CN103466681A - Preparation method of graded spherical cuprous oxide hollow nano particle - Google Patents
Preparation method of graded spherical cuprous oxide hollow nano particle Download PDFInfo
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Abstract
The invention discloses a preparation method of a graded spherical cuprous oxide hollow nano particle. The preparation method of the graded spherical cuprous oxide hollow nano particle is characterized by comprising the following steps of: (1) dissolving copper salt in water, (2) dropwise adding a mixed aqueous solution of hydrazine hydrate and acetate at 5-40 DEG C under a stirring condition, and (3) after dropwise adding, continuing stirring for 10-30min at 5-40 DEG C, centrifuging, washing with water, performing vacuum drying, and obtaining the graded spherical cuprous oxide hollow nano particle, wherein a molar concentration of Cu<2+> is 0.1-4mol/L, and a molar ratio of acetate (CH3COO<->) to hydrazine hydrate (N2H4) to copper salt (Cu<2+>) is (1-3):(0.5-4):1. According to the method, a reaction system is simple, raw materials are cheap and easy to obtain, and the method produces no hazardous waste, meets a green production concept, is simple in process route, easy and simple to operate, mild in reaction condition, short in reaction time and high in efficiency, and is suitable for mass production.
Description
Technical field
The present invention relates to a kind of preparation method of grade cuprous oxide, be specifically related to the preparation method of the spherical Red copper oxide hollow Nano of a kind of classification particle.
Background technology
Red copper oxide is cupprous oxide compound, redness or garnet octahedral isometric system crystalline powder.The Red copper oxide of occurring in nature can be present in the rhombohedral iron ore of reddish-brown.Red copper oxide can be used as catalyzer and uses in organic synthesis, also in fields such as pigment, coating, antiseptic-germicide, electronic products, has a wide range of applications.And grade cuprous oxide is owing to having dimensional effect, thereby there are the character such as special optics, electricity, be with a wide range of applications aspect superconductor, solar cell, catalyzer, sensor.Nano cuprous oxide also has potential application prospect aspect photocatalysis degradation organic contaminant, is subject to environmental research person's strong interest.Nano cuprous oxide will be special with it character application prospect is more widely arranged, therefore, research nano cuprous oxide the preparation method there is certain realistic meaning.
The nano cuprous oxide of synthetic is generally powder type, due to synthetic granular size difference, can show as the multiple colors such as yellow, orange, redness or purple.The method for preparing nano cuprous oxide is of a great variety, roughly can be divided into solid phase method, liquid phase method and vapor phase process three major types.Solid phase method mainly comprises sintering process and low-temperature solid-phase method; Liquid phase method mainly comprises hydrolysis method, chemical precipitation method, electrochemical process, radiation reduction method and sol-gel method; Vapor phase process mainly comprises chemical Vapor deposition process and spray pyrolysis.
Because the pattern of Red copper oxide and structure have impact significantly to its physics and chemistry character, therefore, the micro-nano Red copper oxide of synthetic controllable appearance, structure and size has become focus and the focus of research Red copper oxide material.Murphy, C.J. etc. are used PEG as stablizer, have prepared the cuprous nano cubes (J.Mater.Chem., 2004,14,735) of different size size.L.F.Gou etc. take copper sulfate as copper source, cetyl trimethylammonium bromide and sodium hydroxide as additive, sodium ascorbate is reductive agent, prepared Red copper oxide hollow Nano cubes (Nano.Lett., 2003,3:231-234).The use polyvinylpyrrolidones (PVP) such as Guo Lin have prepared the cuprous nano material (CN 101348275) of the different morphologies such as octahedra shape as stablizer.Fang Yun etc. be take cluster that polyvinylpyrrolidone and sodium lauryl sulphate form as soft template, hydrazine hydrate are reductive agent, and the cupric ion reduction is obtained to Red copper oxide hollow material (CN 101041456).Punishment Lan Lan etc. take neutralized verdigris as copper source, polyvinylpyrrolidone and sodium hydroxide as additive, glucose prepared Red copper oxide open hollow nanometer ball (Hubei University's journal, 2008,30 (3): 267-269) as reductive agent.Xu Yanyan etc. be take cupric chloride as copper source, polyoxyethylene glycol and sodium hydroxide are additive, adopt solvent-thermal method prepared Red copper oxide hollow Nano cubes (J. Phys. Chem. C, 2008,112:16769-16773).Song Jimei etc. utilize reduction in aqueous solution at room temperature method and hydrothermal reaction at low temperature to prepare cubic and spherical Red copper oxide (applied chemistry, 2010,27 (11): 1328-1333).Pay grand firm grade and using various cupric salts as the copper source, polyvinylpyrrolidone, propanediol polyoxypropylene Soxylat A 25-7 etc. are as tween, and sodium borohydride, as reductive agent, has been prepared classification flower-like structure Red copper oxide (CN 102502771A).But these organic surface active agents very easily are adsorbed on the product surface, make troubles to the cleaning of product, finally affect the purity of product, brought a lot of troubles to production.Therefore developing a kind of easy cleaning tensio-active agent and the method that operation is simple synthesizes Red copper oxide and is very important.The reduction neutralized verdigriss such as use hydrazine hydrate, oxammonium hydrochloride such as Liu Yifan are prepared Monodispersion, need to add sodium tartrate (potassium) or glycerine (Acta PhySico-Chimica Sinica in system, 1993,9 (1): 107-110), and this solubleness in water of neutralized verdigris is little, need to add a large amount of water neutralized verdigris is dissolved, so preparation amount is little, is not suitable for scale operation.
