CN106041120A - Preparation method of copper/cuprous oxide core-shell structure nanometer material - Google Patents
Preparation method of copper/cuprous oxide core-shell structure nanometer material Download PDFInfo
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- CN106041120A CN106041120A CN201610478481.6A CN201610478481A CN106041120A CN 106041120 A CN106041120 A CN 106041120A CN 201610478481 A CN201610478481 A CN 201610478481A CN 106041120 A CN106041120 A CN 106041120A
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- copper
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- mantoquita
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- hydrazine hydrate
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000010949 copper Substances 0.000 title claims abstract description 70
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 31
- 239000011258 core-shell material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title abstract description 28
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical group [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title abstract description 5
- 229940112669 cuprous oxide Drugs 0.000 title abstract description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 54
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 54
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 18
- 150000001879 copper Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 76
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical group O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 33
- 239000002086 nanomaterial Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 abstract description 39
- 239000002105 nanoparticle Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 19
- 239000012498 ultrapure water Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 10
- 239000008187 granular material Substances 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 244000061458 Solanum melongena Species 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 241001062009 Indigofera Species 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 206010037211 Psychomotor hyperactivity Diseases 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- 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
-
- 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
Abstract
The invention discloses a preparation method of a copper/cuprous oxide core-shell structure nanometer material. The method comprises the steps that soluble copper salt serves as a copper source, hydrazine hydrate serves as a reduction agent, cetyl trimethyl ammonium bromide (CTAB) serves as a surface active agent, and the copper/cuprous oxide core-shell structure nanometer material with copper nano particles as a core and cuprous oxide as a shell is prepared under the condition of the room temperature. The metal core-shell structure nanometer material prepared through the method can be used for the application research of the fields of photocatalysis, photoelectrocatalysis, solar cells and the like; and the preparation process is controllable, operation is easy, energy consumption is low, and stability is high.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, relate to reducing process under liquid phase environment and prepare monometallic different phase
The method of composite construction, particularly relate to the preparation method of a kind of copper/Red copper oxide core-shell structured nanomaterials.
Background technology
Nano material is also known as ultramicro powder material it is considered to be 21 century " the most promising material ", and nanostructured is existing
The advantages such as the characteristic of nanoparticle such as quantum size effect, small-size effect, skin effect, exist again and are drawn by nanostructured combination
New effect such as quantum coupling effect and the cooperative effect etc. risen, at catalytic reaction, macromolecular material, chemical sensor, solar energy
The many aspects such as battery have important using value.
Core-shell composite nanoparticle is a kind of special nanostructured, with spherical at micron to nano grade of a size
Granule is core, wraps several layers of nano thin-film on its surface and the one that formed is combined heterogeneous structure, has that specific surface area is big, density
The features such as low, superior photoelectric property, and the tune of composite performance can be realized by the control thickness of nucleocapsid, the size etc. of particle diameter
Control.
Nano copper particle and complex thereof have overactivity surface, good electric conductivity, photism and catalytic performance, and honest and clean
Valency is easy to get, and is paid close attention to by the most widely at scientific research field, in view of its every premium properties, has been widely used in catalysis anti-
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, at visible ray
Excited particles can produce the electron-hole pair with Strong oxdiative reproducibility under irradiating, thus there is efficient visible light catalytic
Can, can be applicable to the fields such as photocatalysis, electro-catalysis, solaode, additionally, the most repeatedly report both at home and abroad and made by Red copper oxide
Research for a kind of gas sensor.
Metal/semiconductor nano-core-shell structure is as a kind of novel nano composite material, the spy of this metal/semiconductor
Different combination so that it is be provided simultaneously with the dual property of metal nanoparticle and semi-conductor nano particles, in the phase of both different performances
Mutually under synergism so that it is produce special optical, electrical, the catalytic performance being much better than one-component, so far, have no relevant liquid
Phase reducing process prepares the report of copper/cuprous nano catalyst with core-casing structure.
