CN109956493A - A kind of preparation method of cerium or/and zinc doping cuprous nano material - Google Patents
A kind of preparation method of cerium or/and zinc doping cuprous nano material Download PDFInfo
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- CN109956493A CN109956493A CN201910312169.3A CN201910312169A CN109956493A CN 109956493 A CN109956493 A CN 109956493A CN 201910312169 A CN201910312169 A CN 201910312169A CN 109956493 A CN109956493 A CN 109956493A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
Abstract
The present invention provides a kind of methods that hydro-thermal method prepares zinc, cerium list doping and codope cuprous nano material.Copper acetate and glucose are add to deionized water, suspension is obtained；It is separately or concurrently added in above-mentioned suspension with two water zinc acetates and cerous nitrate hexahydrate, and stir evenly, hydro-thermal reaction is then carried out, after reaction, powder is precipitated, is centrifuged, washs, being drying to obtain zinc, the doping of cerium list and codope cuprous nano material.Operation of the present invention is simple, and safety, equipment is common, and preparation cost is cheap.Made product grain pattern is preferable, it is easy to accomplish industrialization.
Description
Technical field
The present invention relates to the preparation of cuprous oxide and applied technical fields, adulterate and are co-doped in particular to a kind of zinc, cerium list
The preparation method of miscellaneous cuprous oxide material.
Background technique
Doped metallic oxide modification is the important method of development and innovation new material.Cuprous oxide (Cu2It O is) that one kind can
The light-exposed preferable p-type semiconductor material of absorbability, it is the advantages of cheap, nontoxic and abundant raw materials and by favor.It is managed
20% can be up to by incident photon-to-electron conversion efficiency.Pure cuprous oxide (Cu2O) crystal is a kind of octahedral cube structure, is had
Good electric conductivity and stability and be applied to the every field such as photovoltaic device, photocatalysis, hydrogen manufacturing, electrochromism, hull cell.
The method for preparing cuprous oxide has very much.However the battery efficiency that high temperature prepares cuprous oxide substrate is lower, low temperature preparation is system
The standby common method of cuprous oxide；For example low temperature process has electrochemical deposition, cathode oxidation, chemical oxidation and reduction method, reaction magnetic
Control sputtering and hydro-thermal method, are especially worth causing to be concerned with hydro-thermal method, this method economy, low energy consumption, and preparation method is simple.
Glucose, fructose, hydrazine hydrate, sodium borohydride and polyalcohol etc. are all common reducing agents, can by reduction reaction
To obtain the Cu of different shape2O film nano material.Glucose heats easy decomposition under alkaline condition, and glucose itself also has
There is environmentally protective cuprous nano material nontoxic soluble easily in water, therefore can preparing.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, providing one kind, simply and easily zinc, cerium list are adulterated and are total to
The preparation method of cuprous nano material is adulterated, this method device simple, easy to operate, economical, low energy consumption.
In order to achieve the above object, the present invention provides a kind of ceriums (Ce) or/and zinc (Zn) to adulterate cuprous nano material
The preparation method of material, which comprises the following steps:
Step 1: by a water copper acetate (Cu (CH3COO)2·H2) and glucose (C O6H12O6) be add to deionized water it is mixed
It closes uniformly, obtains suspension；
Step 2: by cerous nitrate hexahydrate (Ce (NO3)3·6H2) or/and two water zinc acetate (Zn (CH O3COO)2·
2H2O) be added in the suspension that step 1 obtains, carry out hydro-thermal reaction obtain sediment, be then centrifuged for, wash, dry to get
Cerium or/and zinc doping cuprous nano material.
Preferably, Cu (CH in the step 13COO)2·H2O and C6H12O6Molar ratio be 1:1~1:6.
Preferably, Cu (CH in the step 13COO)2·H2The molar ratio of O and deionized water is 1:2~1:10.
Preferably, Ce (NO is only added in the step 23)3·6H2When O, Cu (CH3COO)2·H2O and Ce (NO3)3·
6H2The molar ratio of O is 1:0.05~1:0.35.
Preferably, Zn (CH is only added in the step 23COO)2·2H2When O, Cu (CH3COO)2·H2O and Zn
(CH3COO)2·2H2The molar ratio of O is 1:0.05~1:0.5.
Preferably, Ce (NO in the step 23)3·6H2O and Zn (CH3COO)2·2H2When O is added, Cu
(CH3COO)2·H2O and Ce (NO3)3·6H2The molar ratio of O is 1:0.05~1:0.2, Cu (CH3COO)2·H2O and Zn
(CH3COO)2·2H2The molar ratio of O is 1:0.05~1:0.2.
Preferably, hydrothermal temperature is 70~90 DEG C in the step 2, and the reaction time is greater than 30min.
Preferably, washing is washed 2~4 times with dehydrated alcohol in the step 2；
Preferably, dry in the step 2 to be placed in vacuum oven at 25~30 DEG C dry 30min.
Key problem in technology of the invention is the selection of reaction raw materials, reaction temperature, material rate is adjusted, in magnetic stirring apparatus
Stirring to obtain unit for uniform suspension, and move on in reaction kettle and be evenly heated, obtain zinc, the doping of cerium list and codope cuprous oxide
Material.
