CN106966422A - A kind of pair of cuprous microballoon of spherical alumina and preparation method thereof - Google Patents
A kind of pair of cuprous microballoon of spherical alumina and preparation method thereof Download PDFInfo
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- CN106966422A CN106966422A CN201710211629.4A CN201710211629A CN106966422A CN 106966422 A CN106966422 A CN 106966422A CN 201710211629 A CN201710211629 A CN 201710211629A CN 106966422 A CN106966422 A CN 106966422A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title description 11
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 49
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- 235000010378 sodium ascorbate Nutrition 0.000 claims abstract description 9
- 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 9
- 229960005055 sodium ascorbate Drugs 0.000 claims abstract description 9
- 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 9
- 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 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910021389 graphene Inorganic materials 0.000 claims description 27
- 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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 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
- 238000012545 processing Methods 0.000 claims description 2
- 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
- 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
- 230000033001 locomotion Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000005286 illumination Methods 0.000 description 10
- 239000011805 ball Substances 0.000 description 9
- 229960002163 hydrogen peroxide Drugs 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- 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 6
- 239000013049 sediment Substances 0.000 description 6
- 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
- 230000015556 catabolic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000006731 degradation reaction Methods 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
- 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
- 229910052760 oxygen Inorganic materials 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
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000001301 oxygen Substances 0.000 description 2
- 239000012071 phase Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 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
- 150000002431 hydrogen Chemical class 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
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 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
-
- 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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- 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
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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
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of double spherical cuprous oxide microballoon and preparation method thereof.By cupric sulfate pentahydrate dissolution of crystals in deionized water, 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, solution initial reaction 5 10 minutes are allowed；Sodium hydroxide solution is added dropwise again, the pH value of regulation reaction system is 7.5 9, and temperature control is 15 40 DEG C, obtains primary product；Primary product is centrifuged, washed, the clean precipitated product of bottom is obtained；Precipitated product is placed in freeze-day with constant temperature in vacuum, target product is obtained.The inventive method is easy, efficient, raw material is easily obtained, subsequent treatment condition is relatively simple, the cuprous oxide microspheres product prepared has obvious 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 method of cuprous oxide microballoon, and in particular to one kind has substantially double spherical structures
Nano balls of cuprous oxide preparation method.
Technical background
Cuprous oxide is as a kind of typical catalysis material, and with narrower electronics energy gap, its electronics energy gap is
2.17eV or so, (ultraviolet spectra is mainly utilized) compared with traditional catalysis material-titanium dioxide, and relatively low electronics energy gap is determined
Having determined cuprous oxide can be with the energy of significantly more efficient absorption solar visible light section, while can be swashed by most of visible ray
Hair, it 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.
Preparing the method for cuprous oxide has a lot, 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, and 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 is built etc. using copper acetate as raw material, and spherical and octahedral bodily form cuprous oxide particle is prepared using solvent-thermal method.Cui
Et al. the method that is reduced with glucose, CTAB prepares cuprous oxide cubic granules as surfactant.
But cuprous oxide particle that current various methods are prepared it is main using single spherical, cube and the octahedral bodily form as
Main, more single shape characteristic is very restricted the application of its excellent photoelectric property.Special symmetrical pattern energy
Enough assign cuprous oxide particle this special performance of class catalysis material；The obvious micro-nano oxygen of double spherical structures in the prior art
The preparation method for changing cuprous microballoon is not yet seen in report.
The content of the invention
There is the substantially micro-nano cuprous oxide microballoon of double spherical structures and its preparation it is an object of the invention to provide a kind of
Method；The micro-nano cuprous oxide microballoon of this pair of spherical structure is easy to be doped with other inorganic material, with relatively single spherical oxygen
Change cuprous stronger sensitiveness and response.
The present invention utilizes Cu2+The nucleation of ion in the basic conditions has sensitiveness, by adjusting Cu in aqueous phase2+Ion
Reduction nucleating condition and corresponding last handling process, realize that the micro-nano cuprous oxide with substantially double spherical structure special appearances is 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, is comprised the steps of：
(1) by cupric sulfate pentahydrate dissolution of crystals in deionized water, fully dissolving in sonic oscillation 10-15 minutes, is prepared dense
Spend the copper-bath for 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 into 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 the reaction solution prepared, solution initial reaction 5-10 minutes are allowed；
(4) sodium hydroxide solution is added dropwise again, the pH value of regulation reaction system is isothermal reaction 2-5 under 7.5-9, magnetic agitation
Hour, temperature control is 15-40 DEG C, obtains primary product；
(5) primary product is centrifuged with supercentrifuge, removes upper strata waste liquid, add deionized water oscillating washing, weight
Multiple above-mentioned centrifugation water-washing process 5-10 time, obtains the precipitated product that bottom is cleaned；
(6) precipitated product is placed in freeze-day with constant temperature in vacuum, obtains target product.