Summary of the invention
The present invention is directed to the disappearance that this field prior art exists, it is provided that a kind of copper/Red copper oxide nuclear shell structure nano material
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 mol ratio, by molten for the mantoquita that concentration is 0.05 ~ 0.08moL/L
Liquid and the hydrazine hydrate solution mixing that concentration is 0.25 ~ 0.43moL/L, stand no less than 1 hour after being stirred by mixed liquor；
(2) the mixed liquor sucking filtration after standing in step (1), cleaning, clean after being neutrality to filtrate, be saved in water by filter cake
Form suspension；
(3) according to the ratio that mass ratio is 1 3.7 ~ 5.8 of step (2) filter cake Yu mantoquita, weighing mantoquita, being configured to concentration is
The copper salt solution of 0.06 ~ 0.11moL/L, then with ratio that the mass ratio of cetyl trimethylammonium bromide Yu mantoquita is 1 44 ~ 56
Example, adds to cetyl trimethylammonium bromide in the copper salt solution that concentration is 0.06 ~ 0.11moL/L, stirs, obtain
Mixed liquor A；
(4) according to the ratio that mol ratio is 12 ~ 2.5 of the mantoquita in step (3) Yu sodium hydroxide, it is 0.23 ~ 0.30 by concentration
The sodium hydroxide solution of moL/L add to step (2) ultrasonic after suspension in, stirring and evenly mixing, obtain mixed liquid B；
(5) while stirring by after the mixed liquor A of step (3) and the mixed liquid B mix homogeneously of step (4), according to hydrazine hydrate and step
Suddenly the ratio that mol ratio is 1 1.2 ~ 1.5 of mantoquita in (3), being rapidly added concentration is 0.33 ~ 0.42moL/L hydrazine hydrate solution,
Continuing stirring, rear chamber is gentle and quiet puts 1 ~ 3h；
(6) solution after standing in step (5) adds 3 ~ 5mL acetone, then carries out sucking filtration, cleaning, after vacuum drying,
To copper/Red copper oxide core-shell structured nanomaterials.
Preferably, step (6) described vacuum drying condition is 60 ~ 80 DEG C of dry 3 ~ 5h.
Preferably, described mantoquita is copper sulfate, copper chloride, copper nitrate or Schweinfurt green.
Beneficial effects of the present invention: the copper prepared by the present invention/Red copper oxide core-shell structured nanomaterials, with other pair of gold
Belonging to and many metal core shell structure is compared, this structure belongs to monometallic heterogeneous composite construction, and purity is high, and preparation cost is low, simultaneously
Maintain the superior function of nucleocapsid structure；This method process control, simple to operate, energy consumption is low, stability is strong, prepared by the method
Cuprio monometallic core-shell structured nanomaterials can be widely applied to grinding of the fields such as photocatalysis, photoelectrocatalysis and solaode
Study carefully.
Accompanying drawing explanation
Fig. 1 is the XRD figure sheet of the copper/Red copper oxide core-shell structured nanomaterials of the embodiment of the present invention 1 preparation；
Fig. 2 is the TEM picture of the copper/Red copper oxide core-shell structured nanomaterials of the embodiment of the present invention 1 preparation；
Fig. 3 is that the copper/Red copper oxide core-shell structured nanomaterials of the embodiment of the present invention 5 preparation carries out photocatalysis experiment sketch.
Detailed description of the invention
Below in conjunction with instantiation, the present invention will be described further.
