CN106041120B - A kind of preparation method of copper/cuprous oxide core-shell structured nanomaterials - Google Patents
A kind of preparation method of copper/cuprous oxide core-shell structured nanomaterials Download PDFInfo
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- CN106041120B CN106041120B CN201610478481.6A CN201610478481A CN106041120B CN 106041120 B CN106041120 B CN 106041120B CN 201610478481 A CN201610478481 A CN 201610478481A CN 106041120 B CN106041120 B CN 106041120B
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- 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
Abstract
The invention discloses a kind of preparation method of copper/cuprous oxide core-shell structured nanomaterials, this method is using soluble copper salt as copper source, and hydrazine hydrate is reducing agent, cetyl trimethylammonium bromide（CTAB）It for surfactant, has been prepared at ambient temperature using copper nano-particle as core, cuprous oxide is copper/cuprous oxide core-shell structured nanomaterials of shell；Metal core-shell structured nanomaterials prepared by this method can be used for the application study in the fields such as photocatalysis, photoelectrocatalysis and solar cell, and preparation process is controllable, easy to operate, low energy consumption, stability is strong.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, are related to reduction method under liquid phase environment and prepare monometallic different phase
The method of composite construction more particularly to a kind of preparation method of copper/cuprous oxide core-shell structured nanomaterials.
Background technology
Nano material is also known as ultramicro powder material, it is considered to be 21 century " most promising material ", nanostructured is existing
The advantages that characteristic of nanoparticle such as quantum size effect, small-size effect, skin effect, and exist to be combined by nanostructured and draw
New effect such as the quantum coupling effect and synergistic effect etc. risen, in catalytic reaction, high molecular material, chemical sensor, solar energy
The many aspects such as battery have important application value.
Core-shell composite nanoparticle is a kind of special nanostructured, with a size micron to nano grade spherical shape
Particle is core, a kind of compound heterogeneous structure that several layers of nano thin-film are wrapped on its surface and are formed, and has large specific surface area, density
The features such as low, superior photoelectric property, and size etc. that can be by controlling the thickness of nucleocapsid, grain size realizes the tune of composite performance
Control.
Nano copper particle and its compound have overactivity surface, good electric conductivity, photism and catalytic performance, and honest and clean
Valency is easy to get, and more and more extensive concern is received in scientific research field, in view of its every excellent performance, it is anti-to be widely used in catalysis
Should, the numerous areas such as electrocondution slurry, petroleum lubricant and pharmaceuticals industry.
Nano cuprous oxide is a kind of important p-type semiconductor material, and energy gap only has 2.0-2.1eV, in visible ray
Irradiation it is lower can electron-hole pair of the excited particles production with Strong oxdiative reproducibility, thus with efficient visible light catalytic
Can, the fields such as photocatalysis, electro-catalysis, solar cell are can be applied to, in addition, also once repeatedly report makees cuprous oxide both at home and abroad
For a kind of research of gas sensor.
Metal/semiconductor nano-core-shell structure is as a kind of new nanocomposite, the spy of this metal/semiconductor
Different combination, makes it be provided simultaneously with the dual property of metal nanoparticle and semi-conductor nano particles, in the phase of the two different performance
Mutually under synergistic effect, its generation is made to be much better than special light, electricity, the catalytic performance of one-component, so far, has no related liquid
Phase reduction method prepares the report of copper/cuprous nano catalyst with core-casing structure.
