CN109956493B - Preparation method of cerium or/and zinc doped cuprous oxide nano material - Google Patents
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Abstract
The invention provides a method for preparing a zinc and cerium single-doped and co-doped cuprous oxide nano material by a hydrothermal method. Adding copper acetate and glucose into deionized water to obtain a suspension; and adding zinc acetate dihydrate and cerium nitrate hexahydrate into the suspension respectively or simultaneously, stirring uniformly, carrying out hydrothermal reaction, separating out powder after the reaction is finished, centrifuging, washing and drying to obtain the zinc and cerium mono-doped and co-doped cuprous oxide nano material. The method has the advantages of simple and safe operation, common equipment and low preparation cost. The prepared product has good particle appearance and is easy to realize industrialization.
Description
Technical Field
The invention relates to the technical field of preparation and application of cuprous oxide, in particular to a preparation method of a zinc and cerium single-doped and co-doped cuprous oxide material.
Background
The doping modification of metal oxides is an important method for developing and innovating new materials. Cuprous oxide (Cu)2O) is a P-type semiconductor material having a good visible light absorption property, and is favored with the advantages of low cost, no toxicity, and abundant raw materials. The theoretical photoelectric conversion efficiency can reach 20 percent. Pure cuprous oxide (Cu)2O) crystal is an octahedral cubic structure, has good conductivity and stability, and is applied to various fields of photovoltaic devices, photocatalysis, hydrogen production, electrochromism, thin-film batteries and the like. There are many ways to produce cuprous oxide. However, high temperature preparation of nitrous oxideThe battery efficiency of the copper substrate is low, and low-temperature preparation is a common method for preparing cuprous oxide; for example, the low temperature methods include electrochemical deposition, cathode oxidation, chemical oxidation and reduction, reactive magnetron sputtering, and hydrothermal methods, and particularly, the hydrothermal methods are of great interest, and are economical, low in energy consumption, and simple in preparation method.
Glucose, fructose, hydrazine hydrate, sodium borohydride, polyhydric alcohol and the like are common reducing agents, and Cu with different forms can be obtained through reduction reaction2O film nano material. The glucose is easy to decompose when being heated under the alkaline condition, and the glucose is non-toxic and easy to dissolve in water, so that the green and environment-friendly cuprous oxide nano material can be prepared.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a simple and convenient preparation method of a zinc and cerium single-doped and co-doped cuprous oxide nano material, which has the advantages of simple equipment, convenience in operation, economy and low energy consumption.
In order to achieve the above object, the present invention provides a method for preparing a cerium (Ce) or/and zinc (Zn) doped cuprous oxide nanomaterial, comprising the steps of:
step 1: adding copper acetate monohydrate (Cu (CH)3COO)2·H2O) and glucose (C)6H12O6) Adding the mixture into deionized water, and uniformly mixing to obtain a suspension;
step 2: cerium nitrate hexahydrate (Ce (NO)3)3·6H2O) or/and zinc acetate dihydrate (Zn (CH)3COO)2·2H2O) is added into the suspension obtained in the step 1, a hydrothermal reaction is carried out to obtain a precipitate, and then the precipitate is centrifuged, washed and dried to obtain the cerium or/and zinc doped cuprous oxide nano material.
Preferably, Cu (CH) in the step 13COO)2·H2O and C6H12O6The molar ratio of (a) to (b) is 1:1 to 1: 6.
Preferably, Cu (CH) in the step 13COO)2·H2The mol ratio of O to deionized water is 1:2 to E1:10。
Preferably, only Ce (NO) is added in the step 23)3·6H2O is Cu (CH)3COO)2·H2O and Ce (NO)3)3·6H2The molar ratio of O is 1: 0.05-1: 0.35.
Preferably, only Zn (CH) is added in the step 23COO)2·2H2O is Cu (CH)3COO)2·H2O and Zn (CH)3COO)2·2H2The molar ratio of O is 1: 0.05-1: 0.5.
Preferably, Ce (NO) in said step 23)3·6H2O and Zn (CH)3COO)2·2H2When O is added, Cu (CH)3COO)2·H2O and Ce (NO)3)3·6H2A molar ratio of O to Cu (CH) of 1:0.05 to 1:0.23COO)2·H2O and Zn (CH)3COO)2·2H2The molar ratio of O is 1: 0.05-1: 0.2.
Preferably, the hydrothermal reaction temperature in the step 2 is 70-90 ℃, and the reaction time is more than 30 min.
Preferably, the washing in the step 2 is washing with absolute ethyl alcohol for 2-4 times;
preferably, the drying in the step 2 is drying in a vacuum drying oven at 25-30 ℃ for 30 min.
The technical key point of the invention is the selection of reaction raw materials and reaction temperature, the adjustment of the raw material proportion, the stirring in a magnetic stirrer to obtain uniform suspension, and the uniform suspension is moved into a reaction kettle to be uniformly heated, so as to obtain the zinc and cerium single-doped and co-doped cuprous oxide material.
