CN102464322B - Cuprous oxide clay nano-sized composition and preparation method thereof - Google Patents
Cuprous oxide clay nano-sized composition and preparation method thereof Download PDFInfo
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- CN102464322B CN102464322B CN201010532871.XA CN201010532871A CN102464322B CN 102464322 B CN102464322 B CN 102464322B CN 201010532871 A CN201010532871 A CN 201010532871A CN 102464322 B CN102464322 B CN 102464322B
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Abstract
The invention discloses a cuprous oxide clay nano-sized composition and a preparation method thereof. The cuprous oxide clay nano-sized composition is prepared through steps that: soluble cupric salt and clay are added to water, such that a mixed solution of cupric salt and clay is prepared; the cupric salt and clay mixed solution is heated to a temperature of 70-80 DEG C; the temperature is maintained, and an alkaline aqueous solution of a reducing agent is dropped into the cupric salt and clay mixed solution; the reaction is continued when dropping is finished, until the solution turns orange, such that the cuprous oxide clay nano-sized composition is obtained. According to the invention, no organic dispersant is required to be added. Cuprous oxide nano-grade particles in the cuprous oxide clay nano-sized composition are adhered on the clay lamellas, such that agglomeration is prevented.
Description
Technical field
The present invention relates to a kind of cuprous oxide clay nano-sized composition and preparation method thereof.
Background technology
Red copper oxide is a kind of broad-spectrum material.As a kind of P-type semiconductor, Red copper oxide is a kind of photoelectric conversion material, and its energy gap and conduction band width are only 2.0eV, under excited by visible light, can produce current carrier, and its efficiency can reach 18%.As a kind of stain control agent of marine ship coating, Red copper oxide is just applied to antifouling paint from the forties in last century.Organotin self-polishing coating, due to the pollution to environment, starts to suffer comprehensive forbidding for 2008 in recent years, has strengthened especially the application of Red copper oxide in antifouling paint field.As a kind of catalytic material, Red copper oxide also can be used as the catalytic decomposition of organic pollutant.In addition Red copper oxide all has application in fields such as sensor, high-temperature superconductor, pigment, tinting material, scolder, sanitass, is a kind of inorganic materials having a extensive future.Nano material is due to its small-size effect, surface-interface effect, quantum size effect and macro quanta tunnel effect etc., in magnetic, catalytic, photoabsorption, the aspect such as thermal resistance and fusing point demonstrates the unrivaled high-performance of conventional material, nano cuprous oxide also becomes the trend of Red copper oxide researchdevelopment, and one of the agglomeration traits of nano cuprous oxide problem that to be also researchist put forth effort solves, a main method that solves agglomeration traits is using organic molecule or polymer as dispersion agent, to be wrapped in the surface of nano cuprous oxide particle, but organic molecule is difficult to remove, can affect the performance of nano cuprous oxide performance.
Summary of the invention
The object of this invention is to provide a kind of cuprous oxide clay nano-sized composition and preparation method thereof.
Cuprous oxide clay nano-sized composition provided by the present invention is to prepare according to the method comprising the steps: solubility cupric salt and clay are added to the water, are mixed with mantoquita clay mixing solutions; Make described mantoquita clay mixing solutions be warming up to 70-80 ℃, maintain described temperature, the alkaline aqueous solution of reductive agent is splashed in described mantoquita clay mixing solutions, dropwise rear continuation reaction, until that reaction soln becomes is orange, obtain cuprous oxide clay nano-sized composition.
Wherein, described solubility cupric salt specifically can be selected from least one in following mantoquita and hydrate thereof: copper sulfate, cupric nitrate, cupric chloride and neutralized verdigris.Described clay can be selected from following at least one: kaolin, polynite and illite.Described reductive agent specifically can be selected from following at least one: hydrazine hydrate, sodium borohydride, S-WAT, glucose, formaldehyde, xitix, inferior sodium phosphate, rongalite, zinc powder and oxyammonia sulfate.
In the present invention, described mantoquita clay mixing solutions specifically can be comprised of the material of following mass parts: solubility cupric salt 0.1-10 part, clay 0.1-10 part, and 100 parts, water; Preferably composed as follows: solubility cupric salt 1-5 part, clay 1-5 part, and 100 parts, water.
The alkaline aqueous solution of described reductive agent is comprised of the material of following mass parts: reductive agent 0.1-10 part, caustic alkali 0.1-5 part, and water 10-100 part; Preferably the material by following mass parts forms: reductive agent 1-10 part, caustic alkali 0.1-1 part, and water 40-100 part; Described caustic alkali is NaOH and/or KOH.