The content of the invention
The present invention provides a kind of copper/cuprous oxide nuclear shell structure nano material for field missing existing in the prior art
The preparation method of material, specifically includes following steps：
（1）It is the ratio of 1 ︰ 1.5 ~ 2.5 according to mantoquita and hydrazine hydrate molar ratio, by the copper that concentration is 0.05 ~ 0.08moL/L
Salting liquid and the hydrazine hydrate solution that concentration is 0.25 ~ 0.43moL/L mix, and it is small that no less than 1 is stood after mixed liquor is stirred evenly
When；
（2）By step（1）Mixed liquor after middle standing filters, cleaning, cleans after being neutral to filtrate, filter cake is stored in
Suspension is formed in water；
（3）According to step（2）The mass ratio of filter cake and mantoquita is the ratio of 1 ︰ 3.7 ~ 5.8, weighs mantoquita, is configured to concentration
For the copper salt solution of 0.06 ~ 0.11moL/L, then using the mass ratio of cetyl trimethylammonium bromide and mantoquita as 1 ︰'s 44 ~ 56
Cetyl trimethylammonium bromide is added in the copper salt solution that concentration is 0.06 ~ 0.11moL/L, stirs evenly, obtain by ratio
To mixed liquor A；
（4）According to step（3）In mantoquita and sodium hydroxide molar ratio be 1 ︰ 2 ~ 2.5 ratio, by concentration for 0.23 ~
The sodium hydroxide solution of 0.30 moL/L is added to step（2）It in suspension after ultrasound, stirs and evenly mixs, obtains mixed liquid B；
（5）While stirring by step（3）Mixed liquor A and step（4）Mixed liquid B after mixing, according to hydrazine hydrate
With step（3）The molar ratio of middle mantoquita is the ratio of 1 ︰ 1.2 ~ 1.5, is rapidly added concentration as 0.33 ~ 0.42moL/L hydrazine hydrates
Solution is stored at room temperature 1 ~ 3h after continuing stirring；
（6）To step（5）3 ~ 5mL acetone is added in solution after middle standing, is then filtered, cleaned, is dried in vacuo
Afterwards, copper/cuprous oxide core-shell structured nanomaterials are obtained.
Preferably, step（6）The vacuum drying condition is 60 ~ 80 DEG C of dry 3 ~ 5h.
Preferably, the mantoquita is copper sulphate, copper chloride, copper nitrate or copper acetate.
Beneficial effects of the present invention：Copper/cuprous oxide core-shell structured nanomaterials prepared by the present invention, with other pair of gold
Belong to and more metal nucleocapsids are compared, this structure belongs to monometallic multiphase composite construction, and purity is high, and manufacturing cost is low, simultaneously
Maintain the superior function of nucleocapsid；This method process control, easy to operate, low energy consumption, stability is strong, prepared by this method
Copper-based monometallic core-shell structured nanomaterials can be widely applied to grinding for the fields such as photocatalysis, photoelectrocatalysis and solar cell
Study carefully.
Description of the drawings
Fig. 1 is the XRD diagram piece of copper/cuprous oxide core-shell structured nanomaterials prepared by the embodiment of the present invention 1；
Fig. 2 is the TEM pictures of copper/cuprous oxide core-shell structured nanomaterials prepared by the embodiment of the present invention 1；
Fig. 3 is that copper/cuprous oxide core-shell structured nanomaterials prepared by the embodiment of the present invention 5 carry out photocatalysis experiment letter
Figure.
Specific embodiment
With reference to specific example, further the present invention will be described.
Embodiment 1
The preparation method of the present embodiment copper/cuprous oxide core-shell structured nanomaterials, specifically includes following steps：
（1）Using cupric sulfate pentahydrate as copper source, weigh 1.0g cupric sulfate pentahydrates and be dissolved in 80mL deionized waters, be configured to dense
The copper-bath for 0.05moL/L is spent, the hydrazine hydrate solution 0.6g that mass fraction is 80% is measured, deionized water is added to be diluted to
30mL is configured to the hydrazine hydrate solution that concentration is 0.32moL/L, then under agitation, rubs according to copper ion and hydrazine hydrate
Your ratio is the ratio of 1 ︰ 2.4, and hydrazine hydrate solution is added dropwise into copper-bath, and solution gradually becomes aubergine by blueness at this time,
Show that copper nano-particle has generated, continue stirring after ten minutes, be stored at room temperature 1h；
（2）By step（1）It after mixed liquor after middle standing filters, is cleaned, after ethyl alcohol cleaning three times, then uses water
After cleaning is neutral to filtrate, filter cake preservation is formed into suspension in water；
（3）According to step（2）The mass ratio of filter cake and mantoquita is the ratio and cetyl trimethylammonium bromide of 1 ︰ 5.8
The ratio that mass ratio with mantoquita is 1 ︰ 50, weighs 1.48g cupric sulfate pentahydrates, 0.03g cetyl trimethylammonium bromides are complete
Fully dissolved stirs evenly in 100mL deionized waters, obtains mixed liquor A；
（4）According to step（3）The molar ratio of middle mantoquita and sodium hydroxide is the ratio of 1 ︰ 2.5, weighs 0.59g sodium hydroxides