Summary of the invention
The technical problem that the present invention solves has been to provide the preparation method of the spherical Red copper oxide hollow Nano of a kind of classification particle, adopt the spherical Red copper oxide hollow Nano of redox precipitation legal system back-up level particle, operation is simple, can within the short period of time under normal temperature condition, prepare in a large number the controlled hollow ball shaped nanometer hierarchy of pattern, the nano cuprous oxide structure and morphology that utilizes this method to prepare is stable, reproducible.
Technical scheme of the present invention is: the preparation method of the spherical Red copper oxide hollow Nano of a kind of classification particle is characterized in that comprising the following steps: (1), mantoquita is dissolved in water, wherein Cu
2+volumetric molar concentration be 0.1-4mol/L; (2), under the condition of 5-40 ℃ of temperature and stirring, drip the mixed aqueous solution of hydrazine hydrate and acetate, wherein the mol ratio of acetate, hydrazine hydrate and mantoquita is n(CH
3cOO
-): n(N
2h
4): n(Cu
2+)=1-3:0.5-4:1; (3), be added dropwise to complete after, continue to stir 10-30min at the temperature of 5-40 ℃, centrifugal, washing, vacuum-drying, make the spherical Red copper oxide hollow Nano of classification particle.
Mantoquita of the present invention is one or more the mixture in cupric chloride, cupric bromide, cupric nitrate or copper sulfate.
Acetate of the present invention is sodium-acetate or Potassium ethanoate.
In step of the present invention (2), stirring velocity is controlled at 250-2000r/min, and the time that drips the mixed aqueous solution of hydrazine hydrate and acetate is 10-20min.
In step of the present invention (3), the vacuum-drying temperature is 30-70 ℃.
The particle diameter of the spherical Red copper oxide hollow Nano of the classification particle that the present invention is prepared is 450-550nm.
Principle of the present invention is: bivalent cupric ion, under the effect of a certain amount of reductive agent hydrazine hydrate, first generates univalent copper ion, and univalent copper ion and acetate ion be rapidly in conjunction with generating cuprous acetate, and cuprous acetate is met water and become rapidly Red copper oxide and separate out.Reaction equation is:
The invention has the beneficial effects as follows:
1, reaction system is simple, only uses mantoquita (cupric chloride, cupric bromide, cupric nitrate or copper sulfate), acetate (sodium-acetate or Potassium ethanoate), water (solvent) and hydrazine hydrate (reductive agent), and they all belong to general chemistry reagent, cheap and easy to get;
2, preparation cost is low, without bazardous waste, produces, and meets the green production theory;
3, technique of the present invention is simple, easy and simple to handle, reaction temperature and, the reaction times is short, efficiency is high, is applicable to scale operation.
The accompanying drawing explanation
Fig. 1 is the XRD figure of the spherical Red copper oxide hollow Nano of the classification particle of the embodiment of the present invention 2 preparations, Fig. 2 is the SEM figure of the spherical Red copper oxide hollow Nano of the classification particle of the embodiment of the present invention 2 preparations, Fig. 3 is the TEM figure of the spherical Red copper oxide hollow Nano of the classification particle of the embodiment of the present invention 2 preparations, and Fig. 4 is the TEM figure of the spherical Red copper oxide hollow Nano of the classification particle of the embodiment of the present invention 3 preparations.