Further to realize the object of the invention, it is preferable that step (2), which is added after surfactant, also to be included adding oxidation stone
Black alkene, then carries out ultrasonic disperse processing；Every gram of cupric sulfate pentahydrate crystal adds 0.2-0.5 grams of graphene oxide；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, the reducing agent ascorbic acid na concn of dropwise addition is 0.2mol/L, and 60- is added dropwise in every gram of cupric sulfate pentahydrate crystal
80 milliliters of reducing agents, were at the uniform velocity dripped 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 speed of the supercentrifuge centrifugation is 10000 revs/min, and centrifugation every time goes residual solution in 5 minutes
Remove.
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
The temperature of freeze-day with constant temperature is that vacuum drying temperature is 55 DEG C in choosing, 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.
Relative to prior art, the present invention has advantages below：
(1) present invention utilizes reducing agent sodium ascorbate and Cu2+Into the sensitiveness of nuclear reaction in alkaline environment, phase is adjusted
The reaction condition answered, is directly reduced into the nano-particle with double spherical structures, what is prepared receives by cuprous oxide in the solution
The double spherical looks of rice cuprous oxide are good.
(2) cuprous oxide (single spherical, cube shaped, the octahedral bodily form of the invention prepared with current most methods
Deng) have notable difference there is provided a kind of approach come realize prepare symmetric double spherical structure cuprous oxide microsphere particles.It is this symmetrical
The cuprous oxide microsphere particles of double spherical structures have bigger specific surface area, it is easier to be doped preparation with other inorganic material
(such as graphene oxide), the two spheres system surface after doping generally has more reactivity sites.These characteristics can
With the photoelectric characteristic for the cuprous oxide microsphere particles for strengthening this pair of spherical structure, promote cuprous oxide under visible ray and ultraviolet light
Electron transition and photohole are produced, numerous areas, such as glucose and peroxide are may apply to using these outstanding features
Change photocatalysis Decomposition and the detection of hydrogen, with more single spherical alumina cuprous stronger sensitiveness and response；The light of organic dyestuff
Degraded, can handle polluted-water at low cost with more efficient；Detect to simple, intuitive the intensive ultraviolet in environment.Therefore it is this double
The cuprous oxide micro-and nano-particles of spherical structure can be prepared by simple synthetic method, with important application value.
(3) make the double ball cuprous nano particle diameters prepared homogeneous present invention introduces proper amount of surfactant,
More excellent photoelectric property can be produced with other materials doping.
(4) the whole preparation method of the present invention is simply controllable, it is not necessary to which complicated reaction condition, post-processing step is relatively easy
Realize, the double ball cuprous oxide product properties prepared are stable.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph for the cuprous micro-and nano-particles of double spherical aluminas that embodiment 1 is synthesized, times magnification
50000 times of number, figure medium scale is 200 nanometers.
Fig. 2 is the far-field scanning electron micrograph for the cuprous micro-and nano-particles of double spherical aluminas that embodiment 1 is synthesized, and is put
Big 5000 times of multiple, figure medium scale is 2 microns.
Fig. 3 is the X-ray diffractogram for the cuprous micro-and nano-particles of double spherical aluminas that embodiment 1 is synthesized.
Fig. 4-1 is the EDX electronic images of the cuprous micro-and nano-particles of double spherical aluminas after the graphene of embodiment 3 adulterates.
Fig. 4-2 is the EDX figures of the cuprous micro-and nano-particles surface C u elements of double spherical aluminas after the graphene of embodiment 3 adulterates
Picture.
Fig. 4-3 is the EDX figures of the cuprous micro-and nano-particles surface O elements of double spherical aluminas after the graphene of embodiment 3 adulterates
Picture.
Fig. 4-4 is the EDX figures of the cuprous micro-and nano-particles surface C element of double spherical aluminas after the graphene of embodiment 3 adulterates
Picture.
Fig. 5-1 is the Tafel curve for the cuprous micro-and nano-particles of single spherical alumina that the graphene of embodiment 3 adulterates.
Fig. 5-2 is the Tafel curve for the cuprous micro-and nano-particles of double spherical aluminas that the graphene of embodiment 3 adulterates.