It is dissolved completely in 50mL deionized waters, the sodium hydroxide solution that concentration is 0.3moL/L is configured to, then by step（2）In
Suspension ultrasound 10 minutes, after being uniformly dispersed, sodium hydroxide solution is added thereto, is stirred and evenly mixed, obtains mixed liquid B；
（5）While stirring by step（3）Mixed liquor A and step（4）Mixed liquid B be uniformly mixed, and according to hydrazine hydrate
With step（3）Middle mantoquita molar ratio be 1 ︰ 1.2 ratio, be rapidly added concentration be 0.33moL/L hydrazine hydrate solution, solution by
Blueness gradually becomes brick-red, shows there is cuprous oxide generation, continues to be stored at room temperature 1h, wherein hydrazine hydrate solution after stirring 30s
Process for preparation be：The hydrazine hydrate 0.31g that mass fraction is 80% is measured, deionized water is added to be diluted to 15mL, being configured to concentration is
The hydrazine hydrate solution of 0.33moL/L；
（6）To step（5）3mL acetone is added in solution after middle standing, then by product collected by suction, respectively with anhydrous
Ethyl alcohol and deionized water rinsing 3 times so that filtrate is in neutrality, and after 60 DEG C are dried in vacuo 4h, obtains copper/cuprous oxide nucleocapsid knot
Structure nano material.
Copper manufactured in the present embodiment/cuprous oxide core-shell structured nanomaterials carries out XRD detections, as shown in Figure 1, from collection of illustrative plates
In as can be seen that clearly, and there are not other miscellaneous peaks in the peak of copper and cuprous oxide, it is pure copper to show the substance prepared
And cuprous oxide, no other substances exist；TEM image such as Fig. 2 understands that prepared substance is really nucleocapsid, nucleocapsid
Layering is apparent, the whole unifonn spherical more smooth in surface, and the deeper inner round portion of color is copper nano particles, outer layer color
Shallower region is cuprous oxide particle.
Embodiment 2
The preparation method of the present embodiment copper/cuprous oxide core-shell structured nanomaterials, specifically includes following steps：
（1）It using Copper dichloride dihydrate as copper source, weighs 1.0g Copper dichloride dihydrates and is dissolved in 100mL deionized waters, configure
Into the copper chloride solution that concentration is 0.06moL/L, the hydrazine hydrate solution 0.79g that mass fraction is 80%, deionized water dilution are measured
To 50mL, the hydrazine hydrate solution that concentration is 0.25moL/L is configured to, then under agitation, according to copper ion and hydrazine hydrate
Molar ratio is the ratio of 1 ︰ 2.1, hydrazine hydrate solution is added dropwise into copper chloride solution, solution is gradually become purplish red by blueness at this time
Color shows that copper nano-particle has generated, and continues stirring after ten minutes, is stored at room temperature 2h；
（2）By step（1）It after mixed liquor after middle standing filters, is cleaned, after ethyl alcohol cleaning three times, then uses water
After cleaning is neutral to filtrate, filter cake preservation is formed into suspension in water；
（3）According to step（2）The mass ratio of filter cake and mantoquita is the ratio and cetyl trimethylammonium bromide of 1 ︰ 3.7
The ratio that mass ratio with mantoquita is 1 ︰ 56, weighs 1.39 g Copper dichloride dihydrates, 0.025g cetyl trimethylammonium bromides
CTAB is dissolved completely in 100mL deionized waters, stirs evenly, obtains mixed liquor A；
（4）According to step（3）The molar ratio of middle mantoquita and sodium hydroxide is the ratio of 1 ︰ 2.3, weighs 0.75g sodium hydroxides
It is dissolved completely in 80mL deionized waters, the sodium hydroxide solution that concentration is 0.23moL/L is configured to, then by step（2）In
Suspension ultrasound 10 minutes, be uniformly dispersed, be added in sodium hydroxide solution, stir and evenly mix, obtain mixed liquid B；
（5）While stirring by step（3）Mixed liquor A and step（4）Mixed liquid B be uniformly mixed, and according to hydrazine hydrate
With step（3）The molar ratio of middle mantoquita is the ratio of 1 ︰ 1.3, is rapidly added the hydrazine hydrate solution of 0.42moL/L, solution is by blueness
It gradually becomes brick-red, shows there is cuprous oxide generation, continue to stir that 2h is stored at room temperature after 30s, wherein hydrazine hydrate solution is matched somebody with somebody
Process processed is：The hydrazine hydrate 0.39g that mass fraction is 80% is measured, deionized water is added to be diluted to 15mL, being configured to concentration is
The hydrazine hydrate solution of 0.42moL/L；
（6）To step（5）4mL acetone is added in solution after middle standing, then by product collected by suction, respectively with anhydrous
Ethyl alcohol and deionized water rinsing 3 times so that filtrate is in neutrality, and after 70 DEG C are dried in vacuo 3h, obtains copper/cuprous oxide nucleocapsid knot
Structure nano material.
