CN106966422B - A kind of pair of spherical cuprous oxide microballoon and preparation method thereof - Google Patents
A kind of pair of spherical cuprous oxide microballoon and preparation method thereof Download PDFInfo
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- CN106966422B CN106966422B CN201710211629.4A CN201710211629A CN106966422B CN 106966422 B CN106966422 B CN 106966422B CN 201710211629 A CN201710211629 A CN 201710211629A CN 106966422 B CN106966422 B CN 106966422B
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 12
- 235000010378 sodium ascorbate Nutrition 0.000 claims abstract description 11
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims abstract description 11
- 229960005055 sodium ascorbate Drugs 0.000 claims abstract description 11
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims abstract description 11
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 230000010355 oscillation Effects 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000012545 processing Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229910021389 graphene Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- -1 Graphite alkene Chemical class 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 16
- 239000004005 microsphere Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 description 43
- 239000011859 microparticle Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 41
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 13
- 239000008103 glucose Substances 0.000 description 13
- 238000005286 illumination Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000011805 ball Substances 0.000 description 9
- 229960002163 hydrogen peroxide Drugs 0.000 description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 239000013049 sediment Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 230000003321 amplification Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OBRMNDMBJQTZHV-UHFFFAOYSA-N cresol red Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(C)C(O)=CC=2)=C1 OBRMNDMBJQTZHV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 241001634884 Cochlicopa lubricella Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000001291 vacuum drying 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- 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
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- 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
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- 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
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- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of double spherical cuprous oxide microballoons and preparation method thereof.In deionized water by cupric sulfate pentahydrate dissolution of crystals, sonic oscillation prepares copper-bath to this method；Surfactant SDS, ultrasonic dissolution are added in copper-bath；Reducing agent sodium ascorbate solution is added dropwise, allows solution initial reaction 5-10 minutes；Sodium hydroxide solution is added dropwise again, the pH value for adjusting reaction system is 7.5-9, and temperature control is 15-40 DEG C, obtains primary product；Primary product is centrifuged, is washed, the clean precipitated product of bottom is obtained；Precipitated product is placed in freeze-day with constant temperature in vacuum, obtains target product.The method of the present invention is easy, efficient, raw material is easily obtained, subsequent processing condition is relatively simple, the cuprous oxide microspheres product prepared has apparent symmetric double spherical structure, compared with the cuprous oxide particle of traditional single ball-type, Cubic and octahedral build, possess more unique properties and application value.
Description
Technical field
The invention mainly relates to a kind of preparation methods of cuprous oxide microballoon, and in particular to one kind having apparent double spherical structures
Nano balls of cuprous oxide preparation method.
Technical background
Cuprous oxide is as a kind of typical catalysis material, and with relatively narrow electronics energy gap, electronics energy gap is
2.17eV or so (mainly utilizes ultraviolet spectra) compared with traditional catalysis material-titanium dioxide, and lower electronics energy gap is determined
Having determined cuprous oxide significantly more efficient can absorb the energy of solar visible light section, while can be swashed by most of visible light
Hair absorbs the upper limit up to 570nm.Compared with other thin pillar materials, cuprous oxide has hypotoxicity, easily property produced etc.
Advantage.Therefore, cuprous oxide has a wide range of applications in field of photocatalytic material.
The method for preparing cuprous oxide has very much, mainly have at present solution reduction, electrochemical process, photochemical syntheses method,
Mechanical Method etc..Wherein, electrochemical process is the higher preparation method of business degree, it mainly has two kinds of sides of electro-deposition and anodic oxidation
Method is widely used because its is easy to operate, easily controllable in states such as America and Europes；And solution reduction is that domestic application is more
Method, beam are built etc. using copper acetate as raw material, and spherical and the octahedral bodily form the cuprous oxide particle is prepared using solvent-thermal method.Cui
Et al. the method that is restored with glucose, CTAB prepares cuprous oxide cubic granules as surfactant.
But the cuprous oxide particle that current various methods prepare is mainly with single spherical, cube and the octahedral bodily form
Main, the application for the photoelectric property that more single shape characteristic keeps its excellent is very restricted.Special symmetrical pattern energy
Enough assign cuprous oxide particle this special performance of a kind of catalysis material；The micro-nano oxygen of apparent double spherical structures in the prior art
The preparation method for changing cuprous microballoon is not yet seen in report.