Embodiment
The embodiment of form by the following examples, foregoing of the present invention is described in further details, but this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
Get 0.1mol/LCuCl
2aqueous solution 100ml adds in reaction flask, under the stirring velocity of 5 ℃ and 250～500r/min, drips the mixed aqueous solution 20ml containing 0.005mol hydrazine hydrate and 0.01molNaOAc, and time for adding is controlled at 10～15min; After adding, continue to stir 10min, centrifugal, washing, be placed in vacuum drying oven, 40 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Get 0.5mol/LCuCl
2aqueous solution 20ml adds in reaction flask, under the stirring velocity of 15 ℃ and 500～1000r/min, drips the mixed aqueous solution 20ml containing 0.01mol hydrazine hydrate and 0.01molNaOAc, and time for adding is controlled at 10～15min; After adding, continue to stir 10min, centrifugal, washing, be placed in vacuum drying oven, 50 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.Fig. 1 has shown the XRD figure spectrum of the spherical Red copper oxide hollow Nano of the classification particle of preparation, by with standard diagram, comparing the product that can find out preparation, be Red copper oxide, Fig. 2 has shown the SEM collection of illustrative plates of the spherical Red copper oxide hollow Nano of the classification particle of preparation, can find out the ball-like structure of Red copper oxide by accompanying drawing, Fig. 3 has shown the TEM collection of illustrative plates of the spherical Red copper oxide hollow Nano of the classification particle of preparation, can find out that by accompanying drawing Red copper oxide is hollow nanostructured, illustration is selected area electron diffraction, can find out for polycrystalline.
Embodiment 3
Get 1mol/LCuCl
2aqueous solution 10ml adds in reaction flask, under the stirring velocity of 25 ℃ and 1000～1500r/min, drips the mixed aqueous solution 20ml containing 0.02mol hydrazine hydrate and 0.01molNaOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 20min, centrifugal, washing, be placed in vacuum drying oven, 60 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.Fig. 4 has shown the TEM collection of illustrative plates of the spherical Red copper oxide hollow Nano of the classification particle of preparation, by accompanying drawing, can find out that Red copper oxide is hierarchy.
Embodiment 4
Get 2mol/LCuCl
2aqueous solution 5ml adds in reaction flask, under the stirring velocity of 40 ℃ and 1500～2000r/min, drips the mixed aqueous solution 20ml containing 0.03mol hydrazine hydrate and 0.02molKOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 20min, centrifugal, washing, be placed in vacuum drying oven, 70 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 5
Get 4mol/LCuCl
2aqueous solution 2.5ml adds in reaction flask, under the stirring velocity of 25 ℃ and 1500～2000r/min, drips the mixed aqueous solution 20ml containing 0.04mol hydrazine hydrate and 0.03molNaOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 30min, centrifugal, washing, be placed in vacuum drying oven, 70 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 6
Get 2.5mol/LCuCl
2aqueous solution 4ml adds in reaction flask, under the stirring velocity of 25 ℃ and 1500～2000r/min, drips the mixed aqueous solution 20ml containing 0.01mol hydrazine hydrate and 0.02molKOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 20min, centrifugal, washing, be placed in vacuum drying oven, 50 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 7
Get 0.1mol/L CuBr
2aqueous solution 100ml adds in reaction flask, under the stirring velocity of 5 ℃ and 250～500r/min, drips the mixed aqueous solution 20ml containing 0.005mol hydrazine hydrate and 0.01molNaOAc, and time for adding is controlled at 10～15min; After adding, continue to stir 10min, centrifugal, washing, be placed in vacuum drying oven, 40 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 8
Get 0.5mol/L CuBr
2aqueous solution 20ml adds in reaction flask, under the stirring velocity of 15 ℃ and 500～1000r/min, drips the mixed aqueous solution 20ml containing 0.01mol hydrazine hydrate and 0.02molKOAc, and time for adding is controlled at 10～15min; After adding, continue to stir 10min, centrifugal, washing, be placed in vacuum drying oven, 50 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 9
Get 1mol/L CuBr
2aqueous solution 10ml adds in reaction flask, under the stirring velocity of 25 ℃ and 1000～1500r/min, drips the mixed aqueous solution 20ml containing 0.02mol hydrazine hydrate and 0.01molNaOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 20min, centrifugal, washing, be placed in vacuum drying oven, 60 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Get 2mol/L CuBr
2aqueous solution 5ml adds in reaction flask, under the stirring velocity of 30 ℃ and 1500～2000r/min, drips the mixed aqueous solution 20ml containing 0.03mol hydrazine hydrate and 0.02molNaOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 30min, centrifugal, washing, be placed in vacuum drying oven, 70 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 11
Get 2.5mol/L CuBr