Embodiment 1
The preparation method of the present embodiment copper/Red copper oxide core-shell structured nanomaterials, specifically includes following steps:
(1) with copper sulphate pentahydrate for copper source, weighing 1.0g copper sulphate pentahydrate and be dissolved in 80mL deionized water, being configured to concentration is
The copper-bath of 0.05moL/L, measures the hydrazine hydrate solution 0.6g that mass fraction is 80%, adds deionized water and be diluted to 30mL,
It is configured to the hydrazine hydrate solution that concentration is 0.32moL/L, the most under agitation, according to copper ion with hydrazine hydrate mol ratio is
The ratio of 1 2.4, drips hydrazine hydrate solution in copper-bath, and now solution is gradually become aubergine by blueness, shows copper
Nanoparticle has generated, and after continuing stirring 10 minutes, room temperature stands 1h；
(2) after the mixed liquor sucking filtration after standing in step (1), it is carried out, after utilizing ethanol purge three times, then cleans with water
After being neutrality to filtrate, filter cake is saved in water formation suspension；
(3) according to step (2) filter cake and the ratio that mass ratio is 1 5.8 of mantoquita and cetyl trimethylammonium bromide and copper
The mass ratio of salt is the ratio of 1 50, weighs 1.48g copper sulphate pentahydrate, and 0.03g cetyl trimethylammonium bromide is the most molten
Solution, in 100mL deionized water, stirs, and obtains mixed liquor A；
(4) according to the ratio that mol ratio is 1 2.5 of mantoquita in step (3) Yu sodium hydroxide, 0.59g sodium hydroxide is weighed complete
It is dissolved in 50mL deionized water, is configured to the sodium hydroxide solution that concentration is 0.3moL/L, then by hanging in step (2)
Ultrasonic 10 minutes of supernatant liquid, after being uniformly dispersed, is added thereto sodium hydroxide solution, stirring and evenly mixing, obtains mixed liquid B；
(5) while stirring by mixed liquor A and the mixed liquid B mix homogeneously of step (4) of step (3), and according to hydrazine hydrate and step
Suddenly in (3), mantoquita mol ratio is the ratio of 1 1.2, is rapidly added the hydrazine hydrate solution that concentration is 0.33moL/L, and solution is by blueness
Gradually becoming brick-red, show have Red copper oxide to generate, continuing stirring, 30s rear chamber is gentle and quiet puts 1h, wherein the joining of hydrazine hydrate solution
Process processed is: measures the hydrazine hydrate 0.31g that mass fraction is 80%, adds deionized water and be diluted to 15mL, and being configured to concentration is
The hydrazine hydrate solution of 0.33moL/L；
(6) solution after standing in step (5) adds 3mL acetone, then by product collected by suction, uses dehydrated alcohol respectively
With deionized water rinsing 3 times so that filtrate is neutrality, after 60 DEG C of vacuum drying 4h, obtain copper/Red copper oxide nucleocapsid structure and receive
Rice material.
Copper prepared by the present embodiment/Red copper oxide core-shell structured nanomaterials carries out XRD detection, as it is shown in figure 1, from collection of illustrative plates
In it can be seen that clearly, and there are not other miscellaneous peaks in the peak of copper and Red copper oxide, show that the material of preparation is pure copper
And Red copper oxide, exist without other materials；TEM image such as Fig. 2 understands, and prepared material is nucleocapsid structure really, nucleocapsid
Substantially, the overall unifonn spherical more smoothed in surface, the deeper inner round portion of color is copper nano particles, outer layer color in layering
Shallower region is Red copper oxide granule.
Embodiment 2
The preparation method of the present embodiment copper/Red copper oxide core-shell structured nanomaterials, specifically includes following steps:
(1) with Copper dichloride dihydrate for copper source, weigh 1.0g Copper dichloride dihydrate and be dissolved in 100mL deionized water, be configured to dense
Degree is the copper chloride solution of 0.06moL/L, measures the hydrazine hydrate solution 0.79g that mass fraction is 80%, and deionized water is diluted to
50mL, is configured to the hydrazine hydrate solution that concentration is 0.25moL/L, the most under agitation, rubs with hydrazine hydrate according to copper ion
Your ratio is the ratio of 1 2.1, drips hydrazine hydrate solution in copper chloride solution, and now solution is gradually become aubergine by blueness,
Showing that copper nano-particle has generated, after continuing stirring 10 minutes, room temperature stands 2h；
(2) after the mixed liquor sucking filtration after standing in step (1), it is carried out, after utilizing ethanol purge three times, then cleans with water
After being neutrality to filtrate, filter cake is saved in water formation suspension；
(3) according to step (2) filter cake and the ratio that mass ratio is 1 3.7 of mantoquita and cetyl trimethylammonium bromide and copper
The mass ratio of salt is the ratio of 1 56, weighs 1.39 g Copper dichloride dihydrates, 0.025g cetyl trimethylammonium bromide CTAB,