Doped Cu of the invention2The O photoelectric material is obtained based on a hydrothermal method, the reaction raw materials are nontoxic, and the reaction solvent is deionized water. Meanwhile, the invention has low reaction temperature, short reaction time, safe and reliable reaction process and no release of harmful gases; the operation is convenient, the synthesis method is simple, and the obtained reaction product has good stability and high purity.
In the preparation process of the invention, a magnetic stirrer is adopted for stirring to ensureThe physical uniformity of the whole reaction suspension is proved to be uniformly doped with Cu2The synthesis of the O photoelectric material provides a good nucleation and growth environment.
In the preparation process, when the reaction temperature is 70-90 ℃, the zinc and cerium single-doped and co-doped cuprous oxide material can be obtained, the reaction temperature is wide, and the control is easy.
In the preparation process of the invention, the reaction time is longer than 30 minutes, and the reaction time is short.
The invention has the beneficial effects that:
the method can realize element doping of Cu2The green synthesis of the O photoelectric material has the advantages of simple process, convenient operation, low reaction temperature, low energy consumption and the like, and the obtained product has the advantages of good stability, high purity and the like, and has great application prospect in the research aspect of photoelectric materials.
Drawings
FIG. 1 is an XRD diagram of a zinc and cerium mono-doped and co-doped cuprous oxide nano material obtained in an example;
FIG. 2 is an SEM image of zinc and cerium single-doped and co-doped cuprous oxide nanomaterial obtained by the example;
FIG. 2(a) is an SEM image of the cerium-doped cuprous oxide nanomaterial obtained in example 1;
FIG. 2(b) is an SEM image of the zinc-doped cuprous oxide nanomaterial obtained in example 2;
FIG. 2(c) is an SEM image of the zinc and cerium co-doped cuprous oxide nanomaterial obtained in example 3;
FIG. 3 is an EDS diagram of the cerium-doped cuprous oxide nanomaterial obtained in example 1;
FIG. 4 is an EDS diagram of the cerium-doped cuprous oxide nanomaterial obtained in example 2;
fig. 5 is an EDS diagram of the cerium-doped cuprous oxide nanomaterial obtained in example 3.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The embodiment provides a preparation method of a cerium (Ce) single-doped cuprous oxide nano material, which comprises the following specific preparation steps:
step 1: 3mmol of Cu (CH)3COO)2·H2O and 6mmol C6H12O6Adding the mixture into 50mL of deionized water, and uniformly mixing to obtain a suspension;
step 2: 0.3mmol of Ce (NO)3)3·6H2O) is added into the suspension obtained in the step 1, the mixture is stirred uniformly at room temperature, then hydrothermal reaction is carried out on a magnetic heating stirrer for 500r/min at the heating temperature of 80 ℃ for 1h, dark red precipitate is obtained after the reaction is finished, the product is centrifuged by a centrifuge at the rotating speed of 2000r/min and is rotated for 1 min, the washing is carried out for 2 times by absolute ethyl alcohol, and the product is placed in a vacuum drying oven to be dried for 8h at the temperature of 50 ℃ to obtain the cerium mono-doped cuprous oxide nano material.
FIG. 3 is an EDS spectrum of the sample, wherein peaks of Cu, O, C and Ce elements are observed, the corresponding molar ratio of Cu, O and Ce is 2:1.12:0.09, and the peak of the C element is derived from conductive carbon adhesive tape.
Example 2
The embodiment provides a preparation method of a zinc (Zn) single-doped cuprous oxide nano material, which comprises the following specific preparation steps:
step 1: 3mmol of Cu (CH)3COO)2·H2O and 6mmol C6H12O6Adding the mixture into 50mL of deionized water, and uniformly mixing to obtain a suspension;
step 2: 0.3mmol of Zn (CH)3COO)2·2H2Adding O into the suspension obtained in the step 1, stirring uniformly at room temperature, then carrying out hydrothermal reaction on a magnetic heating stirrer at the heating temperature of 80 ℃ for 1h, and after the reaction is finishedAnd centrifuging the product by a centrifugal machine at the rotating speed of 2000r/min for 1 minute, washing the product for 2 times by using absolute ethyl alcohol, and drying the product in a vacuum drying oven at the temperature of 50 ℃ for 8 hours to obtain the zinc mono-doped cuprous oxide nano material.
FIG. 4 is an EDS spectrum of the sample, wherein peaks of Cu, O, C and Zn elements are observed, the corresponding molar ratio of Cu, O and Zn is 2:0.97:0.12, wherein the peak of the C element is derived from conductive carbon adhesive tape.
