CN109368684A - A kind of preparation method of cuprous oxide, the cuprous oxide and its application that this method is prepared - Google Patents
A kind of preparation method of cuprous oxide, the cuprous oxide and its application that this method is prepared Download PDFInfo
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- CN109368684A CN109368684A CN201811339996.3A CN201811339996A CN109368684A CN 109368684 A CN109368684 A CN 109368684A CN 201811339996 A CN201811339996 A CN 201811339996A CN 109368684 A CN109368684 A CN 109368684A
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- cuprous oxide
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- copper
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 87
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000007791 liquid phase Substances 0.000 claims abstract description 39
- 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 claims abstract description 18
- 239000000975 dye Substances 0.000 claims abstract description 17
- 239000008103 glucose Substances 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 14
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010792 warming Methods 0.000 claims abstract description 9
- 239000013049 sediment Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 7
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 7
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims description 7
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 7
- 229940012189 methyl orange Drugs 0.000 claims description 7
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 7
- 229940043267 rhodamine b Drugs 0.000 claims description 7
- 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 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 5
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 4
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000007704 wet chemistry method Methods 0.000 description 3
- 241000219095 Vitis Species 0.000 description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 description 2
- 235000014787 Vitis vinifera Nutrition 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- 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
- C01P2004/41—Particle morphology extending in three dimensions octahedron-like
-
- 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
-
- 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
Abstract
The present invention provides a kind of preparation methods of cuprous oxide, the described method comprises the following steps: (1) sodium hydroxide solution being added into copper-bath, obtains the first liquid-phase reaction system；(2) after 40~90 DEG C being warming up in first liquid-phase reaction system, glucose solution is added, isothermal reaction 50~70 minutes, obtains second liquid phase reaction system；(3) by sediment separation, washing, the drying in the second liquid phase reaction system, the cuprous oxide is obtained.The present invention also provides the cuprous oxide that this method is prepared, and the application using the cuprous oxide as photochemical catalyst in degradation of organic dyes.Obtained cuprous oxide has the advantages that environmental-friendly, morphology controllable, epigranular, good dispersion, yield are high, is easily isolated, is easy to operate safe.
Description
Technical field
The present invention relates to nano-oxide technical fields, and in particular to a kind of preparation method of cuprous oxide, party's legal system
Application of the standby obtained cuprous oxide and the cuprous oxide as photochemical catalyst.
Background technique
Cuprous oxide is a kind of important P type metal oxide semiconductor, and forbidden bandwidth is about 2.0eV, in visible light
Under absorption coefficient it is higher, theoretical energy conversion ratio is up to 12%.Due to it has excellent catalytic properties, it is good conductive and
Sensing characteristics, cuprous oxide have in multiple fields such as solar energy conversion, magnetic storage, catalyst, gas sensor, lithium ion batteries
It is widely used.In addition cuprous oxide or a kind of important industrial chemicals, can be used for coating, glass, ceramics, marine antifouling
Priming paint, fungicide agriculturally and glass porcelain glaze colorant etc..
It is well known that the nanometer of different-shape or the cuprous oxide of micrometer structure will lead to its magnetics, optics and electricity etc.
Performance changes.Research hotspot in recent years is concentrated mainly in the regulation of cuprous oxide pattern.Existing document report at present
It successfully synthesizes with cube, polyhedron, nanometer rods, nano wire, nanocages, nanometer or the isostructural oxidation of micrometre hollow sphere
Cuprous (J.Am.Chem.Soc.2012,134,1261-1267； Cryst.Growth Des.2015,15,4969-4974；
J.Phys.Chem.C.2013,117, 24611-24617).In addition, many patents of invention also disclose and prepare different-shape
Method (CN104477969A, CN103771484A, CN104760989A, CN104261457A of cuprous oxide micro nano structure
Deng).Although these methods realize the preparation of the cuprous oxide micro nano structure of different-shape, but there is also some problems, such as
Required reaction system is complex, needs to be added the chemical reagent such as surfactant, stabilizer (SDS, PVP, HMT etc.), usually
These reagents have toxicity, and price is higher.
In conclusion the cuprous oxide for needing to develop different-shape a kind of simple and easy, at low cost and that operation is controllable is micro-
The preparation method of rice structure.Given this present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of cuprous oxide.
The second object of the present invention is to provide the cuprous oxide that this method is prepared.
The third object of the present invention is to provide application of the cuprous oxide as photochemical catalyst.