It is dissolved completely in 100mL deionized water, stirs, obtain mixed liquor A；
(4) according to the ratio that mol ratio is 1 2.3 of mantoquita in step (3) Yu sodium hydroxide, 0.75g sodium hydroxide is weighed complete
It is dissolved in 80mL deionized water, is configured to the sodium hydroxide solution that concentration is 0.23moL/L, then by hanging in step (2)
Ultrasonic 10 minutes of supernatant liquid, is uniformly dispersed, joins in sodium hydroxide solution, and stirring and evenly mixing obtains mixed liquid B；
(5) while stirring by mixed liquor A and the mixed liquid B mix homogeneously of step (4) of step (3), and according to hydrazine hydrate and step
Suddenly the ratio that mol ratio is 1 1.3 of mantoquita in (3), is rapidly added the hydrazine hydrate solution of 0.42moL/L, and solution is by blueness gradually
Becoming brick-red, show have Red copper oxide to generate, continuing stirring, 30s rear chamber is gentle and quiet puts 2h, the wherein preparation of hydrazine hydrate solution
Cheng Wei: measure the hydrazine hydrate 0.39g that mass fraction is 80%, add deionized water and be diluted to 15mL, being configured to concentration is 0.42moL/
The hydrazine hydrate solution of L；
(6) solution after standing in step (5) adds 4mL acetone, then by product collected by suction, uses dehydrated alcohol respectively
With deionized water rinsing 3 times so that filtrate is neutrality, after 70 DEG C of vacuum drying 3h, obtain copper/Red copper oxide nucleocapsid structure and receive
Rice material.
Copper prepared by the present embodiment/Red copper oxide core-shell structured nanomaterials carries out XRD detection, can from collection of illustrative plates
Going out, clearly, and there are not other miscellaneous peaks in the peak of copper and Red copper oxide, shows that the material of preparation is pure copper and oxidation Asia
Copper, exists without other materials；By TEM image, prepared material is nucleocapsid structure really, and nucleocapsid layering is substantially, whole
Body is the unifonn spherical that surface more smooths, and the deeper inner round portion of color is copper nano particles, the region that outer layer color is shallower
For Red copper oxide granule.
Embodiment 3
The preparation method of the present embodiment copper/Red copper oxide core-shell structured nanomaterials, specifically includes following steps:
(1) with Copper dichloride dihydrate for copper source, weigh 1.2g Copper dichloride dihydrate and be dissolved in 100mL ultra-pure water, be configured to concentration
For the copper chloride solution of 0.07moL/L, measuring the hydrazine hydrate solution 1.1g that mass fraction is 80%, ultra-pure water is diluted to 50mL, joins
Make the hydrazine hydrate solution that concentration is 0.35moL/L, the most under agitation, be 1 according to copper ion and hydrazine hydrate mol ratio
The ratio of 2.5, drips hydrazine hydrate solution in copper chloride solution, and now solution is gradually become aubergine by blueness, shows that copper is received
Rice corpuscles has generated, and after continuing stirring 10 minutes, room temperature stands 2h；
(2) after the mixed liquor sucking filtration after standing in step (1), it is carried out, after utilizing ethanol purge three times, then cleans with water
After being neutrality to filtrate, filter cake is saved in water formation suspension；
(3) according to step (2) filter cake and the ratio that mass ratio is 1 4.5 of mantoquita and cetyl trimethylammonium bromide and copper
The mass ratio of salt is the ratio of 1 56, weighs 2.03g copper sulphate pentahydrate, and 0.036g cetyl trimethylammonium bromide is the most molten
Solution, in 100mL ultra-pure water, stirs, and obtains mixed liquor A；
(4) according to the ratio that mol ratio is 1 2.3 of mantoquita in step (3) Yu sodium hydroxide, 0.75g sodium hydroxide is weighed complete
It is dissolved in 80mL ultra-pure water, is configured to the sodium hydroxide solution that concentration is 0.23moL/L, then by the suspension in step (2)
Ultrasonic 10 minutes of liquid, is uniformly dispersed, joins in sodium hydroxide solution, and stirring and evenly mixing obtains mixed liquid B；
(5) while stirring by mixed liquor A and the mixed liquid B mix homogeneously of step (4) of step (3), and according to hydrazine hydrate and step
Suddenly the ratio that mol ratio is 1 1.4 of mantoquita in (3), is rapidly added the hydrazine hydrate solution that concentration is 0.39moL/L, and solution is by indigo plant
Color gradually becomes brick-red, shows have Red copper oxide to generate, continuing stirring, 30s rear chamber is gentle and quiet puts 2h, wherein hydrazine hydrate solution
Process for preparation is: measures the hydrazine hydrate 0.36g that mass fraction is 80%, adds ultra-pure water and be diluted to 15mL, and being configured to concentration is
The hydrazine hydrate solution of 0.39moL/L；
(6) solution after standing in step (5) adds 4mL acetone, then by product collected by suction, uses dehydrated alcohol respectively
With ultrapure water 3 times so that filtrate is neutrality, after 70 DEG C of vacuum drying 3h, obtain copper/Red copper oxide nuclear shell structure nano
Material.