In described reaction system, the volume ratio of the alkaline aqueous solution of the reductive agent adding and mantoquita clay mixing solutions is 1: 1-1: 10; Preferred volume ratio is 1: 1-1: 5.
Described reaction also needs to carry out under whipped state, and the rotating speed of described stirring can be 500～1500rpm; The rate of addition that the described alkaline aqueous solution by reductive agent splashes in described mantoquita clay mixing solutions can be 0.1-0.5mL/min.
Described method also comprises washs cuprous oxide clay nano-sized composition successively water, ethanol dry step, and described dry temperature is 60-70 ℃.
In gained Red copper oxide clay complex of the present invention, Red copper oxide exists with the form of nano particle, and its particle diameter can be 200～500nm.
The present invention compared with prior art, have advantages of that cost is low, environmental protection, without adding organic dispersing agent.In resulting cuprous oxide clay nano-sized composition, cuprous oxide nano particle adheres on clay layer, makes this mixture be difficult for reuniting.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the cuprous oxide clay nano-sized composition of embodiment 1 preparation.
Fig. 2 is kaolinic transmission electron microscope photo.
Fig. 3 is the transmission electron microscope photo of the cuprous oxide clay nano-sized composition of embodiment 1 preparation.
Fig. 4 is the photo of the cuprous oxide clay nano-sized composition aqueous dispersions of embodiment 1 preparation.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, prepare cuprous oxide clay nano-sized composition
To, in two mouthfuls of flasks of 25mL, add 0.1gCuSO
45H
2o, 0.1g kaolin, 10mL water, stir and be warming up to 70 ℃, and stirring velocity is 500rpm.A mouth of two-mouth bottle connects prolong, is used as condensing reflux.Another mouthful connects the feed hopper of 10mL, maintains the temperature of flask at 70 ℃, in flask, slowly drips modulated extremely alkaline reductant solution.The composition of reductant solution is: 0.1gC
6h
12o
6h
2o, 0.04gNaOH, 5mL water.Within 10 minutes, reductant solution dropwises, and continues 10 minutes solution of reaction and becomes orangely completely, obtains cuprous oxide clay nano-sized composition aqueous dispersions (seeing Fig. 4).By this dispersion liquid centrifugation, first with water washing three times to throw out, then use washing with alcohol three times, 60 ℃, baking oven is dry, obtains Red copper oxide clay complex.In gained Red copper oxide clay complex, cuprous oxide nano particle particle diameter is 200～500nm.
The XRD figure spectrum of Red copper oxide clay complex prepared by this embodiment is shown in Fig. 1, and the resulting product that reduces is as shown in Figure 1 Red copper oxide.Its transmission electron microscope photo is shown in Fig. 3, as shown in Figure 3 gained Red copper oxide particle good dispersion.
Embodiment 2, prepare cuprous oxide clay nano-sized composition
To, in two mouthfuls of flasks of 25mL, add 0.2gCuCl
22H
2o, 0.1g polynite, 10mL water, stir and be warming up to 70 ℃, and stirring velocity is 800rpm.A mouth of two-mouth bottle connects prolong, is used as condensing reflux.Another mouthful connects the feed hopper of 10mL, maintains the temperature of flask at 70 ℃, in flask, slowly drips modulated extremely alkaline reductant solution.The composition of reductant solution is: 0.2gNa
2sO
3, 0.03gNaOH, 10mL water.Within 30 minutes, reductant solution dropwises, continue 10 minutes solution of reaction become completely orange, centrifuge washing, 65 ℃ dry, obtains Red copper oxide clay complex.Gained cuprous oxide nano particle particle diameter is 400～500nm.
Embodiment 3, prepare cuprous oxide clay nano-sized composition
To, in two mouthfuls of flasks of 50mL, add 0.2gCu (NO
3)
23H
2o, 0.2g illite, 20mL water, stir and be warming up to 75 ℃, and stirring velocity is 1000rpm.A mouth of two-mouth bottle connects prolong, is used as condensing reflux.Another mouthful connects the feed hopper of 10mL, maintains the temperature of flask at 75 ℃, in flask, slowly drips modulated extremely alkaline reductant solution.The composition of reductant solution is: 0.2g xitix, 0.06gNaOH, 4mL water.Within 20 minutes, reductant solution dropwises, continue 20 minutes solution of reaction become completely orange, centrifuge washing, 70 ℃ dry, obtains Red copper oxide clay complex.In gained Red copper oxide clay complex, cuprous oxide nano particle particle diameter is 200～600nm.
