CN106495204A - A kind of preparation method of single dispersing yolk shell structure C uO microballoons - Google Patents
A kind of preparation method of single dispersing yolk shell structure C uO microballoons Download PDFInfo
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- CN106495204A CN106495204A CN201610828185.4A CN201610828185A CN106495204A CN 106495204 A CN106495204 A CN 106495204A CN 201610828185 A CN201610828185 A CN 201610828185A CN 106495204 A CN106495204 A CN 106495204A
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- yolk
- shell structure
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 210000002969 egg yolk Anatomy 0.000 title abstract 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 7
- 229940043267 rhodamine b Drugs 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 abstract description 11
- 238000000137 annealing Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 108
- 239000000243 solution Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- 229960004643 cupric oxide Drugs 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000005751 Copper oxide Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 229910000431 copper oxide Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000005809 Prunus persica Species 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 240000001949 Taraxacum officinale Species 0.000 description 1
- 235000005187 Taraxacum officinale ssp. officinale Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/39—
-
- B01J35/397—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention discloses a kind of preparation method of single dispersing yolk shell structure C uO microballoons, copper acetate or copper acetate are disperseed fully to dissolve in ethylene glycol with PVP, solution is transferred to heated at constant temperature reaction in autoclave, after question response terminates, natural cooling is settled, remove supernatant liquor, blue solid product is obtained after suction filtration in vacuum drying chamber, dries the CuO microballoon predecessors that there must be single dispersing characteristic yolk shell structures to constant weight；Using the resistance furnace of controllable heating rate, the temperature control annealing in air atmosphere by the predecessor for being obtained is obtained by being cooled to room temperature.The present invention realizes the controllable design to structure cleverly with ethylene glycol simultaneously as organic solvent and structure directing agent；Raw material is easy to get, with low cost, almost pollution-free to environment, and product is easily separated, and purity is high, and pattern is good and homogeneous, and preparation process is simple is easy to operate, and photochemical properties are significantly higher than other structures.
Description
Technical field
A kind of a kind of the present invention relates to preparation method of inorganic functional micro-nanometer structural material, more particularly to single dispersing
The preparation method of yolk-shell structure C uO microballoons.
Background technology
CuO is p-type arrowband based semiconductor, about 1.2 eV of energy gap, suffers from potential application in many fields, such as
Sensor, high-performance electric chemistry capacitor, lithium ion battery negative material, catalysis and photochemical catalyst, solar cell etc..Closely several
Year, as the excellent properties that different size and pattern micro-/ nano CuO materials have have attracted more and more material science scientific researches
The concern of worker.
At present, numerous research groups developed many methods come controllable standby have the CuO of ad hoc structure and pattern micro-/receive
Rice materials application is in these fields, and achieves good effect.Such as tool is prepared in thermal and hydric environment using surfactant
There is the copper oxide nanometer flower-based of chiral structure；In hydro-thermal solvent thermal environment, it is prepared for being formed by self assembly by rhombus nanobelt
Dandelion shape CuO mesoporous crystals；At ambient temperature, it is prepared for recklessly using dehydrating nanometer wire Kocide SD aqueous solution
Peach shape copper oxide nanometer particle；Foliaceous is achieved in microwave radiation technology thermal and hydric environment and prepared by spherical copper oxide nanometer particle；
Overlength lenticular cupric oxide nano line is prepared for by the method for liquid phase chemical at room temperature；Prepared by quick wet chemical method
Copper oxide nano-belt and copper oxide nanometer flower-based；It is prepared for being classified butterfly sheet by the method for being heat-treated copper-based coordination polymer
Copper oxide nano material and hollow oxide copper nanometer tube；By metal-organic framework templated synthesis of the heat treatment based on copper
Go out the octahedral cupric oxide hollow frame of porous.
Inventor has found that a kind of CuO microballoons with single dispersing yolk-shell structures are in photochemical properties application aspect
Can make full use of light multiple reflections and scattering strengthening the capture ability of photon, and then improve the utilization ratio of light, realize
There is highly important Research Significance and practical value to the controllable standby with yolk-shell structure C uO microballoons.However, arriving
So far, the report of correlation technique is had no, and solvent hot preparation is carried out by using a kind of simple, green solvent and is had single point
The CuO microballoons predecessor of scattered yolk-shell structures simultaneously combines simple method for annealing acquisition single dispersing yolk-shell structures
CuO microballoons were not more reported.