Copper manufactured in the present embodiment/cuprous oxide core-shell structured nanomaterials carry out XRD detections, can from collection of illustrative plates
Go out, the peak of copper and cuprous oxide clearly, and other miscellaneous peaks does not occur, shows that the substance prepared is sub- for pure copper and oxidation
Copper, no other substances exist；By TEM image, prepared substance is really nucleocapsid, and nucleocapsid layering is apparent, whole
Body is in the more smooth unifonn spherical in surface, and the deeper inner round portion of color is copper nano particles, the shallower region of outer layer color
For cuprous oxide particle.
Embodiment 3
The preparation method of the present embodiment copper/cuprous oxide core-shell structured nanomaterials, specifically includes following steps：
（1）Using Copper dichloride dihydrate as copper source, weigh 1.2g Copper dichloride dihydrates and be dissolved in 100mL ultra-pure waters, be configured to
Concentration is the copper chloride solution of 0.07moL/L, measures the hydrazine hydrate solution 1.1g that mass fraction is 80%, and ultra-pure water is diluted to
50mL is configured to the hydrazine hydrate solution that concentration is 0.35moL/L, then under agitation, rubs according to copper ion and hydrazine hydrate
Your ratio is the ratio of 1 ︰ 2.5, and hydrazine hydrate solution is added dropwise into copper chloride solution, and solution gradually becomes aubergine by blueness at this time,
Show that copper nano-particle has generated, continue stirring after ten minutes, be stored at room temperature 2h；
（2）By step（1）It after mixed liquor after middle standing filters, is cleaned, after ethyl alcohol cleaning three times, then uses water
After cleaning is neutral to filtrate, filter cake preservation is formed into suspension in water；
（3）According to step（2）The mass ratio of filter cake and mantoquita is the ratio and cetyl trimethylammonium bromide of 1 ︰ 4.5
The ratio that mass ratio with mantoquita is 1 ︰ 56, weighs 2.03g cupric sulfate pentahydrates, 0.036g cetyl trimethylammonium bromides are complete
Fully dissolved stirs evenly in 100mL ultra-pure waters, obtains mixed liquor A；
（4）According to step（3）The molar ratio of middle mantoquita and sodium hydroxide is the ratio of 1 ︰ 2.3, weighs 0.75g sodium hydroxides
It is dissolved completely in 80mL ultra-pure waters, the sodium hydroxide solution that concentration is 0.23moL/L is configured to, then by step（2）In
Suspension ultrasound 10 minutes, is uniformly dispersed, is added in sodium hydroxide solution, stir and evenly mix, obtain mixed liquid B；
（5）While stirring by step（3）Mixed liquor A and step（4）Mixed liquid B be uniformly mixed, and according to hydrazine hydrate
With step（3）The molar ratio of middle mantoquita is the ratio of 1 ︰ 1.4, is rapidly added the hydrazine hydrate solution that concentration is 0.39moL/L, solution
It is gradually become by blueness brick-red, shows there is cuprous oxide generation, continue to be stored at room temperature 2h after stirring 30s, wherein hydrazine hydrate is molten
The process for preparation of liquid is：The hydrazine hydrate 0.36g that mass fraction is 80% is measured, ultra-pure water is added to be diluted to 15mL, being configured to concentration is
The hydrazine hydrate solution of 0.39moL/L；
（6）To step（5）4mL acetone is added in solution after middle standing, then by product collected by suction, respectively with anhydrous
Ethyl alcohol and ultrapure water 3 times so that filtrate is in neutrality, and after 70 DEG C are dried in vacuo 3h, obtains copper/cuprous oxide nucleocapsid
Nano material.