Invention content
The purpose of the present invention is to provide a kind of micro-nano cuprous oxide microballoon with apparent double spherical structures and its preparations
Method；The micro-nano cuprous oxide microballoon of double spherical structures is easy to be doped with other inorganic material, has relatively single spherical oxygen
Change cuprous stronger sensibility and response.
The present invention utilizes Cu2+The nucleation of ion under alkaline condition has sensibility, by adjusting Cu in water phase2+Ion
Reduction nucleating condition and corresponding last handling process, realizing has the micro-nano cuprous oxide of apparent double spherical structure special appearances micro-
The preparation of ball.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of double spherical micro/nano level cuprous oxide, comprises the steps of：
(1) in deionized water by cupric sulfate pentahydrate dissolution of crystals, fully dissolving in sonic oscillation 10-15 minutes, prepares dense
Degree is the copper-bath of 0.002mol/L-0.01mol/L；
(2) Surfactant SDS is added in copper-bath, it is molten that reaction raw materials liquid is carried out ultrasound
Solution 10-15 minutes, is subsequently placed on magnetic stirring apparatus and stirs；Control surface activating agent lauryl sodium sulfate and copper sulphate rub
You are than being 1:4.0-4.2；
(3) reducing agent sodium ascorbate solution is added dropwise in prepared reaction solution, allows solution initial reaction 5-10 minutes；
(4) sodium hydroxide solution is added dropwise again, the pH value for adjusting reaction system is 7.5-9, isothermal reaction 2-5 under magnetic agitation
Hour, temperature control is 15-40 DEG C, obtains primary product；
(5) primary product is centrifuged with supercentrifuge, removes upper layer waste liquid, add deionized water oscillating washing, weight
Multiple above-mentioned centrifugation water-washing process 5-10 times obtains the clean precipitated product of bottom；
(6) precipitated product is placed in freeze-day with constant temperature in vacuum, obtains target product.
To further realize the object of the invention, it is preferable that further include that oxidation stone is added after step (2) addition surfactant
Then black alkene carries out ultrasonic disperse processing；0.2-0.5 grams of graphene oxide is added in every gram of cupric sulfate pentahydrate crystal；It is final to be made
Adulterate double spherical micro/nano level cuprous oxide.
Preferably, it is 200-250 revs/min that magnetic agitation speed is stirred on the magnetic stirring apparatus.
Preferably, 60- is added dropwise in a concentration of 0.2mol/L of reducing agent sodium ascorbate of dropwise addition, every gram of cupric sulfate pentahydrate crystal
80 milliliters of reducing agents, at the uniform velocity drip in 1 minute.
Preferably, the pH value of step (4) reaction system is adjusted between 7.8-8.0, the concentration of sodium hydroxide solution used
For 1mol/L, the isothermal reaction time is 4 hours, and temperature control is 35 DEG C.
Preferably, the rate of the supercentrifuge centrifugation is 10000 revs/min, and centrifugation every time goes residual solution in 5 minutes
It removes.
Preferably, the temperature of freeze-day with constant temperature is 50-60 DEG C in the vacuum, and the dry time is 1-4 hours.It is further excellent
It selects, it is 55 DEG C that the temperature of freeze-day with constant temperature, which is vacuum drying temperature, in the vacuum, 1.5 hours dry time.
Preferably, the copper-bath concentration of preparation is 0.008mol/L.
A kind of double spherical micro/nano level cuprous oxide of the present invention, is made by above-mentioned preparation method.
Compared with the existing technology, the present invention has the following advantages：
(1) present invention utilizes reducing agent sodium ascorbate and Cu2+At the sensibility of nuclear reaction in alkaline environment, phase is adjusted
Cuprous oxide is directly reduced into the nano-particle with double spherical structures by the reaction condition answered in the solution, and what is prepared receives
The double spherical looks of rice cuprous oxide are good.
(2) cuprous oxide (single spherical, cube shaped, octahedral bodily form that the present invention is prepared with current most methods
Deng) there is notable difference, a kind of approach is provided to realize the cuprous oxide microsphere particles for preparing symmetric double spherical structure.It is this symmetrical
The cuprous oxide microsphere particles of double spherical structures have the specific surface area of bigger, it is easier to be doped preparation with other inorganic material
(such as graphene oxide etc.), the two spheres system surface after doping usually have more reactivity sites.These characteristics can
To enhance the photoelectric characteristic of the cuprous oxide microsphere particles of this double spherical structures, promote cuprous oxide under visible light and ultraviolet light
Electron transition and photohole are generated, can be applied to numerous areas, such as glucose and peroxide using these outstanding features
Photocatalysis Decomposition and the detection for changing hydrogen have compared with the stronger sensibility of single spherical shape cuprous oxide and response；The light of organic dyestuff
Degradation, more efficient can handle polluted-water at low cost；Detect to simple, intuitive the intensive ultraviolet in environment.Therefore this double
The cuprous oxide micro-and nano-particles of spherical structure can be prepared by simple synthetic method, have important application value.
