ethylene glycol and stirred at room temperature for 30 min, and then 0.5 mL of 20 mg/mL of CuCl2·2H2O and 0.5 mL of 20 mg/mL CoCl2·6H2Adding the O solution into the solution, transferring the mixed solution into a polytetrafluoroethylene-lined autoclave with the capacity of 20 mL, heating the autoclave at 160 ℃ for 8 hours, naturally cooling the autoclave to room temperature after the reaction is finished, collecting the product, washing the product with ultrapure water and ethanol for three times respectively, drying the product at 60 ℃ overnight, and then calcining the product at 300 ℃ for 1 hour at the speed of 1 ℃/min to obtain the copper-cobalt double-doped octahedral cerium dioxide nano material.
2. The method as claimed in claim 1, wherein the octahedral ceria nanomaterial is synthesized by hydrothermal synthesis in step (1), and then the copper-cobalt noble metal elements are doped into oxygen holes on the surface of the octahedral ceria nanomaterial by a certain chemical reaction in step (2), thereby synthesizing the novel copper-cobalt double-doped octahedral ceria nanomaterial.
Technical Field
The invention relates to preparation of a nano material by taking octahedral cerium dioxide nano particles as a template and doping copper and cobalt on the surface of the octahedral cerium dioxide, belongs to the technical field of nano material preparation, and particularly relates to a preparation method of a copper and cobalt double-doped octahedral cerium dioxide nano material.
Background
Since the rare earth element has a unique 4f structure, the compound is widely applied to the fields of light, electricity, magnetism and the like, and in addition, a new material developed by utilizing the rare earth element is also applied to various fields of electrons, catalysis, energy sources and the like. Among all the known rare earth elements, cerium is the most abundant and the least expensive. In recent years, cerium dioxide rare earth materials are greatly applied to various high-end technical industries at home and abroad, and the demand is continuously increased. The chemical property of cerium element is specially, and the external layer electron filling mode is 4f1，5d1，6s2So that the cerium element is stabilized in the trivalent positive and tetravalent positive states, as well as other rare earth elements, it is the variability of the valence states that gives the compounds formed by the cerium element the very unique properties. Due to the unique physical and chemical properties, the cerium dioxide nano material is widely applied to clinical diagnosis, food detection, environmental management, preparation of fuel cells and the like. Such as Jongmin RohSun, Hye Hwang, Jyongsik Jang,ACS Applied Materials & Interfaces2014, 6, 22, 19825-19832 synthesized Eu-CeO2The composite material is used for preparing the dye-sensitized solar cell, and the performance of the cell is greatly improved; the method comprises the steps of preparing cerium dioxide nano particles with the particle size of 3-5 nm by a micro-emulsion method through Hickman and the like, adopting cerium dioxide with biocompatibility as a neuron supplement culture, and recording the neuron function retention degree through an ultraviolet visible spectrum, a hydrogen peroxide induced oxidative damage test and electrophysiology. However, due to the structural limitation of ceria, ceria cannot completely meet the catalytic and detection requirements of people at times.
Disclosure of Invention
The invention aims to prepare a copper-cobalt double-doped octahedral cerium dioxide nano material. The preparation method comprises the steps of firstly synthesizing octahedral cerium dioxide nanoparticles by a hydrothermal method, then dissolving the octahedral cerium dioxide particles in ultrapure water, dropwise adding aqueous solution of copper chloride and cobalt chloride into aqueous solution of cerium dioxide, and doping copper and cobalt elements on the surface of the octahedral cerium dioxide by high-temperature high-pressure reaction to finally obtain copper and cobalt double-doped octahedral cerium dioxide nanoparticles with the average particle size of about 200 nm.
The technical scheme of the invention is as follows:
the octahedral cerium dioxide nano-particles with larger specific surface area have the size of about 200 nm, and the surface has a large amount of oxygen cavity structures, so that an effective carrier environment is provided for the doping of the copper and cobalt elements, the two elements of copper and cobalt doped on the surface of the octahedral cerium dioxide can improve the catalytic activity of the octahedral cerium dioxide, and simultaneously, the good chemical properties of the cerium dioxide material can be kept, thereby forming the copper and cobalt double-doped octahedral cerium dioxide nano-material.