Fig. 6-1 is the cuprous micro-and nano-particles of double spherical aluminas of the graphene of embodiment 3 doping under visible light illumination in water
In movement locus, light intensity is 43900Lux.
Fig. 6-2 be the graphene of embodiment 3 adulterate the cuprous micro-and nano-particles of double spherical aluminas under ultraviolet light in water
In movement locus, light intensity be 40 × 10-3W/cm2。
Embodiment
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 not limited 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 that concentration is 0.00396mol/L.
(2) 0.66g lauryl sodium sulfate (SDS) powder is taken to add in the copper-bath prepared, sonic oscillation is molten
Solution 15 minutes, then adds magneton, is placed on magnetic stirring apparatus and stirs, and stir speed (S.S.) is 210 revs/min.
(3) the reducing agent sodium ascorbate solution that 3mL solubility is 0.2mol/L, 1 point is added dropwise while stirring in reaction solution
At the uniform velocity dripped off in clock, allow solution initial reaction 5 minutes.
(4) appropriate 1mol/L sodium hydroxide solution is added dropwise again, the pH value of regulation reaction system is perseverance under 8, magnetic agitation
Temperature reaction 4 hours, temperature control is 35 DEG C.
(5) obtain primary product for brick-red sediment, by sediment with 10000 rpms of supercentrifuge from
The heart, removes upper strata waste liquid, adds deionized water oscillating washing, the above-mentioned centrifugation water-washing process of repetition 5 times.Bottom is finally obtained to wash
Net precipitated product.
(6) precipitated product is placed in freeze-day with constant temperature in vacuum, it is 55 DEG C to control temperature, drying time is 1.5 hours, is dried
It is complete to obtain the cuprous product of double spherical aluminas.
(7) 1 milligram of cuprous micro-and nano-particles of the double spherical aluminas prepared and the single ball obtained in the conventional way are taken
Shape cuprous oxide micro-and nano-particles, intensity of illumination for 43900Lux visible ray green glow irradiation under, respectively with concentration be 10 ×
10-3The glucose solution and concentration of mol/L are 0.1 × 10-3Mol/L hydrogenperoxide steam generator reaction, 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 multiplication factor is 50000 times, and its medium scale is 200 nanometers, prepared by display
Cuprous oxide out has obvious double spherical structures, and Fig. 2 is the far field SEM figures of double ball cuprous oxide particles, and multiplication factor is
5000 times, figure medium scale is 2 microns, and showing the particle size of preparation has preferable homogeneity.Fig. 3 is the double of the synthesis
The X-ray diffractogram of the cuprous micro-and nano-particles of spherical alumina, contrasts (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 the cuprous micro-and nano-particles photocatalysis performance of double spherical aluminas of table 1
Table 1 is to reduce Cu with traditional reducing agent (sodium ascorbate)2+The list for preparing of method it is spherical with the institute of the present embodiment 1
Obtain double reaction time of the cuprous micro-and nano-particles of spherical alumina 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 glow,
Intensity is 43900Lux.The cuprous micro-and nano-particles of double spherical aluminas prepared are compared with list is spherical, 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 has bigger specific surface area under equal quality, micro- when by visible light exposure
Electron transition occurs for ball surface, and the structure of double balls can produce 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.Bigger specific surface area means oxidation
It is cuprous to solve area and touch opportunity with testing bigger the connecing of solution, and acted on by the bigger illumination of area, generation is a large amount of certainly
By electronics and photohole, so as to strengthen the catalytic action to glucose and hydrogen peroxide.
The cuprous oxide micro-and nano-particles of this pair of spherical structure of the invention are with very excellent photocatalysis performance and oxidation
Degradation property (test and accompanying drawing for seeing below embodiment are proved), 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 be preserved more than two months in natural environment, and traditional cuprous oxide powder due to
The effect meeting rapid deterioration of photoetch, and for the visible light source in environment and ultraviolet source and organic-fuel and glucose
Solution etc., possesses sensitive reactivity due to the huge reactivity site in surface.Such performance makes double spherical structures
Microballoon can be applied in the glucose without enzyme and hydrogen peroxide context of detection, possess higher sensitivity and stability, and can
To substantially reduce testing cost.By detecting the change 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 that concentration is 0.00396mol/L.
(2) 0.66g lauryl sodium sulfate (SDS) powder is taken to add in the copper-bath prepared, sonic oscillation is molten
Solution 15 minutes, then adds magneton, is placed on magnetic stirring apparatus and stirs, and stir speed (S.S.) is 210 revs/min.