Copper prepared by the present embodiment/Red copper oxide core-shell structured nanomaterials carries out XRD detection, can from collection of illustrative plates
Going out, clearly, and there are not other miscellaneous peaks in the peak of copper and Red copper oxide, shows that the material of preparation is pure copper and oxidation Asia
Copper, exists without other materials；By TEM image, prepared material is nucleocapsid structure really, and nucleocapsid layering is substantially, whole
Body is the unifonn spherical that surface more smooths, and the deeper inner round portion of color is copper nano particles, the region that outer layer color is shallower
For Red copper oxide granule.
Embodiment 4
The preparation method of the present embodiment copper/Red copper oxide core-shell structured nanomaterials, specifically includes following steps:
(1) with copper nitrate for copper source, weighing 1.35g copper nitrate and be dissolved in 100mL ultra-pure water, being configured to concentration is 0.072moL/
The copper nitrate solution of L, measures the hydrazine hydrate solution 0.68g that mass fraction is 80%, and ultra-pure water is diluted to 25mL, is configured to concentration
For the hydrazine hydrate solution of 0.43moL/L, the most under agitation, according to the ratio that copper ion and hydrazine hydrate mol ratio are 1 1.5
Example, drips hydrazine hydrate solution in copper nitrate solution, and now solution is gradually become aubergine by blueness, shows that copper nano-particle is
Through generating, after continuing stirring 10 minutes, room temperature stands 3h；
(2) after the mixed liquor sucking filtration after standing in step (1), it is carried out, after utilizing ethanol purge three times, then cleans with water
After being neutrality to filtrate, filter cake is saved in water formation suspension；
(3) according to step (2) filter cake and the ratio that mass ratio is 1 4.3 of mantoquita and cetyl trimethylammonium bromide and copper
The mass ratio of salt is the ratio of 1 50, weighs 1.98 g copper nitrates, 0.04g cetyl trimethylammonium bromide, is dissolved completely in
In 100mL ultra-pure water, stir, obtain mixed liquor A；
(4) according to the ratio that mol ratio is 12 of mantoquita in step (3) Yu sodium hydroxide, 0.84g sodium hydroxide is weighed the most molten
Solution, in 80mL ultra-pure water, is configured to the sodium hydroxide solution that concentration is 0.26moL/L, then by the suspension in step (2)
Ultrasonic 15 minutes, it is uniformly dispersed, adds in sodium hydroxide solution, stirring and evenly mixing, obtain mixed liquid B；
(5) while stirring by mixed liquor A and the mixed liquid B mix homogeneously of step (4) of step (3), and according to hydrazine hydrate and step
Suddenly the ratio that mol ratio is 1 1.45 of mantoquita in (3), is rapidly added the hydrazine hydrate solution that concentration is 0.37moL/L, solution by
Blueness gradually becomes brick-red, shows have Red copper oxide to generate, and continuing stirring, 30s rear chamber is gentle and quiet puts 3h, wherein hydrazine hydrate solution
Process for preparation be: measuring the hydrazine hydrate 0.46g that mass fraction is 80%, add ultra-pure water and be diluted to 20mL, being configured to concentration is
The hydrazine hydrate solution of 0.37moL/L；
(6) solution after standing in step (5) adds 4mL acetone, then by product collected by suction, uses dehydrated alcohol respectively
With ultrapure water 3 times so that filtrate is neutrality, after 80 DEG C of vacuum drying 4h, obtain copper/Red copper oxide nuclear shell structure nano
Material.