2aqueous solution 4ml adds in reaction flask, under the stirring velocity of 40 ℃ and 1500～2000r/min, drips the mixed aqueous solution 20ml containing 0.04mol hydrazine hydrate and 0.03molNaOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 30min, centrifugal, washing, be placed in vacuum drying oven, 70 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 12
Get 0.1mol/L CuSO
4aqueous solution 100ml adds in reaction flask, under the stirring velocity of 5 ℃ and 250～500r/min, drips the mixed aqueous solution 20ml containing 0.005mol hydrazine hydrate and 0.01molKOAc, and time for adding is controlled at 10～15min; After adding, continue to stir 10min, centrifugal, washing, be placed in vacuum drying oven, 40 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 13
Get 0.2mol/L CuSO
4aqueous solution 50ml adds in reaction flask, under the stirring velocity of 15 ℃ and 500～1000r/min, drips the mixed aqueous solution 20ml containing 0.01mol hydrazine hydrate and 0.01molKOAc, and time for adding is controlled at 10～15min; After adding, continue to stir 20min, centrifugal, washing, be placed in vacuum drying oven, 50 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 14
Get 0.5mol/L CuSO
4aqueous solution 20ml adds in reaction flask, under the stirring velocity of 25 ℃ and 1000～1500r/min, drips the mixed aqueous solution 20ml containing 0.02mol hydrazine hydrate and 0.02molNaOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 30min, centrifugal, washing, be placed in vacuum drying oven, 60 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 15
Get 1mol/L CuSO
4aqueous solution 10ml adds in reaction flask, under the stirring velocity of 30 ℃ and 1500～2000r/min, drips the mixed aqueous solution 20ml containing 0.03mol hydrazine hydrate and 0.03molNaOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 30min, centrifugal, washing, be placed in vacuum drying oven, 70 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 16
Get 1mol/L CuSO
4aqueous solution 10ml adds in reaction flask, under the stirring velocity of 40 ℃ and 1500～2000r/min, drips the mixed aqueous solution 20ml containing 0.04mol hydrazine hydrate and 0.02molNaOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 20min, centrifugal, washing, be placed in vacuum drying oven, 70 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 17
Get 0.1mol/L Cu (NO
3)
2aqueous solution 100ml adds in reaction flask, under the stirring velocity of 5 ℃ and 250～500r/min, drips the mixed aqueous solution 20ml containing 0.005mol hydrazine hydrate and 0.01molNaOAc, and time for adding is controlled at 10～15min; After adding, continue to stir 10min, centrifugal, washing, be placed in vacuum drying oven, 40 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 18
Get 0.2mol/L Cu (NO
3)
2aqueous solution 50ml adds in reaction flask, under the stirring velocity of 15 ℃ and 500～1000r/min, drips the mixed aqueous solution 20ml containing 0.01mol hydrazine hydrate and 0.02molNaOAc, and time for adding is controlled at 10～15min; After adding, continue to stir 20min, centrifugal, washing, be placed in vacuum drying oven, 50 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 19
Get 0.5mol/L Cu (NO
3)
2aqueous solution 20ml adds in reaction flask, under the stirring velocity of 25 ℃ and 1000～1500r/min, drips the mixed aqueous solution 20ml containing 0.02mol hydrazine hydrate and 0.03molNaOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 30min, centrifugal, washing, be placed in vacuum drying oven, 60 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Get 1mol/L Cu (NO
3)
2aqueous solution 10ml adds in reaction flask, under the stirring velocity of 30 ℃ and 1500～2000r/min, drips the mixed aqueous solution 20ml containing 0.03mol hydrazine hydrate and 0.03molNaOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 30min, centrifugal, washing, be placed in vacuum drying oven, 70 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Embodiment 21
Get 1mol/L Cu (NO
3)
2aqueous solution 10ml adds in reaction flask, under the stirring velocity of 40 ℃ and 1500～2000r/min, drips the mixed aqueous solution 20ml containing 0.04mol hydrazine hydrate and 0.02molKOAc, and time for adding is controlled at 15～20min; After adding, continue to stir 30min, centrifugal, washing, be placed in vacuum drying oven, 60 ℃ of dryings, obtains the spherical Red copper oxide hollow Nano of red classification particle.
Above embodiment has described ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; under the scope that does not break away from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.
Claims (7)
1. the preparation method of the spherical Red copper oxide hollow Nano of a classification particle is characterized in that comprising the following steps: (1), mantoquita is dissolved in water, wherein Cu
2+volumetric molar concentration be 0.1-4mol/L; (2), under the condition of 5-40 ℃ of temperature and stirring, drip the mixed aqueous solution of hydrazine hydrate and acetate, wherein the mol ratio of acetate, hydrazine hydrate and mantoquita is n(CH
3cOO
-): n(N
2h
4): n(Cu
2+)=1-3:0.5-4:1; (3), be added dropwise to complete after, continue to stir 10-30min at the temperature of 5-40 ℃, centrifugal, washing, vacuum-drying, make the spherical Red copper oxide hollow Nano of classification particle.