To achieve the above object, technical scheme is as follows:
The present invention relates to a kind of preparation methods of cuprous oxide, the described method comprises the following steps:
(1) sodium hydroxide solution is added into copper-bath, obtains the first liquid-phase reaction system；
(2) after 40~90 DEG C being warming up in first liquid-phase reaction system, glucose solution, isothermal reaction 50 is added
~70 minutes, obtain second liquid phase reaction system；
(3) by sediment separation, washing, the drying in the second liquid phase reaction system, the cuprous oxide is obtained.
Preferably, in the step (1), the molar ratio of the copper sulphate and sodium hydroxide is 1:(2~5).
Preferably, in the step (1), the concentration of the copper-bath is 0.1~2mol/l, and the sodium hydroxide is molten
The concentration of liquid is 1~5mol/l.
Preferably, in the step (2), the molar ratio of the copper sulphate and glucose is 1:(0.5~3).
Preferably, in the step (2), the concentration of the glucose solution is 0.1~1mol/l.
Preferably, in the step (3), the second liquid phase reaction system is centrifugated, obtained sediment is used
Deionized water and ethanol washing are for several times, finally 20~30 hours dry at 60~90 DEG C, obtain the cuprous oxide.
The invention further relates to the cuprous oxide that the method is prepared.
Preferably, the structure of the cuprous oxide is octahedra, rescinded angle octahedron, the tetrakaidecahedron or spherical, and partial size is
0.5~10 micron.
The invention further relates to application of the cuprous oxide in degradation of organic dyes.
Preferably, the degradation carries out under visible light.
Preferably, the organic dyestuff selected from methyl orange, rhodamine B, crystal violet, methyl blue, methylene blue, it is Congo red in
At least one.
For the present invention using copper sulphate, sodium hydroxide, glucose as raw material, the oxidation for carrying out different-shape using wet chemistry method is sub-
The preparation of copper, has the advantage that
(1) reagent toxicity used in the present invention is smaller, and is reacted with environmental-friendly glucose reduction bivalent cupric ion
Condition is milder；
(2) present invention product morphology controllable obtained, from octahedra, rescinded angle is octahedra, the tetrakaidecahedron and spherical
It can get；
(3) present invention product cut size uniform, controllable obtained, it is micron available from 500 nanometers to 10.
(4) photochemical catalyst preparation method of the present invention is simple, easily operated, convenient for large-scale production.
Detailed description of the invention
Fig. 1 is the XRD spectra of the obtained cuprous oxide micrometer structure of embodiment 1；
Fig. 2 is the stereoscan photograph for the cuprous oxide micrometer structure that embodiment 1 obtains；
Fig. 3 is the stereoscan photograph for the cuprous oxide micrometer structure that embodiment 2 obtains；
Fig. 4 is the stereoscan photograph for the cuprous oxide micrometer structure that embodiment 3 obtains；
Fig. 5 is the stereoscan photograph for the cuprous oxide micrometer structure that embodiment 3 obtains；
Fig. 6 is the stereoscan photograph for the cuprous oxide micrometer structure that embodiment 3 obtains；
Fig. 7 is the stereoscan photograph for the cuprous oxide micrometer structure that embodiment 4 obtains；
Fig. 8 is the stereoscan photograph for the cuprous oxide micrometer structure that embodiment 4 obtains；
Fig. 9 is the stereoscan photograph for the cuprous oxide micrometer structure that embodiment 4 obtains；
Figure 10 is the stereoscan photograph for the cuprous oxide micrometer structure that embodiment 5 obtains；
Figure 11 is the stereoscan photograph for the cuprous oxide micrometer structure that embodiment 5 obtains；
Figure 12 is the stereoscan photograph for the cuprous oxide micrometer structure that embodiment 5 obtains；
Figure 13 is photocatalytic degradation figure of the obtained octahedra cuprous oxide of embodiment 6 to dyestuff；
Figure 14 is photocatalytic degradation figure of the obtained rescinded angle octahedron cuprous oxide of embodiment 7 to dyestuff；
Figure 15 is photocatalytic degradation figure of the obtained tetrakaidecahedron cuprous oxide of embodiment 8 to dyestuff.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
The present embodiments relate to a kind of preparation methods of cuprous oxide, method includes the following steps:
(1) sodium hydroxide solution is added into copper-bath, obtains the first liquid-phase reaction system, following reaction occurs:
CuSO4+ 2NaOH=Na2SO4+Cu(OH)2↓
That is: after sodium hydroxide solution being added into the copper-bath of blue, the flocculent deposit of Kocide SD blue is generated, such as
Both fruits reaction completely just, then the blue of solution is taken off.In one embodiment of the invention, in order to keep copper sulphate abundant
It generates and precipitates, the molar ratio of copper sulphate and sodium hydroxide is 1:(2~5).