Content of the invention
In order to solve the deficiencies in the prior art, it is an object of the invention to provide a kind of simple, green solvent
Hot legal system is got everything ready the CuO microballoon predecessors of the yolk-shell structures for having single dispersing characteristic, by directly entering in air ambient
Row annealing, realizes the preparation of the CuO microballoons of the yolk-shell structures with single dispersing characteristic.
For reaching above-mentioned purpose, the technology used in the present invention means are：A kind of single dispersing yolk-shell structure C uO are micro-
The preparation method of ball, step include：
First, the mixture of a certain amount of copper acetate or copper acetate and polyvinylpyrrolidone is taken, the appearance equipped with ethylene glycol is dispersed in
In device, stir to fully dissolving, form as clear as crystal blue solution；
2nd, the blue solution obtained in step one is transferred in autoclave, 140～200 DEG C of heated at constant temperature reaction 1～
3h；
3rd, the product after terminate step 2 heating response is cooled to room temperature, through sedimentation, removes supernatant liquor, obtains after suction filtration
Blue solid thing；
4th, by the blue solid thing obtained in step 3 in vacuum drying chamber, 40～60 DEG C dry to constant weight, obtain with list
The CuO microballoon predecessors of dispersing characteristic yolk-shell structures；
5th, using controllable heating rate resistance furnace, by the predecessor obtained in step 4 in air atmosphere with certain temperature
Annealed under the conditions of degree, obtained the CuO microballoons with single dispersing characteristic yolk-shell structure.
Further, the mass ratio 1～3 of the copper acetate and polyvinylpyrrolidone：1～4, the copper acetate and second two
The mass volume ratio of alcohol is 1～3：280～320 g/ml；Or copper acetate and the mixture and ethylene glycol of polyvinylpyrrolidone
Mass volume ratio is 2～7：280～320 g/ml.
Further, the autoclave in the step 2 is with teflon-lined autoclave.
Further, in the step 4, the blue solid thing for obtaining need not be washed, vacuum is directly placed into and does after suction filtration
In dry case, 0.08～0.09MPa of vacuum is set, is dried to constant weight.
Further, in the step 5, the resistance furnace heating rate of controllable heating rate is 1～3 DEG C/per minute, from
Room temperature maintains 1～2 h to 350～400 DEG C at 350～400 DEG C.
Further, the single dispersing yolk-shell structure Cs uO microballoons are referred to, in photocatalytic system, addition concentration is
25～28% H2O2, realize reaching rhodamine B in 30min more than 92% degradation effect.
The invention has the beneficial effects as follows：The yolk- with single dispersing characteristic is prepared using simple, green solvent-thermal method
The CuO microballoon predecessors of shell structures, by directly annealing in air ambient, realize the yolk- with single dispersing characteristic
The CuO microballoons of shell structures；, at 1.7～2.1 μm, the distance between surface crust and kernel are about for the CuO microsphere diameters of the structure
200nm, composition detection result show without other impurities；This method has cleverly used ethylene glycol so as to simultaneously as organic
Solvent and structure directing agent, realize designing yolk-shell structure-controllables；Raw material is easy to get, with low cost, to environment almost without
Pollution, product are easily separated, and purity is high, and pattern is good and homogeneous, preparation process is simple, it is easy to operate；The single dispersing yolk- for being obtained
Shell structure C uO microballoons have excellent photochemical properties, the tool compared with the CuO of other structures, particularly with same amount
The CuO microballoons for having solid construction are compared, and can significantly improve the photocatalysis performance of material.
Description of the drawings
The invention will be further elaborated with reference to the accompanying drawings and examples.