(3) present invention introduces proper amount of surfactant to keep the double ball cuprous nano particle diameters prepared uniform,
More excellent photoelectric property can be generated with other materials doping.
(4) the entire preparation method of the present invention is simply controllable, does not need complicated reaction condition, post-processing step is relatively easy
It realizes, the double ball cuprous oxide product properties prepared are stablized.
Description of the drawings
Fig. 1 is the electron scanning micrograph for double spherical cuprous oxide micro-and nano-particles that embodiment 1 synthesizes, times magnification
50000 times of number, figure medium scale are 200 nanometers.
Fig. 2 is the far-field scanning electron micrograph for double spherical cuprous oxide micro-and nano-particles that embodiment 1 synthesizes, and is put
Big 5000 times of multiple, figure medium scale are 2 microns.
Fig. 3 is the X-ray diffractogram for double spherical cuprous oxide micro-and nano-particles that embodiment 1 synthesizes.
Fig. 4-1 is the EDX electronic images of double spherical cuprous oxide micro-and nano-particles after the doping of 3 graphene of embodiment.
Fig. 4-2 is the EDX figures of double spherical cuprous oxide micro-and nano-particles surface C u elements after the doping of 3 graphene of embodiment
Picture.
Fig. 4-3 is the EDX figures of double spherical cuprous oxide micro-and nano-particles surfaces O elements after the doping of 3 graphene of embodiment
Picture.
Fig. 4-4 is the EDX figures of double spherical cuprous oxide micro-and nano-particles surface C elements after the doping of 3 graphene of embodiment
Picture.
Fig. 5-1 is the Tafel curve of single spherical cuprous oxide micro-and nano-particles of 3 graphene of embodiment doping.
Fig. 5-2 is the Tafel curve of double spherical cuprous oxide micro-and nano-particles of 3 graphene of embodiment doping.
Fig. 6-1 is double spherical cuprous oxide micro-and nano-particles of 3 graphene of embodiment doping under visible light illumination in water
In movement locus, light intensity 43900Lux.
Fig. 6-2 be the doping of 3 graphene of embodiment double spherical cuprous oxide micro-and nano-particles under ultraviolet light in water
In movement locus, light intensity be 40 × 10-3W/cm2。
Specific implementation mode
To more fully understand the present invention, the present invention is further illustrated with reference to the accompanying drawings and examples, but this hair
Bright embodiment is unlimited in this way, embodiment should not be understood limiting the scope of the invention.
Embodiment 1
(1) by 0.0495g cupric sulfate pentahydrates dissolution of crystals in 50mL deionized waters, sonic oscillation 10 minutes is fully molten
Solution, obtains the light blue copper-bath of a concentration of 0.00396mol/L.
(2) 0.66g lauryl sodium sulfate (SDS) powder is taken to be added in prepared copper-bath, sonic oscillation is molten
Solution 15 minutes, is then added magneton, is placed on magnetic stirring apparatus and stirs, and stir speed (S.S.) is 210 revs/min.
(3) be added dropwise while stirring in reaction solution 3mL solubility be 0.2mol/L reducing agent sodium ascorbate solution, 1 point
It is at the uniform velocity dripped off in clock, allows solution initial reaction 5 minutes.
(4) sodium hydroxide solution of appropriate 1mol/L is added dropwise again, the pH value for adjusting reaction system is 8, permanent under magnetic agitation
Temperature reaction 4 hours, temperature control are 35 DEG C.
(5) it is brick-red sediment to obtain primary product, by sediment with 10000 rpms of supercentrifuge from
The heart removes upper layer waste liquid, adds deionized water oscillating washing, repeats above-mentioned centrifugation water-washing process 5 times.Bottom is finally obtained to wash
Net precipitated product.
(6) precipitated product is placed in freeze-day with constant temperature in vacuum, controlled at 55 DEG C, drying time is 1.5 hours, dry
It is complete to obtain double spherical cuprous oxide products.