Doping Cu of the invention2O photoelectric material is obtained based on hydro-thermal method, and reaction raw materials are nontoxic, and reaction dissolvent is deionization
Water.Meanwhile reaction temperature of the invention is low, the reaction time is short, and reaction process is safe and reliable, does not discharge pernicious gas；Operation side
Just, synthetic method is simple, and gained reaction product stability is good, with high purity.
In preparation process of the invention, using magnetic stirrer, guarantee that the physics of entire reaction suspension is uniform
Property, it is Uniform Doped Cu2The synthesis of O photoelectric material provides good forming core and growing environment.
In preparation process of the invention, when reaction temperature is at 70~90 DEG C, it can obtain zinc, the doping of cerium list and be co-doped with
Miscellaneous cuprous oxide material, reaction temperature is wider, is easy to control.
In preparation process of the invention, the reaction time is greater than 30 minutes, and the reaction time is short.
The beneficial effects of the present invention are:
Element doping Cu can be realized by means of the present invention2The green syt of O photoelectric material has simple process, behaviour
Make the advantages that convenient, reaction temperature is low, energy consumption is small, products therefrom has many advantages, such as that stability is good, with high purity, it will in photoelectricity material
Major application prospect is had in terms of the research of material.
Detailed description of the invention
Fig. 1 is the XRD diagram of the cuprous nano material of zinc, the doping of cerium list and codope that embodiment obtains；
Fig. 2 is the SEM figure of the cuprous nano material of zinc, the doping of cerium list and codope that embodiment obtains；
Fig. 2 (a) is that the SEM of the obtained cerium dopping cuprous nano material of embodiment 1 schemes；
Fig. 2 (b) is that the SEM of the obtained zinc doping cuprous nano material of embodiment 2 schemes；
Fig. 2 (c) is the SEM figure of the obtained zinc of embodiment 3, cerium codope cuprous nano material；
Fig. 3 is the EDS figure for the cerium dopping cuprous nano material that embodiment 1 obtains；
Fig. 4 is the EDS figure for the cerium dopping cuprous nano material that embodiment 2 obtains；
Fig. 5 is the EDS figure for the cerium dopping cuprous nano material that embodiment 3 obtains.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
Present embodiments provide a kind of preparation method of cerium (Ce) list doping cuprous nano material, specific preparation step
It is as follows:
Step 1: by 3mmol Cu (CH3COO)2·H2O and 6mmol C6H12O6It is added in 50mL deionized water and mixes
It is even, obtain suspension；
Step 2: by 0.3mmol Ce (NO3)3·6H2O it) is added in the suspension that step 1 obtains, is stirred at room temperature
Uniformly, it then carries out carrying out hydro-thermal reaction 500r/min in magnetic heating stirrer, 80 DEG C of heating temperature, heating time is
1h obtains dark red precipitate after reaction, and product is centrifuged by centrifuge, and revolving speed is 2000r/min and rotates 1 minute, uses
Dehydrated alcohol washs 2 times, is placed in a vacuum drying oven at 50 DEG C dry 8h to get to cerium list and adulterates cuprous nano material
Material.
Fig. 3 is the EDS energy spectrum diagram of the sample, and the peak of Cu, O, C, Ce element, the correspondence of Cu, O and Ce are observed from map
Molar ratio is 2:1.12:0.09, wherein the peak of C element derives from conductive carbon adhesive tape.
Embodiment 2
Present embodiments provide a kind of preparation method of zinc (Zn) list doping cuprous nano material, specific preparation step
It is as follows:
Step 1: by 3mmol Cu (CH3COO)2·H2O and 6mmol C6H12O6It is added in 50mL deionized water and mixes
It is even, obtain suspension；
Step 2: by 0.3mmol Zn (CH3COO)2·2H2O is added in the suspension that step 1 obtains, and is stirred at room temperature
It mixes uniformly, then carries out carrying out hydro-thermal reaction in magnetic heating stirrer, 80 DEG C of heating temperature, heating time 1h, react
After, dark red precipitate is obtained, product is centrifuged by centrifuge, and revolving speed is 2000r/min and rotates 1 minute, with anhydrous second
Alcohol washs 2 times, is placed in a vacuum drying oven at 50 DEG C dry 8h to get to zinc list and adulterates cuprous nano material.
Fig. 4 is the EDS energy spectrum diagram of the sample, and the peak of Cu, O, C, Zn element, the correspondence of Cu, O and Zn are observed from map
Molar ratio is 2:0.97:0.12, wherein the peak of C element derives from conductive carbon adhesive tape.