Fig. 1 gained of the present invention has the X-ray diffraction of the CuO microballoon predecessors of single dispersing characteristic yolk-shell structure
(XRD) collection of illustrative plates；
Fig. 2 gained of the present invention has the scanning electron microscopy electricity of the CuO microballoon predecessors of single dispersing characteristic yolk-shell structure
Mirror photo；Fig. 3 gained of the present invention has the transmission electron microscopy of the CuO microballoon predecessors of single dispersing characteristic yolk-shell structure
Mirror photo；
Fig. 4 gained of the present invention has X-ray diffraction (XRD) collection of illustrative plates of the CuO microballoons of single dispersing characteristic yolk-shell structure；
Fig. 5 gained of the present invention has the scanning electron microscopy electromicroscopic photograph of the CuO microballoons of single dispersing characteristic yolk-shell structure；
The 500nm transmission electron microscopes that Fig. 6 gained of the present invention has the CuO microballoons of single dispersing characteristic yolk-shell structure shine
Piece；
The 100nm transmission electron microscopes that Fig. 7 gained of the present invention has the CuO microballoons of single dispersing characteristic yolk-shell structure shine
Piece；
Fig. 8 gained of the present invention has the CuO microballoons of single dispersing characteristic yolk-shell structure with CuO other dependency structure materials
Photochemical properties comparison diagram on a timeline；
Fig. 9 gained of the present invention has the CuO microballoons of single dispersing characteristic yolk-shell structure with CuO other dependency structure materials
Photodegradation rate comparison diagram.
Specific embodiment
Embodiment 1
A kind of preparation method of single dispersing yolk-shell structure Cs uO microballoons, comprises the following steps：
(1) copper acetate (Cu (CH of 0.242g are accurately weighed3COO)2·H2O), which is dispersed in the container equipped with ethylene glycol,
Fully dissolve in the presence of magnetic agitation, form as clear as crystal blue solution；
(2) the as clear as crystal blue solution obtained in step (1) is transferred in autoclave, anti-in 180 DEG C of heated at constant temperature
Answer 1h；
(3) reaction is cooled to room temperature after terminating, and after settlement, supernatant liquor is removed, and obtains blue solid product after suction filtration；
(4) the blue solid product obtained in step (3) in vacuum drying chamber is dried for 40～60 DEG C and is had to constant weight
The CuO microballoon predecessors of single dispersing characteristic yolk-shell structure are standby；
(5) using the resistance furnace of controllable heating rate, the product that step (4) is obtained with heating rate is in air atmosphere
2 DEG C per minute to be warming up to 350 DEG C resistance furnace, and heated at constant temperature 1 hour at such a temperature, is had by being cooled to room temperature
The CuO microballoons of single dispersing characteristic yolk-shell structure.
Embodiment 2
A kind of preparation method of single dispersing yolk-shell structure Cs uO microballoons, comprises the following steps：
(1) copper acetate (Cu (CH of 0.242g are accurately weighed3COO)2·H2) and 0.1g, 0.2g, 0.3g or 0.4g polyethylene O
Pyrrolidones (PVP), is dispersed in which in container equipped with ethylene glycol, fully dissolves in the presence of magnetic agitation, is formed clear
Clear transparent blue solution；
(2) the as clear as crystal blue solution obtained in step (1) is transferred in autoclave, anti-in 140 DEG C of heated at constant temperature
Answer 1h or 3h；
(3) reaction is cooled to room temperature after terminating, and after settlement, supernatant liquor is removed, and obtains blue solid product after suction filtration；
(4) the blue solid product obtained in step (3) in vacuum drying chamber is dried for 40～60 DEG C and is had to constant weight
The CuO microballoon predecessors of single dispersing characteristic yolk-shell structure are standby；
(5) using the resistance furnace of controllable heating rate, the product that step (4) is obtained with heating rate is in air atmosphere
2 DEG C per minute to be warming up to 350 DEG C resistance furnace, and heated at constant temperature 1 hour at such a temperature, is had by being cooled to room temperature
The CuO microballoons of single dispersing characteristic yolk-shell structure.