Copper prepared by the present embodiment/Red copper oxide core-shell structured nanomaterials carries out XRD detection, can from collection of illustrative plates
Going out, clearly, and there are not other miscellaneous peaks in the peak of copper and Red copper oxide, shows that the material of preparation is pure copper and oxidation Asia
Copper, exists without other materials；By TEM image, prepared material is nucleocapsid structure really, and nucleocapsid layering is substantially, whole
Body is the unifonn spherical that surface more smooths, and the deeper inner round portion of color is copper nano particles, the region that outer layer color is shallower
For Red copper oxide granule.
Embodiment 5
The preparation method of the present embodiment copper/Red copper oxide core-shell structured nanomaterials, specifically includes following steps:
(1) with Schweinfurt green for copper source, weighing 1.6g Schweinfurt green and be dissolved in 100mL ultra-pure water, being configured to concentration is 0.08moL/L
Schweinfurt green solution, measure the hydrazine hydrate solution 0.79g that mass fraction is 80%, ultra-pure water is diluted to 50mL, is configured to concentration and is
The hydrazine hydrate solution of 0.25moL/L, the most under agitation, according to the ratio that copper ion and hydrazine hydrate mol ratio are 1 1.56
Example, drips hydrazine hydrate solution in Schweinfurt green solution, and now solution is gradually become aubergine by blueness, shows that copper nano-particle is
Through generating, after continuing stirring 10 minutes, room temperature stands 1h；
(2) after the mixed liquor sucking filtration after standing in step (1), it is carried out, after utilizing ethanol purge three times, then cleans with water
After being neutrality to filtrate, filter cake is saved in water formation suspension；
(3) according to step (2) filter cake and the ratio that mass ratio is 1 4.3 of mantoquita and cetyl trimethylammonium bromide and copper
The mass ratio of salt is the ratio of 1 44, weighs 2.2 1g Schweinfurt greens, and 0.05g cetyl trimethylammonium bromide CTAB is the most molten
Solution, in 100mL ultra-pure water, stirs, and obtains mixed liquor A；
(4) according to the ratio that mol ratio is 1 2.3 of mantoquita in step (3) Yu sodium hydroxide, 1.02g sodium hydroxide is weighed complete
It is dissolved in 100mL ultra-pure water, is configured to the sodium hydroxide solution that concentration is 0.25moL/L, then by hanging in step (2)
Ultrasonic 20 minutes of supernatant liquid, is uniformly dispersed, joins in sodium hydroxide solution, and stirring and evenly mixing obtains mixed liquid B；
(5) while stirring by mixed liquor A and the mixed liquid B mix homogeneously of step (4) of step (3), and according to hydrazine hydrate and step
Suddenly the ratio that mol ratio is 1 1.5 of mantoquita in (3), is rapidly added the hydrazine hydrate solution that concentration is 0.37moL/L, and solution is by indigo plant
Color gradually becomes brick-red, shows have Red copper oxide to generate, continuing stirring, 30s rear chamber is gentle and quiet puts 1h, wherein hydrazine hydrate solution
Process for preparation is: measures the hydrazine hydrate 0.46g that mass fraction is 80%, adds ultra-pure water and be diluted to 20mL, and being configured to concentration is
The hydrazine hydrate solution of 0.37moL/L；
(6) solution after standing in step (5) adds 5mL acetone, then by product collected by suction, uses dehydrated alcohol respectively
With ultrapure water 3 times so that filtrate is neutrality, after 65 DEG C of vacuum drying 5h, obtain copper/Red copper oxide nuclear shell structure nano
Material.