(7) 1 milligram of double spherical cuprous oxide micro-and nano-particles being prepared and the single ball obtained in the conventional way are taken
Shape cuprous oxide micro-and nano-particles, under the visible light green light irradiation that intensity of illumination is 43900Lux, respectively with a concentration of 10 ×
10-3The glucose solution of mol/L and a concentration of 0.1 × 10-3The hydrogenperoxide steam generator of mol/L reacts, obtain sample for
The test result of glucose and hydrogen peroxide photocatalysis performance.
Fig. 1 is the SEM shape appearance figures of the product, and amplification factor is 50000 times, and medium scale is 200 nanometers, prepared by display
It is the far field SEM figures of double ball cuprous oxide particles that cuprous oxide out, which has apparent double spherical structures, Fig. 2, and amplification factor is
5000 times, figure medium scale is 2 microns, shows that the particle size of preparation has preferable homogeneity.Fig. 3 is the double of the synthesis
The X-ray diffractogram of spherical cuprous oxide micro-and nano-particles compares (PDF No.050667), card with the PDF cards of cuprous oxide
The micro-and nano-particles that bright this method is prepared are cuprous oxide sample.
The single spherical test result with double spherical cuprous oxide micro-and nano-particles photocatalysis performances of table 1
Table 1 is to restore Cu with traditional reducing agent (sodium ascorbate)2+Single spherical and 1 institute of the present embodiment for preparing of method
Obtain reaction time of double spherical cuprous oxide micro-and nano-particles in glucose and hydrogenperoxide steam generator and microballoon mean motion speed
Rate test result, wherein the glucose tested, hydrogen peroxide use are 2 milliliters, the visible light source used in test system is green light,
Intensity is 43900Lux.The double spherical cuprous oxide micro-and nano-particles prepared are compared with single spherical shape, for glucose and peroxidating
Hydrogen all has the shorter reaction time, and the mean motion speed of double spherical sample particles is relatively single spherical big, mainly due to
The cuprous oxide microballoon of double spherical structures specific surface area with bigger under equal quality, it is micro- when by visible light exposure
Electron transition occurs for ball surface, and the structure of double balls can generate more free electrons pair and the photohole of strong oxidizing property, this
The photohole of a little strong oxidizing properties is distributed in cuprous oxide surface, can aoxidize the glucose in solution, and transition is freely electric
It is sub then tend to promote catalytic action of the cuprous oxide to glucose or hydrogen peroxide.The specific surface area of bigger means to aoxidize
It is cuprous to connect solution area and touch opportunity with test solution bigger, and acted on by the illumination of area bigger, generate largely from
By electronics and photohole, the catalytic action to enhancing to glucose and hydrogen peroxide.
The cuprous oxide micro-and nano-particles of this double spherical structures of the present invention have very excellent photocatalysis performance and oxidation
Degradation property (test and attached drawing for seeing below embodiment prove), can be under visible light illumination in Direct Catalytic Oxidation solution
Glucose and organic dyestuff etc., and possess the characteristic of very strong anti-light corrosion, with good stability, 1 milligram is double spherical
Cuprous oxide micro-and nano-particles sample can preserve two months or more in the natural environment, and traditional cuprous oxide powder due to
The effect meeting rapid deterioration of photoetch, and for the visible light source and ultraviolet source and organic-fuel and glucose in environment
Solution etc. has sensitive reactivity due to the huge reactivity site in surface.Such performance makes double spherical structures
Microballoon can apply the glucose and hydrogen peroxide context of detection in no enzyme, have higher sensitivity and stability, and can
To substantially reduce testing cost.By detecting the variation of sample particle movement velocity, preliminary estimation grape can be concisely and efficiently
The content of sugar and hydrogen peroxide.
Embodiment 2
(1) by 0.0495g cupric sulfate pentahydrates dissolution of crystals in 50mL deionized waters, sonic oscillation 10 minutes is fully molten
Solution, obtains the light blue copper-bath of a concentration of 0.00396mol/L.
(2) 0.66g lauryl sodium sulfate (SDS) powder is taken to be added in prepared copper-bath, sonic oscillation is molten
Solution 15 minutes, is then added magneton, is placed on magnetic stirring apparatus and stirs, and stir speed (S.S.) is 210 revs/min.
(3) be added dropwise while stirring in reaction solution 3mL solubility be 0.2mol/L reducing agent sodium ascorbate solution, 1 point
It is at the uniform velocity dripped off in clock, allows solution initial reaction 5 minutes.