Embodiment 3
A kind of preparation method of single dispersing yolk-shell structure Cs uO microballoons, comprises the following steps：
(1) copper acetate (Cu (CH of 0.242g are accurately weighed3COO)2·H2) and 0.1g, 0.2g, 0.3g or 0.4g polyethylene O
Pyrrolidones (PVP), is dispersed in which in container equipped with ethylene glycol, fully dissolves in the presence of magnetic agitation, is formed clear
Clear transparent blue solution；
(2) the as clear as crystal blue solution obtained in step (1) is transferred in autoclave, anti-in 160 DEG C of heated at constant temperature
Answer 1h or 3h；
(3) reaction is cooled to room temperature after terminating, and after settlement, supernatant liquor is removed, and obtains blue solid product after suction filtration；
(4) the blue solid product obtained in step (3) in vacuum drying chamber is dried for 40～60 DEG C and is had to constant weight
The CuO microballoon predecessors of single dispersing characteristic yolk-shell structure are standby；
(5) using the resistance furnace of controllable heating rate, the product that step (4) is obtained with heating rate is in air atmosphere
2 DEG C per minute to be warming up to 350 DEG C resistance furnace, and heated at constant temperature 1 hour at such a temperature, is had by being cooled to room temperature
The CuO microballoons of single dispersing characteristic yolk-shell structure.
Embodiment 4
A kind of preparation method of single dispersing yolk-shell structure Cs uO microballoons, comprises the following steps：
(1) copper acetate (Cu (CH of 0.242g are accurately weighed3COO)2·H2) and 0.1g, 0.2g or 0.3g polyvinylpyrrolidine O
Ketone (PVP), is dispersed in which in container equipped with ethylene glycol, fully dissolves in the presence of magnetic agitation, is formed as clear as crystal
Blue solution；
(2) the as clear as crystal blue solution obtained in step (1) is transferred in autoclave, anti-in 180 DEG C of heated at constant temperature
Answer 1h or 3h；
(3) reaction is cooled to room temperature after terminating, and after settlement, supernatant liquor is removed, and obtains blue solid product after suction filtration；
(4) the blue solid product obtained in step (3) in vacuum drying chamber is dried for 40～60 DEG C and is had to constant weight
The CuO microballoon predecessors of single dispersing characteristic yolk-shell structure are standby；
(5) using the resistance furnace of controllable heating rate, the product that step (4) is obtained with heating rate is in air atmosphere
2 DEG C per minute to be warming up to 360 DEG C resistance furnace, and heated at constant temperature 1 hour at such a temperature, is had by being cooled to room temperature
The CuO microballoons of single dispersing characteristic yolk-shell structure.
Embodiment 5
A kind of preparation method of single dispersing yolk-shell structure Cs uO microballoons, comprises the following steps：
(1) copper acetate (Cu (CH of 0.242g are accurately weighed3COO)2·H2) and 0.1g, 0.2g or 0.3g polyvinylpyrrolidine O
Ketone (PVP), is dispersed in which in container equipped with ethylene glycol, fully dissolves in the presence of magnetic agitation, is formed as clear as crystal
Blue solution；
(2) the as clear as crystal blue solution obtained in step (1) is transferred in autoclave, anti-in 200 DEG C of heated at constant temperature
Answer 1h or 3h；
(3) reaction is cooled to room temperature after terminating, and after settlement, supernatant liquor is removed, and obtains blue solid product after suction filtration；
(4) the blue solid product obtained in step (3) in vacuum drying chamber is dried for 40～60 DEG C and is had to constant weight
The CuO microballoon predecessors of single dispersing characteristic yolk-shell structure are standby；
(5) using the resistance furnace of controllable heating rate, the product that step (4) is obtained with heating rate is in air atmosphere
2 DEG C per minute to be warming up to 380 DEG C resistance furnace, and heated at constant temperature 1 hour at such a temperature, is had by being cooled to room temperature
The CuO microballoons of single dispersing characteristic yolk-shell structure.
Embodiment 6
As shown in figs. 1-7, the CuO microballoon predecessors with single dispersing characteristic yolk-shell structure obtained by embodiment 1-5
Photo with the CuO microballoons with single dispersing characteristic yolk-shell structure.
By the single dispersing yolk-shell structure C uO microballoons obtained in above-described embodiment under visible light illumination, carry out
Photochemistry is tested, and is comprised the following steps：
(1) precise 20mg has the CuO microballoons of yolk-shell structures, is put into volume capacity in 100ml beakers, its
In, the beaker is 10 equipped with concentration-5The rhodamine B solution 50ml of M and concentration are 25～28% H2O25ml.