Copper prepared by the present embodiment/Red copper oxide core-shell structured nanomaterials carries out XRD detection, can from collection of illustrative plates
Going out, clearly, and there are not other miscellaneous peaks in the peak of copper and Red copper oxide, shows that the material of preparation is pure copper and oxidation Asia
Copper, exists without other materials；By TEM image, prepared material is nucleocapsid structure really, and nucleocapsid layering is substantially, whole
Body is the unifonn spherical that surface more smooths, and the deeper inner round portion of color is copper nano particles, the region that outer layer color is shallower
For Red copper oxide granule.
Copper prepared by the present embodiment/Red copper oxide core-shell structured nanomaterials is applied to the experiment of photocatalytic degradation Cr VI,
Concrete operations are: configuration 150mL initial concentration is the potassium bichromate solution of 10.0mg/L, as Cr(VI) reactant liquor, utilize dilute
It is 3 that sulphuric acid regulates its pH；Weigh 1.0g NaCL and 0.5g KI and be dissolved in 150mL ultra-pure water, catch respectively as electrolyte and hole
Obtaining agent, with platinized platinum as negative electrode, the FTO electro-conductive glass of supported catalyst is anode, and experiment sketch 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 result display embodiment
Copper/Red copper oxide core-shell structured nanomaterials has good photocatalysis effect.
Examples detailed above is used for illustrating the present invention rather than limiting the invention, in spirit and the power of the present invention
In the protection domain that profit requires, any modifications and changes that the present invention is made, each fall within protection scope of the present invention.
Claims (3)
1. the preparation method of copper/Red copper oxide core-shell structured nanomaterials, it is characterised in that specifically include following steps:
(1) it is the ratio of 1 1.5 ~ 2.5 according to mantoquita and hydrazine hydrate mol ratio, by molten for the mantoquita that concentration is 0.05 ~ 0.08moL/L
Liquid and the hydrazine hydrate solution mixing that concentration is 0.25 ~ 0.43moL/L, stand no less than 1 hour after being stirred by mixed liquor；
(2) the mixed liquor sucking filtration after standing in step (1), cleaning, clean after being neutrality to filtrate, be saved in water by filter cake
Form suspension；
(3) according to the ratio that mass ratio is 1 3.7 ~ 5.8 of step (2) filter cake Yu mantoquita, weighing mantoquita, being configured to concentration is
The copper salt solution of 0.06 ~ 0.11moL/L, then with ratio that the mass ratio of cetyl trimethylammonium bromide Yu mantoquita is 1 44 ~ 56
Example, adds to cetyl trimethylammonium bromide in the copper salt solution that concentration is 0.06 ~ 0.11moL/L, stirs, obtain
Mixed liquor A；
(4) according to the ratio that mol ratio is 12 ~ 2.5 of the mantoquita in step (3) Yu sodium hydroxide, by concentration be 0.23 ~
The sodium hydroxide solution of 0.30moL/L add to step (2) ultrasonic after suspension in, stirring and evenly mixing, obtain mixed liquid B；
(5) while stirring by after the mixed liquor A of step (3) and the mixed liquid B mix homogeneously of step (4), according to hydrazine hydrate and step
Suddenly the ratio that mol ratio is 1 1.2 ~ 1.5 of mantoquita in (3), being rapidly added concentration is 0.33 ~ 0.42moL/L hydrazine hydrate solution,
Continuing stirring, rear chamber is gentle and quiet puts 1 ~ 3h；
(6) solution after standing in step (5) adds 3 ~ 5mL acetone, then carries out sucking filtration, cleaning, after vacuum drying,
To copper/Red copper oxide core-shell structured nanomaterials.
The preparation method of copper/Red copper oxide core-shell structured nanomaterials the most according to claim 1, it is characterised in that described
Mantoquita is copper sulfate, copper chloride, copper nitrate or Schweinfurt green.
The preparation method of copper/Red copper oxide core-shell structured nanomaterials the most according to claim 1, it is characterised in that step
(6) described vacuum drying condition is 60 ~ 80 DEG C of dry 3 ~ 5h.
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