To, in two mouthfuls of flasks of 25mL, add 0.3gCuSO
45H
2o, 0.1g polynite and kaolin mixture (mass ratio 1: 1), 10mL water, stir and be warming up to 70 ℃, and stirring velocity is 600rpm.A mouth of two-mouth bottle connects prolong, is used as condensing reflux.Another mouthful connects the feed hopper of 10mL, maintains the temperature of flask at 70 ℃, in flask, slowly drips modulated extremely alkaline reductant solution.The composition of reductant solution is: 0.6gC
6h
12o
6h
2o, 0.04gNaOH, 5mL water.Within 10 minutes, reductant solution dropwises, and continues 15 minutes solution of reaction and becomes orange completely.Centrifuge washing, 60 ℃ dry, obtains Red copper oxide clay complex.In gained Red copper oxide clay complex, cuprous oxide nano particle particle diameter is 300～550nm.
Embodiment 5, prepare cuprous oxide clay nano-sized composition
To, in two mouthfuls of flasks of 25mL, add 0.2gCuSO
45H
2o, 0.5g polynite, 10mL water, stir and be warming up to 80 ℃, and stirring velocity is 800rpm.A mouth of two-mouth bottle connects prolong, is used as condensing reflux.Another mouthful connects the feed hopper of 10mL, maintains the temperature of flask at 80 ℃, in flask, slowly drips modulated extremely alkaline reductant solution.The composition of reductant solution is: 0.8g inferior sodium phosphate, 0.05gKOH, 8mL water.Within 20 minutes, reductant solution dropwises, continue 10 minutes solution of reaction become completely orange, centrifuge washing, 60 ℃ dry, obtains Red copper oxide clay complex.In gained Red copper oxide clay complex, cuprous oxide nano particle particle diameter is 250～500nm.
Embodiment 6, prepare cuprous oxide clay nano-sized composition
To, in two mouthfuls of flasks of 25mL, add 0.3gCuSO
45H
2o, 0.1g kaolin, 10mL water, stir and be warming up to 75 ℃, and stirring velocity is 500rpm.A mouth of two-mouth bottle connects prolong, is used as condensing reflux.Another mouthful connects the feed hopper of 10mL, maintains the temperature of flask at 75 ℃, in flask, slowly drips modulated extremely alkaline reductant solution.The composition of reductant solution is: 0.3g oxyammonia sulfate, 0.06gNaOH, 5mL water.Within 10 minutes, reductant solution dropwises, and continues 20 minutes solution of reaction and becomes orange completely.Centrifuge washing, 70 ℃ dry.Gained cuprous oxide nano particle particle diameter is 400～600nm.
Claims (2)
1. a method of preparing Red copper oxide clay complex, comprises the steps: solubility cupric salt and clay to be added to the water, and is mixed with mantoquita clay mixing solutions; Make described mantoquita clay mixing solutions be warming up to 70-80 ℃, maintain described temperature, the alkaline aqueous solution of reductive agent is splashed in described mantoquita clay mixing solutions, dropwise rear continuation reaction, until that reaction soln becomes is orange, obtain Red copper oxide clay complex;
Described solubility cupric salt is selected from least one in following mantoquita and hydrate thereof: copper sulfate, cupric nitrate, cupric chloride and neutralized verdigris;
Described clay be selected from following at least one: kaolin, polynite and illite;
Described reductive agent be selected from following at least one: hydrazine hydrate, sodium borohydride, S-WAT, glucose, formaldehyde, xitix, inferior sodium phosphate, rongalite, zinc powder and oxyammonia sulfate;
Described mantoquita clay mixing solutions is comprised of the material of following mass parts: solubility cupric salt 1-5 part, clay 1-5 part, and 100 parts, water;
The alkaline aqueous solution of described reductive agent is comprised of the material of following mass parts: reductive agent 1-10 part, caustic alkali 0.1-1 part, and water 40-100 part; Described caustic alkali is NaOH and/or KOH;
The volume ratio of the alkaline aqueous solution of described reductive agent and mantoquita clay mixing solutions is 1:1-1:5;
Described reaction is carried out under whipped state, and the rotating speed of described stirring is 500～1500rpm; The rate of addition that the described alkaline aqueous solution by reductive agent splashes in described mantoquita clay mixing solutions is 0.1-0.5mL/min.
2. method according to claim 1, is characterized in that: described method also comprises: Red copper oxide clay complex successively water, ethanol are washed and dry step, and described dry temperature is 60-70 ℃.
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| CN113881135B (en) * | 2021-08-25 | 2022-08-26 | 广东粤港澳大湾区国家纳米科技创新研究院 | Nano cuprous oxide antibacterial and mildewproof master batch, preparation method thereof, plastic product and preparation method thereof |
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