(2) in dark room conditions, in the presence of magnetic agitation so that the CuO microballoons pair with yolk-shell structures
Rhodamine B reaches adsorption equilibrium.
(3) under the irradiation of 500W xenon lamps, photochemical properties test experiments are carried out, at interval of 15min to rhodamine B concentration
It is monitored, after 45 minutes, completes photochemical properties test experiments.
In terms of contrast test includes three below：
1. without any catalyst and H2O2Under conditions of, under the irradiation of 500W xenon lamps, photochemistry reality is carried out to rhodamine B solution
Test；2. remove and do not add H in system2O2Outward, the photochemistry test experiments step of commercial CuO samples is ibid；3. commercialization CuO samples and
There is the photochemistry test experiments step of CuO samples of solid construction ibid.Photochemistry test experiments institute test curve result is such as
Fig. 8,9.
Above example is the section Example that we enumerate, and for checking under different experimental conditions, can obtain
Corresponding experimental result.
It is not difficult to find out from above-described embodiment, the present invention has advantages below compared with the prior art：
1st, the CuO microballoon forerunner of the yolk-shell structure with single dispersing characteristic is prepared using simple, green solvent-thermal method
Thing, through X-ray diffractometer (XRD；Philips X’pert Pro X-ray diffractometer with Cu-Kα
Radiation (1.5418)) analysis, prepared predecessor is Cu- ethylene glycol complexs (such as Fig. 1)；
By being scanned electron microscope (NEC's SEM (JEOL-6610-LV), accelerating potential to which
10KV) divide with transmission electron microscope (NEC's transmission electron microscope (JEOL-JEM-2100), accelerating potential 200KV)
Analysis, it can be found that obtained predecessor has the yolk-shell structures of single dispersing characteristic, its particle diameter is in 1.7～2.1 μ
M (as Fig. 2,3).
Using the resistance furnace of controllable heating rate, the Cu- ethylene glycol complexs for being obtained is in air atmosphere and certain
Temperature conditionss under annealed, you can obtain have single dispersing characteristic yolk-shell structure CuO microballoons.Through X ray
Diffractometer is analyzed, and obtained product is CuO, occurs (such as Fig. 4) without other impurity diffraction maximums；
By being scanned electron microscope and tem study to which, it can be found that before its structure is still maintained
Drive the yolk-shell structures of the had single dispersing characteristic of thing Cu- ethylene glycol complexs, the surface of this yolk-shell structures
Shell and the distance between kernel about 200nm (such as Fig. 5,6,7).
2nd, the present invention has cleverly used ethylene glycol as organic solvent and structure directing agent, realizes tying yolk-shell
The controllable design of structure；
3rd, raw material be easy to get, Costco Wholesale cheap, environment is almost pollution-free, and product can be easily separated, and products therefrom purity is high, and pattern is good
And homogeneous, preparation process and process is simple, it is easy to operate；
4th, the single dispersing yolk-shell structure C uO microballoons for being obtained have excellent photochemical properties, when in light reaction system
Middle addition 5mLH2O2(concentration is 25～28%), it is possible to achieve the degradation effect that more than 92% is reached in 30min to rhodamine B,
Compared with the CuO of other dependency structures, particularly compared with the CuO microballoons with solid construction of same amount (such as Fig. 8), energy
The photocatalysis performance of the material is significantly improved, its reason can be attributed to can be fully sharp with yolk-shell structure C uO microballoons
The capture ability (as shown in illustration in Fig. 9) of photon is enhanced with multiple reflections and the scattering of light, its photocatalysis is improve
Degradation efficiency, the result have also further fully demonstrated the excellent specific property with yolk-shell structure C uO micro-sphere materials.
Disclosed embodiment of this invention is the explanation to technical scheme, it is impossible to used as to present invention
Restriction, those skilled in the art's simple change on the basis of the present invention, still within the scope of the present invention.