A preparation method of a copper-cobalt double-doped octahedral cerium dioxide nano material is characterized by comprising the following steps:
(1) preparation of octahedral cerium dioxide nano material: 0.4-0.5 g Ce (NO)3)3·6H2Dissolving O in 5-10 mL of ultrapure water, stirring to form a clear solution, adding 0.007-0.008 g of Na3PO4·12H2O was dissolved in 30-40 mL of ultrapure water, and then Ce (NO) was added under stirring3)3The aqueous solution of (A) is poured with Na3PO4Stirring the aqueous solution for 10 min, performing ultrasonic treatment for 5 min, transferring the obtained mixed solution into a polytetrafluoroethylene-lined high-pressure kettle with the capacity of 50 mL, putting the high-pressure kettle into an oven for reaction at 190 ℃ for 20 h, after the reaction kettle is naturally cooled to room temperature, centrifuging at 8000 rpm for 10 min, collecting a product, washing the product with ethanol and water for three times respectively, and finally, drying the product at 60 ℃ overnight to obtain the octahedral cerium dioxide nano material;
(2) preparing a copper-cobalt double-doped octahedral cerium dioxide nano material: 800-1000 mg octahedral CeO2And 200-300 mg polyvinylpyrrolidone in 15-20 mL of ethylene glycol, stirring at room temperature for 30 min, and adding 0.5-1.0 mL of 20 mg/mL CuCl2·2H2O and 0.5-1.0 mL of 20 mg/mL CoCl2·6H2Adding O solution into the solution, transferring the mixed solution into a polytetrafluoroethylene-lined autoclave with the capacity of 20 mL, heating the autoclave at 160 ℃ for 8 hours, naturally cooling the autoclave to room temperature after the reaction is finished, collecting the product, washing the product with ultrapure water and ethanol for three times respectively, drying the product at 60 ℃ overnight, and then calcining the product at 300 ℃ for 1 hour at the speed of 1 ℃/min to obtain the product of copper-cobalt double-doped octahedral cerium dioxide nano material, wherein the scanning electron microscope and transmission electron microscope characterization of the copper-cobalt double-doped octahedral cerium dioxide nano material is shown in attached figures 1 and 2.
The invention has the beneficial effects that:
(1) the preparation method of the copper-cobalt double-doped octahedral cerium dioxide nano material is simple to operate, has mild reaction conditions, and is a green and environment-friendly nano material synthesis method.
(2) The doping of copper and cobalt elements can greatly improve the morphology and the electrocatalytic activity of cerium dioxide.
(3) The copper-cobalt double-doped octahedral cerium dioxide nano material has a good application prospect in the field of biosensing.
Description of the drawings:
the invention is described in further detail below with reference to the following figures and detailed description:
FIG. 1 is a Scanning Electron Microscope (SEM) of copper cobalt double-doped octahedral cerium dioxide nanomaterial;
figure 2 is an X-ray energy spectrum (EDS) of a copper cobalt double-doped octahedral ceria nanomaterial.
Detailed Description
A preparation method of a copper-cobalt double-doped octahedral cerium dioxide nano material is characterized by comprising the following steps:
(1) preparation of octahedral cerium dioxide nano material: 0.434 g Ce(NO3)3·6H2Dissolving O in 5 mL of ultrapure water, stirring to form a clear solution, adding 0.0076 g of Na3PO4·12H2O was dissolved in 35 mL of ultrapure water, and then Ce (NO) was added under stirring3)3The aqueous solution of (A) is poured with Na3PO4Stirring the aqueous solution for 10 min, performing ultrasonic treatment for 5 min, transferring the obtained mixed solution into a polytetrafluoroethylene-lined high-pressure kettle with the capacity of 50 mL, putting the high-pressure kettle into an oven for reaction at 190 ℃ for 20 h, after the reaction kettle is naturally cooled to room temperature, centrifuging at 8000 rpm for 10 min, collecting a product, washing the product with ethanol and water for three times respectively, and finally, drying the product at 60 ℃ overnight to obtain the octahedral cerium dioxide nano material;
(2) preparing a copper-cobalt double-doped octahedral cerium dioxide nano material: 800 mg of octahedral CeO2And 200 mg of polyvinylpyrrolidone in 15 mL of ethylene glycol and stirred at room temperature for 30 min, and then 0.5 mL of 20 mg/mL of CuCl2·2H2O and 0.5 mL of 20 mg/mL CoCl2·6H2Adding the O solution into the solution, transferring the mixed solution into a polytetrafluoroethylene-lined autoclave with the capacity of 20 mL, heating the autoclave at 160 ℃ for 8 hours, naturally cooling the autoclave to room temperature after the reaction is finished, collecting the product, washing the product with ultrapure water and ethanol for three times respectively, drying the product at 60 ℃ overnight, and then calcining the product at 300 ℃ for 1 hour at the speed of 1 ℃/min to obtain the copper-cobalt double-doped octahedral cerium dioxide nano material.