2. the preparation method of the spherical Red copper oxide hollow Nano of classification according to claim 1 particle is characterized in that: described mantoquita is one or more the mixture in cupric chloride, cupric bromide, cupric nitrate or copper sulfate.
3. the preparation method of the spherical Red copper oxide hollow Nano of classification according to claim 1 particle, it is characterized in that: described acetate is sodium-acetate or Potassium ethanoate.
4. the preparation method of the spherical Red copper oxide hollow Nano of classification according to claim 1 particle, it is characterized in that: in described step (2), stirring velocity is controlled at 250-2000r/min, and the time that drips the mixed aqueous solution of hydrazine hydrate and acetate is 10-20min.
5. the preparation method of the spherical Red copper oxide hollow Nano of classification according to claim 1 particle is characterized in that: in described step (3), the vacuum-drying temperature is 30-70 ℃.
6. the preparation method of the spherical Red copper oxide hollow Nano of classification according to claim 1 particle, it is characterized in that: the particle diameter of the spherical Red copper oxide hollow Nano of prepared classification particle is 450-550nm.
7. the preparation method of the spherical Red copper oxide hollow Nano of classification according to claim 1 particle is characterized in that the principal reaction equation in preparation process is:
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016400A (en) * | 2014-06-18 | 2014-09-03 | 黄山永新股份有限公司 | Nanoscale cuprous oxide particle and synthesis method thereof |
| CN104192889A (en) * | 2014-08-04 | 2014-12-10 | 上海交通大学 | Method for preparing monodisperse cuprous oxide hollow sphere |
| CN104311888A (en) * | 2014-08-29 | 2015-01-28 | 河南赛沃思生物科技有限公司 | Cuprous oxide/chitosan composite material, sensitive membrane, biosensor, preparation method and applications |
| CN104445358A (en) * | 2014-11-06 | 2015-03-25 | 国核电力规划设计研究院 | Cuprous oxide nano microspheres in double-layered structure and preparation method thereof |
| CN105126868A (en) * | 2015-08-15 | 2015-12-09 | 淮北师范大学 | Highly active visible catalyst Ag / Cu2O hierarchy structural microsphere preparation method |
| CN113289645A (en) * | 2021-06-09 | 2021-08-24 | 淮北师范大学 | One-dimensional self-assembly composite photocatalyst and preparation method and application thereof |
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| CN101805010A (en) * | 2010-04-02 | 2010-08-18 | 青岛科技大学 | Method for preparing hollow sphere made from cuprous oxide |
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| CN101805010A (en) * | 2010-04-02 | 2010-08-18 | 青岛科技大学 | Method for preparing hollow sphere made from cuprous oxide |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016400A (en) * | 2014-06-18 | 2014-09-03 | 黄山永新股份有限公司 | Nanoscale cuprous oxide particle and synthesis method thereof |
| CN104016400B (en) * | 2014-06-18 | 2015-10-28 | 黄山永新股份有限公司 | Grade cuprous oxide particle and synthetic method thereof |
| CN104192889A (en) * | 2014-08-04 | 2014-12-10 | 上海交通大学 | Method for preparing monodisperse cuprous oxide hollow sphere |
| CN104311888A (en) * | 2014-08-29 | 2015-01-28 | 河南赛沃思生物科技有限公司 | Cuprous oxide/chitosan composite material, sensitive membrane, biosensor, preparation method and applications |
| CN104445358A (en) * | 2014-11-06 | 2015-03-25 | 国核电力规划设计研究院 | Cuprous oxide nano microspheres in double-layered structure and preparation method thereof |
| CN104445358B (en) * | 2014-11-06 | 2016-06-22 | 国核电力规划设计研究院 | A kind of double-decker cuprous nano microsphere and preparation method thereof |
| CN105126868A (en) * | 2015-08-15 | 2015-12-09 | 淮北师范大学 | Highly active visible catalyst Ag / Cu2O hierarchy structural microsphere preparation method |
| CN105126868B (en) * | 2015-08-15 | 2017-09-01 | 淮北师范大学 | High-activity visible light catalyst Ag/Cu2O hierarchy method for preparing microsphere |
| CN113289645A (en) * | 2021-06-09 | 2021-08-24 | 淮北师范大学 | One-dimensional self-assembly composite photocatalyst and preparation method and application thereof |
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Application publication date: 20131225 |