Claims (6)
1. a kind of preparation method of single dispersing yolk-shell structure Cs uO microballoons, step include：
First, the mixture of a certain amount of copper acetate or copper acetate and polyvinylpyrrolidone is taken, the appearance equipped with ethylene glycol is dispersed in
In device, stir to fully dissolving, form as clear as crystal blue solution；
2nd, the blue solution obtained in step one is transferred in autoclave, 140～200 DEG C of heated at constant temperature reaction 1～
3h；
3rd, the product after terminate step 2 heating response is cooled to room temperature, through sedimentation, removes supernatant liquor, obtains after suction filtration
Blue solid thing；
4th, by the blue solid thing obtained in step 3 in vacuum drying chamber, 40～60 DEG C dry to constant weight, obtain with list
The CuO microballoon predecessors of dispersing characteristic yolk-shell structures；
5th, using controllable heating rate resistance furnace, by the predecessor obtained in step 4 in air atmosphere with certain temperature
Annealed under the conditions of degree, obtained the CuO microballoons with single dispersing characteristic yolk-shell structure.
2. the preparation method of single dispersing yolk-shell structure Cs uO microballoons according to claim 1, it is characterised in that：Institute
State the mass ratio 1～3 of copper acetate and polyvinylpyrrolidone：1～4, the mass volume ratio of the copper acetate and ethylene glycol is 1～
3：280～320 g/ml；Or copper acetate is 2～7 with the mixture of polyvinylpyrrolidone and the mass volume ratio of ethylene glycol：
280～320 g/ml.
3. the preparation method of single dispersing yolk-shell structure Cs uO microballoons according to claim 1, it is characterised in that：Institute
It is with teflon-lined autoclave to state the autoclave in step 2.
4. the preparation method of single dispersing yolk-shell structure Cs uO microballoons according to claim 1, it is characterised in that：Institute
State in step 4, the blue solid thing for obtaining need not be washed, be directly placed in vacuum drying chamber, vacuum is set after suction filtration
0.08～0.09MPa, dries to constant weight.
5. the preparation method of single dispersing yolk-shell structure Cs uO microballoons according to claim 1, it is characterised in that：Institute
State in step 5, the resistance furnace heating rate of controllable heating rate is 1～3 DEG C/per minute, from room temperature to 350～400
DEG C, 1～2 h is maintained at 350～400 DEG C.
6. the preparation method of single dispersing yolk-shell structure Cs uO microballoons according to claim 1, it is characterised in that：Institute
State single dispersing yolk-shell structure C uO microballoons to refer to, it is 25～28% H to add concentration in photocatalytic system2O2, it is right to realize
Rhodamine B reaches more than 92% degradation effect in 30min.
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Cited By (4)
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| CN108238648A (en) * | 2018-03-26 | 2018-07-03 | 淮北师范大学 | A kind of preparation method of lithium ion battery negative material |
| CN108346782A (en) * | 2017-12-28 | 2018-07-31 | 杭州电子科技大学 | Porous copper oxide microballoon/multi-layer graphene composite material and preparation method |
| CN109110797A (en) * | 2018-09-20 | 2019-01-01 | 西安凯立新材料股份有限公司 | A kind of preparation method of sector multi-layer cupric oxide powder |
| CN111943155A (en) * | 2020-07-08 | 2020-11-17 | 江西师范大学 | Preparation method of composite cobalt phosphide nano polyhedron with yolk shell structure |
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| CN104692445A (en) * | 2015-02-03 | 2015-06-10 | 合肥师范学院 | Preparation and application of copper oxide nanometer hollow spheres |
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| CN104692445A (en) * | 2015-02-03 | 2015-06-10 | 合肥师范学院 | Preparation and application of copper oxide nanometer hollow spheres |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108346782A (en) * | 2017-12-28 | 2018-07-31 | 杭州电子科技大学 | Porous copper oxide microballoon/multi-layer graphene composite material and preparation method |
| CN108238648A (en) * | 2018-03-26 | 2018-07-03 | 淮北师范大学 | A kind of preparation method of lithium ion battery negative material |
| CN109110797A (en) * | 2018-09-20 | 2019-01-01 | 西安凯立新材料股份有限公司 | A kind of preparation method of sector multi-layer cupric oxide powder |
| CN109110797B (en) * | 2018-09-20 | 2020-09-01 | 西安凯立新材料股份有限公司 | Preparation method of sector multi-layer copper oxide powder |
| CN111943155A (en) * | 2020-07-08 | 2020-11-17 | 江西师范大学 | Preparation method of composite cobalt phosphide nano polyhedron with yolk shell structure |
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