Example 3
The embodiment provides a preparation method of a zinc and cerium co-doped cuprous oxide nano material, which comprises the following specific preparation steps:
step 1: 3mmol of Cu (CH)3COO)2·H2O and 6mmol C6H12O6Adding the mixture into 50mL of deionized water, and uniformly mixing to obtain a suspension;
step 2: 0.3mmol of Ce (NO)3)3·6H2O) and 0.3mmol Zn (CH)3COO)2·2H2And (2) adding O into the suspension obtained in the step (1), stirring uniformly at room temperature, performing hydrothermal reaction on a magnetic heating stirrer at the heating temperature of 80 ℃ for 1h to obtain a dark red precipitate after the reaction is finished, centrifuging the product by using a centrifuge at the rotating speed of 2000r/min for 1 min, washing the product for 2 times by using absolute ethyl alcohol, and drying the product in a vacuum drying oven at the temperature of 50 ℃ for 8h to obtain the zinc and cerium co-doped cuprous oxide nanomaterial.
FIG. 5 is an EDS spectrum of the sample, from which peaks of Cu, O, C, Ce and Zn elements are observed, and the corresponding molar ratio of Cu, O, Ce and Zn is 2:0.89:0.07:0.08, wherein the peak of C element is derived from conductive carbon adhesive tape.
As shown in fig. 1: (1) the cerium-doped cuprous oxide nano material 2 theta is 29.58 degrees, 36.44 degrees, 42.32 degrees, 61.40 degrees, 73.55 degrees and 77.41 degrees and respectively corresponds to cubic phase Cu2The 6 peaks of O are (110), (111), (200), (220), (311), (222) planes. (2) The zinc-doped cuprous oxide nano material 2 theta is 29.56 degrees, 36.42 degrees, 42.30 degrees, 61.37 degrees, 73.51 degrees and 77.37 degrees and respectively corresponds to cubic phase Cu26 peaks of O are (110)) Planes of (111), (200), (220), (311), (222). (3) The zinc and cerium doped cuprous oxide nanomaterial 2 θ is 29.56 °, 36.42 °, 42.30 °, 61.37 °, 73.51 °, 77.37 °, and corresponds to the planes of (110), (111), (200), (220), (311), and (222) of the cubic phase Cu2O, respectively. As is clear from fig. 1, the position of the cuprous oxide peak was not greatly changed, and no impurity peak was observed.
FIGS. 2(a) and (b) are crystal images at 7k magnification under SEM, and FIG. 2(c) is a crystal image at 10k magnification under SEM; as can be seen from FIG. 2, the appearance of cuprous oxide is obviously changed, the agglomeration of particles is strong, and the cuprous oxide is changed from cube to polyhedron or spheroidal structure. Therefore, it is presumed that the atoms of Zn and Ce may replace Cu2A certain atom in the O cubic crystal is vacant.
Claims (2)
1. The preparation method of the cerium or/and zinc doped cuprous oxide nano material is characterized by comprising the following steps of:
step 1: mixing Cu (CH)3COO)2·H2O and C6H12O6Adding the mixture into deionized water, and uniformly mixing to obtain a suspension; the Cu (CH)3COO)2·H2O and C6H12O6The molar ratio of (a) to (b) is 1:1 to 1: 6; cu (CH)3COO)2·H2The molar ratio of O to deionized water is 1: 2-1: 10;
step 2: adding Ce (NO)3)3·6H2O or/and Zn (CH)3COO)2·2H2Adding O into the suspension obtained in the step (1), carrying out hydrothermal reaction to obtain a precipitate, and then centrifuging, washing and drying to obtain a cerium or/and zinc doped cuprous oxide nano material; addition of only Ce (NO)3)3·6H2O is Cu (CH)3COO)2·H2O and Ce (NO)3)3·6H2The molar ratio of O is 1: 0.05-1: 0.35; addition of Zn (CH) only3COO)2·2H2O is Cu (CH)3COO)2·H2O and Zn (CH)3COO)2·2H2The molar ratio of O is 1: 0.05-1: 0.5; ce (NO)3)3·6H2O and Zn (CH)3COO)2·2H2When O is added, Cu (CH)3COO)2·H2O and Ce (NO)3)3·6H2A molar ratio of O to Cu (CH) of 1:0.05 to 1:0.23COO)2·H2O and Zn (CH)3COO)2·2H2The molar ratio of O is 1: 0.05-1: 0.2; the hydrothermal reaction temperature is 70-90 ℃, and the reaction time is more than 30 min.
2. The method for preparing the cerium-and/or zinc-doped cuprous oxide nanomaterial as claimed in claim 1, wherein the washing in the step 2 is washing with anhydrous ethanol for 2-4 times; the drying is carried out in a vacuum drying oven at 25-30 ℃ for 30 min.
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| CN110467215B (en) * | 2019-08-06 | 2021-02-26 | 西安交通大学 | Preparation method of shape-controllable iron and zinc ion co-doped cuprous oxide crystal |
| CN110841649B (en) * | 2019-10-17 | 2022-12-06 | 华南师范大学 | Preparation method of copper-cerium bimetal Fenton catalytic material, prepared catalytic material and application thereof |
| CN111362299A (en) * | 2020-05-13 | 2020-07-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of yttrium-doped modified tin dioxide nano material, product and application thereof |
| CN113060754B (en) * | 2021-03-16 | 2021-10-19 | 江苏理工学院 | Doped cuprous dechlorinating agent and preparation method and application thereof |
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