Copper manufactured in the present embodiment/cuprous oxide core-shell structured nanomaterials carry out XRD detections, can from collection of illustrative plates
Go out, the peak of copper and cuprous oxide clearly, and other miscellaneous peaks does not occur, shows that the substance prepared is sub- for pure copper and oxidation
Copper, no other substances exist；By TEM image, prepared substance is really nucleocapsid, and nucleocapsid layering is apparent, whole
Body is in the more smooth unifonn spherical in surface, and the deeper inner round portion of color is copper nano particles, the shallower region of outer layer color
For cuprous oxide particle.
Embodiment 4
The preparation method of the present embodiment copper/cuprous oxide core-shell structured nanomaterials, specifically includes following steps：
（1）It using copper nitrate as copper source, weighs 1.35g copper nitrates and is dissolved in 100mL ultra-pure waters, being configured to concentration is
The copper nitrate solution of 0.072moL/L, measures the hydrazine hydrate solution 0.68g that mass fraction is 80%, and ultra-pure water is diluted to 25mL, matches somebody with somebody
The hydrazine hydrate solution that concentration is 0.43moL/L is made, is 1 ︰ according to copper ion and hydrazine hydrate molar ratio then under agitation
Hydrazine hydrate solution is added dropwise into copper nitrate solution for 1.5 ratio, and solution gradually becomes aubergine by blueness at this time, shows that copper is received
Rice corpuscles has generated, and continues stirring after ten minutes, is stored at room temperature 3h；
（2）By step（1）It after mixed liquor after middle standing filters, is cleaned, after ethyl alcohol cleaning three times, then uses water
After cleaning is neutral to filtrate, filter cake preservation is formed into suspension in water；
（3）According to step（2）The mass ratio of filter cake and mantoquita is the ratio and cetyl trimethylammonium bromide of 1 ︰ 4.3
The ratio that mass ratio with mantoquita is 1 ︰ 50, weighs 1.98 g copper nitrates, and 0.04g cetyl trimethylammonium bromides are completely molten
Solution stirs evenly in 100mL ultra-pure waters, obtains mixed liquor A；
（4）According to step（3）The molar ratio of middle mantoquita and sodium hydroxide is the ratio of 1 ︰ 2, and it is complete to weigh 0.84g sodium hydroxides
Fully dissolved is configured to the sodium hydroxide solution that concentration is 0.26moL/L, then by step in 80mL ultra-pure waters（2）In it is outstanding
Supernatant liquid ultrasound 15 minutes, is uniformly dispersed, and adds in sodium hydroxide solution, stirs and evenly mixs, obtain mixed liquid B；
（5）While stirring by step（3）Mixed liquor A and step（4）Mixed liquid B be uniformly mixed, and according to hydrazine hydrate
With step（3）The molar ratio of middle mantoquita is the ratio of 1 ︰ 1.45, is rapidly added the hydrazine hydrate solution that concentration is 0.37moL/L, molten
Liquid is gradually become brick-red by blueness, shows there is cuprous oxide generation, continues to be stored at room temperature 3h, wherein hydrazine hydrate after stirring 30s
The process for preparation of solution is：The hydrazine hydrate 0.46g that mass fraction is 80% is measured, ultra-pure water is added to be diluted to 20mL, is configured to concentration
For the hydrazine hydrate solution of 0.37moL/L；
（6）To step（5）4mL acetone is added in solution after middle standing, then by product collected by suction, respectively with anhydrous
Ethyl alcohol and ultrapure water 3 times so that filtrate is in neutrality, and after 80 DEG C are dried in vacuo 4h, obtains copper/cuprous oxide nucleocapsid
Nano material.