(3) the reducing agent sodium ascorbate solution that 3mL solubility is 0.2mol/L, 1 point is added dropwise while stirring in reaction solution
At the uniform velocity dripped off in clock, allow solution initial reaction 5 minutes.
(4) appropriate 1mol/L sodium hydroxide solution is added dropwise again, the pH value of regulation reaction system is perseverance under 8, magnetic agitation
Temperature reaction 4 hours, temperature control is 35 DEG C.
(5) obtain primary product for brick-red sediment, by sediment with 10000 rpms of supercentrifuge from
The heart, removes upper strata waste liquid, adds deionized water oscillating washing, the above-mentioned centrifugation water-washing process of repetition 5 times.Bottom is finally obtained to wash
Net precipitated product.
(6) precipitated product is placed in freeze-day with constant temperature in vacuum, it is 55 DEG C to control temperature, drying time is 1.5 hours.Dry
It is complete to obtain the cuprous product of double spherical aluminas.
(7) 1 milligram of cuprous micro-and nano-particles of the double spherical aluminas prepared and the single ball obtained in the conventional way are taken
Shape cuprous oxide micro-and nano-particles, intensity of illumination for 43900Lux visible ray green glow irradiation under, respectively with concentration be 1 ×
10-4G/l cresol red solution and concentration be 1 × 10-4G/l methyl orange solution reaction, obtain sample for organic dyestuff
The test result of degradation property.
The single spherical test result with the cuprous micro-and nano-particles degradation property of double spherical aluminas of table 2
Table 2 is to reduce Cu with traditional reducing agent (sodium ascorbate)2+The list for preparing of method it is spherical with the institute of the present embodiment 2
Complete reaction time for common are at two kinds in machine dye solution of double cuprous micro-and nano-particles of spherical alumina is averaged with microballoon
The test result of movement rate, wherein the cresol red solution and the consumption of methyl orange solution tested are 2 milliliters, test system institute
Visible light source is green glow, and intensity is 43900Lux.And the cuprous micro-and nano-particles of double spherical aluminas prepared and single spherical phase
Than, it is all shorter for the reaction time of both organic dyestuff, and possess faster single particle motion speed.Due to double spherical
Cuprous oxide micro-and nano-particles have larger specific surface area, therefore relatively single spherical bigger for 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 that concentration is 0.00396mol/L.
(2) 0.66g lauryl sodium sulfate (SDS) powder is taken to add in the copper-bath prepared, sonic oscillation is molten
Solution 15 minutes.
(3) after above-mentioned solution fully dissolves, 0.01g graphene oxides are taken to add reaction solution, sonic oscillation 1.5 hours fills
Divide scattered graphene oxide and reaction solution, magneton is then added in reaction solution, be placed on magnetic stirring apparatus and stir, stir speed (S.S.)
For 250 revs/min.
(4) the reducing agent sodium ascorbate solution that 3mL solubility is 0.2mol/L, 1 point is added dropwise while stirring in reaction solution
At the uniform velocity dripped off in clock, allow solution initial reaction 10 minutes.
(5) appropriate 1mol/L sodium hydroxide solution is added dropwise again, the pH value of regulation reaction system is perseverance under 8, magnetic agitation
Temperature reaction 5 hours, temperature control is 35 DEG C.
(6) obtain primary product for brick-red sediment, by sediment with 10000 rpms of supercentrifuge from
The heart, removes upper strata waste liquid, adds deionized water oscillating washing, the above-mentioned centrifugation water-washing process of repetition 10 times.Finally obtain bottom
Clean precipitated product.
(7) precipitated product is placed in freeze-day with constant temperature in vacuum, it is 55 DEG C to control temperature, drying time is 2 hours.After drying
Obtain the cuprous product of double spherical aluminas containing doping graphene oxide.
Fig. 4-1 is the EDX electronic images of the cuprous micro-and nano-particles of double spherical aluminas after graphene adulterates, and Fig. 4-2 is stone
The EDX images of the cuprous micro-and nano-particles surface C u elements of double spherical aluminas after black alkene doping, Fig. 4-3 is after graphene adulterates
The EDX images of double cuprous micro-and nano-particles surface O elements of spherical alumina, Fig. 4-4 is that double spherical aluminas after graphene adulterates are sub-
The EDX images of copper micro-and nano-particles surface C element, multiplication factor is 50000 times, and figure medium scale is 1 micron.Can be obvious
See the characteristics of cuprous oxide micro-and nano-particles of the double spherical structures of the gained of the present embodiment 3 are due in its structure, can be by simple
Inorganic material is doped compound preparation by the method for doping, such as graphene.The double balls containing graphene prepared
From EDX it can be seen from the figure thats, it has good pattern, and surface C u, O, C element point to structure cuprous oxide micro-and nano-particles
Cloth is uniform.