In one embodiment of the invention, the concentration of copper-bath be 0.1-2mol/l, sodium hydroxide solution it is dense
Degree is 1-5mol/l.
(2) after 40-90 DEG C being warming up in the first liquid-phase reaction system, glucose solution, isothermal reaction 50~70 is added
Minute, obtain second liquid phase reaction system.Glucose is reduced to cuprous oxide as reducing agent, by Kocide SD, occurs following
Reaction:
C5H11O5-CHO+2Cu(OH)2=C5H11O5-COOH+Cu2O↓+2H2O
In one embodiment of the invention, in order to make Kocide SD be fully converted into cuprous oxide, copper sulphate and grape
The molar ratio of sugar is 1:(0.5~3).
In one embodiment of the invention, the concentration of glucose solution is 0.1-1mol/l.
(3) by sediment separation, washing, the drying in second liquid phase reaction system, cuprous oxide is obtained.
In one embodiment of the invention, sediment is separated from second liquid phase reaction system by being centrifuged, will
The sediment deionized water and ethanol washing arrived for several times after, dry 20~30 hours at 60~90 DEG C, obtain target product
Cuprous oxide.
The embodiment of the present invention further relates to the cuprous oxide that method is prepared.By changing preparation condition, available knot
Structure is octahedron, rescinded angle octahedron, the tetrakaidecahedron or spherical cuprous oxide, and partial size is 0.5 to 10 microns.
The embodiment of the present invention further relates to application of the cuprous oxide in degradation of organic dyes.
Degradation can be carried out under visible light, the cuprous oxide for methyl orange, rhodamine B, crystal violet, methyl blue,
The organic dyestuff such as methylene blue, Congo red have degradation effect.
Embodiment 1
1) 5g Salzburg vitriol is added in the three-necked flask for filling 20ml water at 25 DEG C, stirs 10 minutes, makes sulfuric acid
Copper is completely dissolved, and obtains the light blue copper-bath of 1.0mol/l；
2) sodium hydroxide solution of 20ml 3.125mol/l is added in above-mentioned resulting copper-bath, continues to stir
20 minutes, obtain the first liquid-phase reaction system；
3) above-mentioned first liquid-phase reaction system is warming up to 55 DEG C, the glucose for rapidly joining 20ml 0.125mol/l is molten
Liquid isothermal reaction 60 minutes, obtains second liquid phase reaction system；
4) the second liquid phase reaction system obtained step 3) is centrifugated, for several times with deionized water and ethanol washing, most
Drying for 24 hours, obtains brick-red cuprous oxide in 80 DEG C of vacuum oven afterwards.
Fig. 1 is the XRD spectra of the obtained cuprous oxide of embodiment 1, the standard x RD spectrogram (PDF-# with cuprous oxide
It 05-0677) coincide, it was demonstrated that 1 products therefrom of embodiment is cuprous oxide, and the XRD spectra of other embodiments products therefrom is and Fig. 1
It is identical, show that products therefrom is cuprous oxide.
Fig. 2 is the stereoscan photograph of the obtained cuprous oxide of embodiment 1.As can be seen from Figure, cuprous oxide
Pattern is octahedral structure, and partial size is about 873 nanometers.
Embodiment 2
1) 5g Salzburg vitriol is added in the three-necked flask for filling 20ml water at 25 DEG C, stirs 10 minutes, makes sulfuric acid
Copper is completely dissolved, and obtains the light blue copper-bath of 1.0mol/l；
2) sodium hydroxide solution of 20ml 3.125mol/l is added in above-mentioned resulting copper-bath, continues to stir
20 minutes, obtain the first liquid-phase reaction system；
3) above-mentioned resulting first liquid-phase reaction system is warming up to 55 DEG C, rapidly joins the Portugal of 20ml 0.225mol/l
Grape sugar juice isothermal reaction 60 minutes, obtains second liquid phase reaction system；
4) the second liquid phase reaction system obtained step 3) is centrifugated, for several times with deionized water and ethanol washing, most
Drying for 24 hours, obtains brick-red cuprous oxide in 80 DEG C of vacuum oven afterwards.
Fig. 3 is the stereoscan photograph of the obtained cuprous oxide of embodiment 2.As can be seen from Figure, cuprous oxide
Pattern is octahedral structure, about 1.18 microns of partial size.