(4) sodium hydroxide solution of appropriate 1mol/L is added dropwise again, the pH value for adjusting reaction system is 8, permanent under magnetic agitation
Temperature reaction 4 hours, temperature control are 35 DEG C.
(5) it is brick-red sediment to obtain primary product, by sediment with 10000 rpms of supercentrifuge from
The heart removes upper layer waste liquid, adds deionized water oscillating washing, repeats above-mentioned centrifugation water-washing process 5 times.Bottom is finally obtained to wash
Net precipitated product.
(6) precipitated product is placed in freeze-day with constant temperature in vacuum, controlled at 55 DEG C, drying time is 1.5 hours.It is dry
It is complete to obtain double spherical cuprous oxide products.
(7) 1 milligram of double spherical cuprous oxide micro-and nano-particles being prepared and the single ball obtained in the conventional way are taken
Shape cuprous oxide micro-and nano-particles, under the visible light green light irradiation that intensity of illumination is 43900Lux, respectively with a concentration of 1 ×
10-4The cresol red solution of grams per liter and a concentration of 1 × 10-4The methyl orange solution of grams per liter reacts, and obtains sample for organic dyestuff
The test result of degradation property.
The single spherical test result with double spherical cuprous oxide micro-and nano-particles degradation properties of table 2
Table 2 is to restore Cu with traditional reducing agent (sodium ascorbate)2+Single spherical and 2 institute of the present embodiment for preparing of method
Double spherical cuprous oxide micro-and nano-particles common are complete reaction time in machine dye solution at two kinds and microballoon is average
The test result of movement rate, wherein the dosage of the cresol red solution and methyl orange solution tested is 2 milliliters, test system institute
Visible light source is green light, intensity 43900Lux.And the double spherical cuprous oxide micro-and nano-particles prepared and single spherical phase
Than, it is all shorter for the reaction time of both organic dyestuff, and possess faster single particle motion rate.Due to double spherical shapes
Cuprous oxide micro-and nano-particles have a larger specific surface area, therefore for the relatively single spherical bigger of the contact surface of organic dyestuff, because
This can greatly enhance degradation of the cuprous oxide for organic dyestuff.
Embodiment 3
(1) by 0.0495g cupric sulfate pentahydrates dissolution of crystals in 50mL deionized waters, sonic oscillation 10 minutes is fully molten
Solution, obtains the light blue copper-bath of a concentration of 0.00396mol/L.
(2) 0.66g lauryl sodium sulfate (SDS) powder is taken to be added in prepared copper-bath, sonic oscillation is molten
Solution 15 minutes.
(3) after above-mentioned solution fully dissolves, take 0.01g graphene oxides that reaction solution is added, sonic oscillation 1.5 hours fills
Dispersion graphene oxide and reaction solution, magneton is then added in reaction solution, is placed on magnetic stirring apparatus and stirs, stir speed (S.S.)
It is 250 revs/min.
(4) be added dropwise while stirring in reaction solution 3mL solubility be 0.2mol/L reducing agent sodium ascorbate solution, 1 point
It is at the uniform velocity dripped off in clock, allows solution initial reaction 10 minutes.
(5) sodium hydroxide solution of appropriate 1mol/L is added dropwise again, the pH value for adjusting reaction system is 8, permanent under magnetic agitation
Temperature reaction 5 hours, temperature control are 35 DEG C.
(6) it is brick-red sediment to obtain primary product, by sediment with 10000 rpms of supercentrifuge from
The heart removes upper layer waste liquid, adds deionized water oscillating washing, repeats above-mentioned centrifugation water-washing process 10 times.Finally obtain bottom
Clean precipitated product.
(7) precipitated product is placed in freeze-day with constant temperature in vacuum, controlled at 55 DEG C, drying time is 2 hours.After drying
Obtain double spherical cuprous oxide products containing doping graphene oxide.