Copper manufactured in the present embodiment/cuprous oxide core-shell structured nanomaterials carry out XRD detections, can from collection of illustrative plates
Go out, the peak of copper and cuprous oxide clearly, and other miscellaneous peaks does not occur, shows that the substance prepared is sub- for pure copper and oxidation
Copper, no other substances exist；By TEM image, prepared substance is really nucleocapsid, and nucleocapsid layering is apparent, whole
Body is in the more smooth unifonn spherical in surface, and the deeper inner round portion of color is copper nano particles, the shallower region of outer layer color
For cuprous oxide particle.
Embodiment 5
The preparation method of the present embodiment copper/cuprous oxide core-shell structured nanomaterials, specifically includes following steps：
（1）It using copper acetate as copper source, weighs 1.6g copper acetates and is dissolved in 100mL ultra-pure waters, being configured to concentration is
The acetic acid copper solution of 0.08moL/L, measures the hydrazine hydrate solution 0.79g that mass fraction is 80%, and ultra-pure water is diluted to 50mL, matches somebody with somebody
The hydrazine hydrate solution that concentration is 0.25moL/L is made, is 1 ︰ according to copper ion and hydrazine hydrate molar ratio then under agitation
Hydrazine hydrate solution is added dropwise into acetic acid copper solution for 1.56 ratio, and solution gradually becomes aubergine by blueness at this time, shows that copper is received
Rice corpuscles has generated, and continues stirring after ten minutes, is stored at room temperature 1h；
（2）By step（1）It after mixed liquor after middle standing filters, is cleaned, after ethyl alcohol cleaning three times, then uses water
After cleaning is neutral to filtrate, filter cake preservation is formed into suspension in water；
（3）According to step（2）The mass ratio of filter cake and mantoquita is the ratio and cetyl trimethylammonium bromide of 1 ︰ 4.3
With the ratio that the mass ratio of mantoquita is 1 ︰ 44,2.2 1g copper acetates are weighed, 0.05g cetyl trimethylammonium bromides CTAB is complete
Fully dissolved stirs evenly in 100mL ultra-pure waters, obtains mixed liquor A；
（4）According to step（3）The molar ratio of middle mantoquita and sodium hydroxide is the ratio of 1 ︰ 2.3, weighs 1.02g sodium hydroxides
It is dissolved completely in 100mL ultra-pure waters, the sodium hydroxide solution that concentration is 0.25moL/L is configured to, then by step（2）In
Suspension ultrasound 20 minutes, be uniformly dispersed, be added in sodium hydroxide solution, stir and evenly mix, obtain mixed liquid B；
（5）While stirring by step（3）Mixed liquor A and step（4）Mixed liquid B be uniformly mixed, and according to hydrazine hydrate
With step（3）The molar ratio of middle mantoquita is the ratio of 1 ︰ 1.5, is rapidly added the hydrazine hydrate solution that concentration is 0.37moL/L, solution
It is gradually become by blueness brick-red, shows there is cuprous oxide generation, continue to be stored at room temperature 1h after stirring 30s, wherein hydrazine hydrate is molten
The process for preparation of liquid is：The hydrazine hydrate 0.46g that mass fraction is 80% is measured, ultra-pure water is added to be diluted to 20mL, being configured to concentration is
The hydrazine hydrate solution of 0.37moL/L；
（6）To step（5）5mL acetone is added in solution after middle standing, then by product collected by suction, respectively with anhydrous
Ethyl alcohol and ultrapure water 3 times so that filtrate is in neutrality, and after 65 DEG C are dried in vacuo 5h, obtains copper/cuprous oxide nucleocapsid
Nano material.