Embodiment 3
1) 5g Salzburg vitriol is added in the three-necked flask for filling 20ml water at 25 DEG C, stirs 10 minutes, makes sulfuric acid
Copper is completely dissolved, and obtains the light blue copper-bath of 1.0mol/l；
2) sodium hydroxide solution of 20ml 3.125mol/l is added in above-mentioned resulting copper-bath, continues to stir
20 minutes, obtain the first liquid-phase reaction system；
3) above-mentioned resulting first liquid-phase reaction system is warming up to 55 DEG C, rapidly joins the Portugal of 20ml 0.25mol/l
Grape sugar juice isothermal reaction 60 minutes, obtains second liquid phase reaction system；
4) the second liquid phase reaction system obtained step 3) is centrifugated, for several times with deionized water and ethanol washing, most
Drying for 24 hours, obtains brick-red cuprous oxide in 80 DEG C of vacuum oven afterwards.
Fig. 4, Fig. 5, Fig. 6 are the stereoscan photograph of the obtained cuprous oxide of embodiment 3.As can be seen from Figure, oxygen
Change cuprous pattern be rescinded angle octahedral structure and uniform particle sizes, about 1.41 microns of partial size.
Embodiment 4
1) 5g Salzburg vitriol is added in the three-necked flask for filling 20ml water at 25 DEG C, stirs 10 minutes, makes sulfuric acid
Copper is completely dissolved, and obtains the light blue copper-bath of 1.0mol/l；
2) sodium hydroxide solution of 20ml 3.125mol/l is added in above-mentioned resulting copper-bath, continues to stir
20 minutes, obtain the first liquid-phase reaction system；
3) above-mentioned resulting first liquid-phase reaction system is warming up to 55 DEG C, rapidly joins the grape of 20ml 0.5mol/l
Sugar juice isothermal reaction 60 minutes, obtains second liquid phase reaction system；
4) the second liquid phase reaction system obtained step 3) is centrifugated, for several times with deionized water and ethanol washing, most
Drying for 24 hours, obtains brick-red cuprous oxide in 80 DEG C of vacuum oven afterwards.
Fig. 7, Fig. 8, Fig. 9 are the stereoscan photograph of the obtained cuprous oxide of embodiment 4.As can be seen from Figure, oxygen
Change cuprous pattern be tetrakaidecahedron structure and uniform particle sizes, about 1.11 microns of partial size.
Embodiment 5
1) 5g Salzburg vitriol is added in the three-necked flask for filling 20ml water at 25 DEG C, stirs 10 minutes, makes sulfuric acid
Copper is completely dissolved, and obtains the light blue copper-bath of 1.0mol/l；
2) sodium hydroxide solution of 20ml 3.125mol/l is added in above-mentioned resulting copper-bath, continues to stir
20 minutes, obtain the first liquid-phase reaction system；
3) above-mentioned resulting first liquid-phase reaction system is warming up to 55 DEG C, rapidly joins the Portugal of 20ml 0.625mol/l
Grape sugar juice isothermal reaction 60 minutes, obtains second liquid phase reaction system；
4) the second liquid phase reaction system obtained step 3) is centrifugated, for several times with deionized water and ethanol washing, most
Drying for 24 hours, obtains brick-red cuprous oxide in 80 DEG C of vacuum oven afterwards.
Figure 10, Figure 11, Figure 12 are the stereoscan photograph of the obtained cuprous oxide of embodiment 5.As can be seen from Figure,
The pattern of cuprous oxide be spherical structure and uniform particle sizes, about 1.14 microns of partial size.
Test case 1
It takes octahedra cuprous oxide obtained by 30mg embodiment 2 as photochemical catalyst, is divided into 6 parts, be distributed into 6
In quartz test tube.Then take six kinds of dye solutions (it is methyl orange, rhodamine B, crystal violet, methyl blue, methylene blue, Congo red, just
Beginning concentration is 15mg/l) each 10ml, it is separately added into 6 test tubes, quartz test tube is put into light-catalyzed reaction instrument, dark item
0.5h is stirred under part, dyestuff is made to reach adsorption-desorption balance in catalyst surface.Then light source is opened, is carried out wait react
Light source is closed when 180min.By the liquid centrifugation in all quartz ampoules, takes supernatant liquor to be put into ultraviolet-visual spectrometer and test
Its absorbance.By concentration-absorbance working curve of various dyestuffs, the concentration of dyestuff after reaction is calculated.