Fig. 4-1 is the EDX electronic images of double spherical cuprous oxide micro-and nano-particles after graphene doping, and Fig. 4-2 is stone
The EDX images of double spherical cuprous oxide micro-and nano-particles surface C u elements after black alkene doping, Fig. 4-3 are after graphene adulterates
The EDX images of double spherical shape cuprous oxide micro-and nano-particles surfaces O elements, Fig. 4-4 are that double spherical oxidations after graphene doping are sub-
The EDX images of copper micro-and nano-particles surface C element, amplification factor are 50000 times, and figure medium scale is 1 micron.It can be apparent
See that the cuprous oxide micro-and nano-particles of the double spherical structures of 3 gained of the present embodiment, can be by simple due to the feature in its structure
Inorganic material is doped compound preparation, such as graphene etc. by the method for doping.The double balls containing graphene being prepared
Structure cuprous oxide micro-and nano-particles from EDX it can be seen from the figure thats its with good pattern, and surface C u, O, C element point
Cloth is uniform.
Fig. 5-1 is the Tafel curve of single spherical cuprous oxide micro-and nano-particles of graphene doping, and Fig. 5-2 is graphene
The Tafel curve of double spherical cuprous oxide micro-and nano-particles of doping, the visible light source of irradiation is green light, and intensity is
43900Lux (wherein solid line is particle surface potential before illumination, and dotted line is particle surface potential after illumination).Graphene in Fig. 5-1
The front and back surface potential difference Δ E generated of single spherical cuprous oxide micro-and nano-particles illumination of doping is 10mV, graphene in Fig. 5-2
Double spherical front and back surface potential difference Δ E generated of cuprous oxide micro-and nano-particles illumination of doping are 25mV, it is seen that double spherical structures
Cuprous oxide can be by the wider array of visible light exposure of area, so as to cause the electricity of bigger in the case of identical quality sample
Potential difference.Using the variation relation of this potential difference, double spherical cuprous oxide micro-and nano-particles of graphene-containing can be used in pair
In the detection and sensing of light, Fig. 6-1 be double spherical cuprous oxide micro-and nano-particles of graphene doping under visible light illumination
Movement locus in water, light intensity 43900Lux.Fig. 6-2 is that double spherical cuprous oxide micro-and nano-particles of graphene doping exist
Movement locus under ultraviolet light in water, light intensity are 40 × 10-3W/cm2.It is micro-nano by observing double spherical cuprous oxide
The different motion conditions of particle, can detect the ultraviolet ray intensity in environment.Single spherical shape cuprous oxide micro-and nano-particles are certain
Under the ultraviolet light of intensity, since photoetch acts on stronger, the variation unobvious of the universal motion conditions of particle, therefore it is right
The sensitivity of stronger ultraviolet light detection is very low in environment, does not have applicable value.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all the present invention
All any modification, equivalent and improvement etc., should be included in the protection of the claims in the present invention made by within spirit and principle
Within the scope of.
Claims (8)
1. a kind of preparation method of double spherical micro/nano level cuprous oxide, it is characterised in that comprise the steps of：
(1) in deionized water by cupric sulfate pentahydrate dissolution of crystals, sonic oscillation 10-15 minutes fully dissolving, compound concentration is
The copper-bath of 0.002mol/L-0.01mol/L；
(2) Surfactant SDS is added in copper-bath, reaction raw materials liquid is subjected to ultrasonic dissolution 10-
15 minutes；Graphene oxide is added, then carries out ultrasonic disperse processing；0.2-0.5 grams of oxygen is added in every gram of cupric sulfate pentahydrate crystal
Graphite alkene；It is subsequently placed on magnetic stirring apparatus and stirs；Mole of control surface activating agent lauryl sodium sulfate and copper sulphate
Than being 1:4.0-4.2；
(3) reducing agent sodium ascorbate solution is added dropwise in prepared reaction solution, allows solution initial reaction 5-10 minutes；
(4) sodium hydroxide solution is added dropwise again, adjusts the pH value of reaction system as 7.5-9, isothermal reaction 2-5 is small under magnetic agitation
When, temperature control is 15-40 DEG C, obtains primary product；
(5) primary product is centrifuged with supercentrifuge, removes upper layer waste liquid, add deionized water oscillating washing, in repetition
It states centrifugation water-washing process 5-10 times, obtains the clean precipitated product of bottom；
(6) precipitated product is placed in freeze-day with constant temperature in vacuum, obtains target product.
2. preparation method according to claim 1, it is characterised in that：The reducing agent sodium ascorbate of dropwise addition is a concentration of
0.2mol/L, every gram of cupric sulfate pentahydrate crystal are added dropwise 60-80 milliliters of reducing agents, are at the uniform velocity dripped in 1 minute.
3. preparation method according to claim 1, it is characterised in that：Magnetic agitation speed is stirred on the magnetic stirring apparatus
It is 200-250 revs/min.