Fig. 5-1 is the Tafel curve for the cuprous micro-and nano-particles of single spherical alumina that graphene adulterates, and Fig. 5-2 is graphene
The Tafel curve of the cuprous micro-and nano-particles of double spherical aluminas of doping, the visible light source of irradiation is green glow, 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 surface potential difference Δ E produced before and after the cuprous micro-and nano-particles illumination of single spherical alumina of doping is graphene in 10mV, Fig. 5-2
The surface potential difference Δ E produced before and after the cuprous micro-and nano-particles illumination of double spherical aluminas of doping is 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 bigger electricity in the case of identical quality sample
Potential difference.Using the variation relation of this electrical potential difference, can by the cuprous micro-and nano-particles of double spherical aluminas of graphene-containing be used in pair
In the detection and sensing of light, Fig. 6-1 be graphene adulterate the cuprous micro-and nano-particles of double spherical aluminas under visible light illumination
Movement locus in water, light intensity is 43900Lux.Fig. 6-2 is that the cuprous micro-and nano-particles of double spherical aluminas that graphene adulterates exist
Movement locus under ultraviolet light in water, light intensity is 40 × 10-3W/cm2.It is cuprous micro-nano by the double spherical aluminas of observation
The different motion conditions of particle, can detect the ultraviolet ray intensity in environment.Single cuprous micro-and nano-particles of spherical alumina are certain
Under the ultraviolet light of intensity, because photoetch acts on stronger, the change of the universal motion conditions of its particle is not obvious therefore right
The sensitivity of stronger ultraviolet light detection is very low in environment, does not possess applicable value.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Embodiment restriction.For those of ordinary skill in the field, it can also make on the basis of the above description
Other various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all the present invention
Any modifications, equivalent substitutions and improvements made within spirit and principle etc., should be included in the protection of the claims in the present invention
Within the scope of.
Claims (10)
1. a kind of preparation method of double spherical micro/nano level cuprous oxide, it is characterised in that comprise the steps of：
(1) by cupric sulfate pentahydrate dissolution of crystals in deionized water, fully dissolve within sonic oscillation 10-15 minutes, compound concentration is
0.002mol/L-0.01mol/L copper-bath；
(2) Surfactant SDS is added in copper-bath, reaction raw materials liquid is subjected to ultrasonic dissolution 10-
15 minutes, it is subsequently placed on magnetic stirring apparatus and stirs；The mol ratio of control surface activating agent lauryl sodium sulfate and copper sulphate
For 1:4.0-4.2；
(3) reducing agent sodium ascorbate solution is added dropwise in the reaction solution prepared, solution initial reaction 5-10 minutes are allowed；
(4) sodium hydroxide solution is added dropwise again, the pH value of reaction system is adjusted for 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 strata waste liquid, added in deionized water oscillating washing, repetition
State centrifugation water-washing process 5-10 times, obtain 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：Step (2), which is added after surfactant, also to be included adding
Enter graphene oxide, then carry out ultrasonic disperse processing；Every gram of cupric sulfate pentahydrate crystal adds 0.2-0.5 grams of graphene oxide；
It is final that doping double spherical micro/nano level cuprous oxide is made.
3. preparation method according to claim 1, it is characterised in that：The reducing agent ascorbic acid na concn of dropwise addition is
60-80 milliliters of reducing agents are added dropwise in 0.2mol/L, every gram of cupric sulfate pentahydrate crystal, are at the uniform velocity dripped in 1 minute.
4. preparation method according to claim 1, it is characterised in that：Magnetic agitation speed is stirred on the magnetic stirring apparatus
For 200-250 revs/min.
5. 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, the concentration of sodium hydroxide solution used is 1mol/L, and the isothermal reaction time is 4 hours, and temperature control is 35 DEG C.
6. preparation method according to claim 1, it is characterised in that：The speed of the supercentrifuge centrifugation is 10000
Rev/min, centrifugation every time removes residual solution in 5 minutes.
7. 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.
8. preparation method according to claim 7, 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.
9. preparation method according to claim 1, it is characterised in that：The copper-bath concentration of preparation is 0.008mol/
L。
10. a kind of double spherical micro/nano level cuprous oxide, it is characterised in that it is by the optional preparation side of claim 1-9
Method is made.
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