Copper manufactured in the present embodiment/cuprous oxide core-shell structured nanomaterials carry out XRD detections, can from collection of illustrative plates
Go out, the peak of copper and cuprous oxide clearly, and other miscellaneous peaks does not occur, shows that the substance prepared is sub- for pure copper and oxidation
Copper, no other substances exist；By TEM image, prepared substance is really nucleocapsid, and nucleocapsid layering is apparent, whole
Body is in the more smooth unifonn spherical in surface, and the deeper inner round portion of color is copper nano particles, the shallower region of outer layer color
For cuprous oxide particle.
Copper manufactured in the present embodiment/cuprous oxide core-shell structured nanomaterials are tested applied to photocatalytic degradation Cr VI,
Concrete operations are：The potassium bichromate solution that 150mL initial concentrations are 10.0mg/L is configured, as Cr（VI）Reaction solution, utilization are dilute
Sulfuric acid adjusts its pH as 3；It weighs 1.0g NaCL and 0.5g KI and is dissolved in 150mL ultra-pure waters, caught respectively as electrolyte and hole
Agent is obtained, using platinized platinum as cathode, the FTO electro-conductive glass of supported catalyst is anode, and experiment schematic diagram is illustrated in fig. 3 shown below, by visible
After photo-irradiation reaction 36h, Cr（VI）Concentration become 0.9mg/L, degradation rate reaches 91%, prepared by the results show embodiment
Copper/cuprous oxide core-shell structured nanomaterials have good photocatalysis effect.
Examples detailed above is used for illustrating the present invention rather than limiting the invention, in the spirit and power of the present invention
In the protection domain of profit requirement, to any modifications and changes that the present invention makes, protection scope of the present invention is each fallen within.
Claims (3)
1. the preparation method of a kind of copper/cuprous oxide core-shell structured nanomaterials, which is characterized in that specifically include following steps：
（1）It is the ratio of 1 ︰ 1.5 ~ 2.5 according to mantoquita and hydrazine hydrate molar ratio, concentration is molten for the mantoquita of 0.05 ~ 0.08moL/L
Liquid and the hydrazine hydrate solution that concentration is 0.25 ~ 0.43moL/L mix, when standing no less than 1 is small after mixed liquor is stirred evenly；
（2）By step（1）Mixed liquor after middle standing filters, cleaning, cleans after being neutral to filtrate, and filter cake is preserved in water
Form suspension；
（3）According to step（2）The mass ratio of filter cake and mantoquita is the ratio of 1 ︰ 3.7 ~ 5.8, weighs mantoquita, being configured to concentration is
The copper salt solution of 0.06 ~ 0.11moL/L, then using the mass ratio of cetyl trimethylammonium bromide and mantoquita as the ratio of 1 ︰ 44 ~ 56
Cetyl trimethylammonium bromide is added in the copper salt solution that concentration is 0.06 ~ 0.11moL/L, stirs evenly, obtain by example
Mixed liquor A；
（4）According to step（3）In mantoquita and sodium hydroxide molar ratio be 1 ︰ 2 ~ 2.5 ratio, by concentration for 0.23 ~
The sodium hydroxide solution of 0.30moL/L is added to step（2）Suspension in, sodium hydroxide solution addition before to suspension carry out
It is ultrasonically treated, is stirred and evenly mixed after addition, obtain mixed liquid B；
（5）While stirring by step（3）Mixed liquor A and step（4）Mixed liquid B after mixing, according to hydrazine hydrate with step
Suddenly（3）The molar ratio of middle mantoquita is the ratio of 1 ︰ 1.2 ~ 1.5, is rapidly added concentration as 0.33 ~ 0.42moL/L hydrazine hydrate solutions,
1 ~ 3h is stored at room temperature after continuing stirring；
（6）To step（5）3 ~ 5mL acetone is added in solution after middle standing, is then filtered, cleaned, after vacuum drying, obtained
To copper/cuprous oxide core-shell structured nanomaterials.
2. the preparation method of copper/cuprous oxide core-shell structured nanomaterials according to claim 1, which is characterized in that described
Mantoquita is copper sulphate, copper chloride, copper nitrate or copper acetate.
3. the preparation method of copper/cuprous oxide core-shell structured nanomaterials according to claim 1, which is characterized in that step
（6）The vacuum drying condition is 60 ~ 80 DEG C of dry 3 ~ 5h.
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