4. preparation method according to claim 1, it is characterised in that：The pH value of step (4) reaction system is adjusted to 7.8-
Between 8.0, a concentration of 1mol/L of sodium hydroxide solution used, the isothermal reaction time is 4 hours, and temperature control is 35 DEG C.
5. preparation method according to claim 1, it is characterised in that：The rate of the supercentrifuge centrifugation is 10000
Rev/min, centrifugation every time removes residual solution in 5 minutes.
6. preparation method according to claim 1, it is characterised in that：The temperature of freeze-day with constant temperature is 50-60 in the vacuum
DEG C, the dry time is 1-4 hours.
7. preparation method according to claim 6, it is characterised in that：The temperature of freeze-day with constant temperature is dry for vacuum in the vacuum
Dry temperature is 55 DEG C, 1.5 hours dry time.
8. preparation method according to claim 1, it is characterised in that：The copper-bath concentration of preparation is 0.008mol/
L。
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032151A (en) * | 1987-09-24 | 1989-04-05 | 中国科学院化工冶金研究所 | Process for preparing Cu 2 O |
| CN101805010A (en) * | 2010-04-02 | 2010-08-18 | 青岛科技大学 | Method for preparing hollow sphere made from cuprous oxide |
| CN101805011A (en) * | 2010-04-06 | 2010-08-18 | 厦门大学 | Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof |
| CN103172104A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Preparation method of nano cuprous oxide |
| CN103387258A (en) * | 2013-08-07 | 2013-11-13 | 武汉理工大学 | Cuprous oxide nano hollow spheres as well as synthetic method and application method thereof |
| CN103435089A (en) * | 2013-07-16 | 2013-12-11 | 上海应用技术学院 | Spherical cuprous oxide micro-nano particles with roughness surface and preparation method thereof |
| CN104016400A (en) * | 2014-06-18 | 2014-09-03 | 黄山永新股份有限公司 | Nanoscale cuprous oxide particle and synthesis method thereof |
| CN104098121A (en) * | 2014-06-27 | 2014-10-15 | 江苏华东锂电技术研究院有限公司 | Preparation method for cuprous oxide |
| CN104477969A (en) * | 2014-12-22 | 2015-04-01 | 中国矿业大学 | Preparation method of sphere-like and bookmark-shaped cuprous oxide nano-particles |
| CN105905936A (en) * | 2016-04-14 | 2016-08-31 | 青岛大学 | Cuprous oxide nanocrystalline assembly |
-
2017
- 2017-04-01 CN CN201710211629.4A patent/CN106966422B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032151A (en) * | 1987-09-24 | 1989-04-05 | 中国科学院化工冶金研究所 | Process for preparing Cu 2 O |
| CN101805010A (en) * | 2010-04-02 | 2010-08-18 | 青岛科技大学 | Method for preparing hollow sphere made from cuprous oxide |
| CN101805011A (en) * | 2010-04-06 | 2010-08-18 | 厦门大学 | Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof |
| CN103172104A (en) * | 2013-04-03 | 2013-06-26 | 浙江理工大学 | Preparation method of nano cuprous oxide |
| CN103435089A (en) * | 2013-07-16 | 2013-12-11 | 上海应用技术学院 | Spherical cuprous oxide micro-nano particles with roughness surface and preparation method thereof |
| CN103387258A (en) * | 2013-08-07 | 2013-11-13 | 武汉理工大学 | Cuprous oxide nano hollow spheres as well as synthetic method and application method thereof |
| CN104016400A (en) * | 2014-06-18 | 2014-09-03 | 黄山永新股份有限公司 | Nanoscale cuprous oxide particle and synthesis method thereof |
| CN104098121A (en) * | 2014-06-27 | 2014-10-15 | 江苏华东锂电技术研究院有限公司 | Preparation method for cuprous oxide |
| CN104477969A (en) * | 2014-12-22 | 2015-04-01 | 中国矿业大学 | Preparation method of sphere-like and bookmark-shaped cuprous oxide nano-particles |
| CN105905936A (en) * | 2016-04-14 | 2016-08-31 | 青岛大学 | Cuprous oxide nanocrystalline assembly |
Non-Patent Citations (1)
| Title |
|---|
| "液相合成不同形貌的Cu_2O微晶";李宗臻等;《青岛科技大学学报(自然科学版)》;20091231;第30卷(第6期);第483-486页 * |
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