Embodiment 3
Present embodiments provide the preparation method of a kind of zinc, cerium codope cuprous nano material, specific preparation step
It is as follows:
Step 1: by 3mmol Cu (CH3COO)2·H2O and 6mmol C6H12O6It is added in 50mL deionized water and mixes
It is even, obtain suspension；
Step 2: by 0.3mmol Ce (NO3)3·6H2) and 0.3mmol Zn (CH O3COO)2·2H2O is added to step 1 and obtains
To suspension in, be stirred at room temperature uniformly, then carry out carrying out hydro-thermal reaction, heating temperature in magnetic heating stirrer
80 DEG C, heating time 1h, after reaction, dark red precipitate is obtained, product is centrifuged by centrifuge, revolving speed 2000r/
Min and rotation 1 minute, are washed 2 times with dehydrated alcohol, are placed in a vacuum drying oven at 50 DEG C dry 8h to get total to zinc, cerium
Adulterate cuprous nano material.
Fig. 5 is the EDS energy spectrum diagram of the sample, and the peak of Cu, O, C, Ce, Zn element, Cu, O, Ce and Zn are observed from map
Correspondence molar ratio be 2:0.89:0.07:0.08, wherein the peak of C element derive from conductive carbon adhesive tape.
2 θ=29.58 ° of (1) cerium dopping cuprous nano material as shown in Figure 1:, 36.44 °, 42.32 °, 61.40 °,
73.55 °, 77.41 °, respectively correspond cubic phase Cu26 peaks of O are (110), (111), (200), (220), (311), (222)
Plane.(2) 2 θ=29.56 ° of zinc doping cuprous nano material, 36.42 °, 42.30 °, 61.37 °, 73.51 °, 77.37 ° points
Cubic phase Cu is not corresponded to26 peaks of O are (110), (111), (200), (220), (311), the plane of (222).(3) zinc, cerium are mixed
Miscellaneous 2 θ=29.56 ° of cuprous nano material, 42.30 °, 61.37 °, 73.51 °, 77.37 °, respectively correspond cube by 36.42 °
(110) of phase Cu2O, (111), (200), (220), (311), the plane of (222).Known by Fig. 1, the position at cuprous oxide peak does not have
There is generation large variation, and free from admixture peak occurs.
Fig. 2 (a) and (b) are the crystal patterns for amplifying 7k times in the secure execution mode (sem, and Fig. 2 (c) amplifies 10k times of crystal pattern in the secure execution mode (sem；
Apparent variation has occurred in the pattern of cuprous oxide as seen from Figure 2, and particle agglomeration is stronger, from cube to multi-panel
Body, the transformation of near-spherical structure.Therefore speculating may be Zn, Ce atom instead of Cu2Some atom vacancy in O cubic crystal.
Claims (4)
1. the preparation method of a kind of cerium or/and zinc doping cuprous nano material, which comprises the following steps:
Step 1: by Cu (CH3COO)2·H2O and C6H12O6It is add to deionized water uniformly mixed, obtains suspension；
Step 2: by Ce (NO3)3·6H2O or/and Zn (CH3COO)2·2H2O is added in the suspension that step 1 obtains, and is carried out
Hydro-thermal reaction obtains sediment, is then centrifuged for, washs, drying to get cerium or/and zinc doping cuprous nano material.
2. the preparation method of cerium as described in claim 1 or/and zinc doping cuprous nano material, which is characterized in that described
Cu (CH in step 13COO)2·H2O and C6H12O6Molar ratio be 1:1~1:6；Cu(CH3COO)2·H2O and deionized water
Molar ratio is 1:2~1:10.
3. the preparation method of cerium as described in claim 1 or/and zinc doping cuprous nano material, which is characterized in that described
Ce (NO will only be added in step 23)3·6H2When O, Cu (CH3COO)2·H2O and Ce (NO3)3·6H2The molar ratio of O is 1:0.05
~1:0.35；Zn (CH is only added3COO)2·2H2When O, Cu (CH3COO)2·H2O and Zn (CH3COO)2·2H2The molar ratio of O is
1:0.05~1:0.5；Ce(NO3)3·6H2O and Zn (CH3COO)2·2H2When O is added, Cu (CH3COO)2·H2O and Ce
(NO3)3·6H2The molar ratio of O is 1:0.05~1:0.2, Cu (CH3COO)2·H2O and Zn (CH3COO)2·2H2The molar ratio of O
For 1:0.05~1:0.2.
4. the preparation method of cerium as described in claim 1 or/and zinc doping cuprous nano material, which is characterized in that described
Hydrothermal temperature is 70~90 DEG C in step 2, and the reaction time is greater than 30min；Washing is washed 2~4 times with dehydrated alcohol；It is dry
It is dry to be placed in vacuum oven at 25~30 DEG C dry 30min.
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| CN110467215A (en) * | 2019-08-06 | 2019-11-19 | 西安交通大学 | A kind of iron of morphology controllable, zinc ion codope cuprous oxide crystal preparation method |
| CN110841649A (en) * | 2019-10-17 | 2020-02-28 | 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 |
| CN113060754A (en) * | 2021-03-16 | 2021-07-02 | 江苏理工学院 | Doped cuprous dechlorinating agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN110841649A (en) * | 2019-10-17 | 2020-02-28 | 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 |
| CN113060754A (en) * | 2021-03-16 | 2021-07-02 | 江苏理工学院 | Doped cuprous dechlorinating agent and preparation method 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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