Figure 13 show the obtained octahedra cuprous oxide catalysis agent of embodiment 2 to the degradation rate figure of six kinds of dyestuffs.Its
In, for same dyestuff, the histogram graph representation initial concentration in left side, the concentration after the histogram graph representation degradation on right side.From figure
In as can be seen that methyl orange, rhodamine B, crystal violet, methyl blue, methylene blue, Congo red concentration become original respectively
24.496%, 85.528%, 95.337%, 38.872%, 88.469%, 13.524%.
Test case 2
The resulting top rake octahedron cuprous oxide catalysis agent of 30mg embodiment 3 is taken, is grasped according to the process of test case 1
Make.
Figure 14 show the obtained top rake octahedron cuprous oxide catalysis agent of embodiment 3 to the degradation rate of six kinds of dyestuffs
Figure.Wherein, for same dyestuff, the histogram graph representation initial concentration in left side, the concentration after the histogram graph representation degradation on right side.
It can be seen from the figure that methyl orange, rhodamine B, crystal violet, methyl blue, methylene blue, Congo red concentration become original respectively
12.365%, 87.016%, 86.59%, 56.054%, 53.802%, 7.036%.
Test case 3
The resulting tetrakaidecahedron cuprous oxide catalysis agent of 30mg embodiment 4 is taken, is operated according to the process of test case 1.
Figure 15 show the obtained tetrakaidecahedron cuprous oxide catalysis agent of embodiment 4 to the degradation rate figure of six kinds of dyestuffs.
Wherein, for same dyestuff, the histogram graph representation initial concentration in left side, the concentration after the histogram graph representation degradation on right side.From
As can be seen that methyl orange, rhodamine B, crystal violet, methyl blue, methylene blue, Congo red concentration become original respectively in figure
14.356%, 74.186%, 74.186%, 45.009%, 50.440%, 3.4966%.
The present invention carries out not similar shape using copper sulphate cheap and easy to get, sodium hydroxide, glucose as raw material, using wet chemistry method
The preparation of the cuprous oxide of looks.It prepares a series of cuprous oxide photocatalyst of different-shapes using the method at present and is used for
The research of various different dyes degradation reactions has not been reported under visible light.
Simple wet chemistry method of the present invention synthesizes a series of different-shapes by regulating and controlling the dosage of glucose
Cuprous oxide photocatalyst, reaction system is simple, does not need that any surfactant and stabilizer is added.This method is urged
Agent epigranular, good dispersion, yield are high, are easily isolated, safety easy to operate, have to exploitation novel photocatalysis material important
Theoretical and practical significance.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of preparation method of cuprous oxide, which is characterized in that the described method comprises the following steps:
(1) sodium hydroxide solution is added into copper-bath, obtains the first liquid-phase reaction system；
(2) after 40~90 DEG C being warming up in first liquid-phase reaction system, glucose solution, isothermal reaction 50~70 is added
Minute, obtain second liquid phase reaction system；
(3) by sediment separation, washing, the drying in the second liquid phase reaction system, the cuprous oxide is obtained.
2. the method according to claim 1, wherein in the step (1), the copper sulphate and sodium hydroxide
Molar ratio is 1:(2~5).
3. the method according to claim 1, wherein in the step (1), the concentration of the copper-bath is
0.1~2mol/l, the concentration of the sodium hydroxide solution are 1~5mol/l.
4. the method according to claim 1, wherein in the step (2), the copper sulphate and glucose rub
You are than being 1:(0.5~3).
5. the method according to claim 1, wherein in the step (2), the concentration of the glucose solution is
0.1~1mol/l.
6. the method according to claim 1, wherein in the step (3), by the second liquid phase reaction system
Centrifuge separation, for several times by obtained sediment deionized water and ethanol washing, finally drying 20~30 is small at 60~90 DEG C
When, obtain the cuprous oxide.
7. according to claim 1 to the cuprous oxide that any one of 6 the methods are prepared.
8. cuprous oxide according to claim 7, which is characterized in that the structure of the cuprous oxide is octahedra, rescinded angle
The octahedra, tetrakaidecahedron or spherical, partial size are 0.5~10 micron.
9. application of the cuprous oxide as claimed in claim 7 in degradation of organic dyes.
10. application according to claim 9, which is characterized in that the organic dyestuff is selected from methyl orange, rhodamine B, methyl
At least one of purple, methyl blue, methylene blue, Congo red.
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| CN110227457A (en) * | 2019-06-26 | 2019-09-13 | 成都理工大学 | A kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst |
| CN113856704A (en) * | 2021-11-16 | 2021-12-31 | 四川轻化工大学 | Photocatalyst for efficiently degrading antibiotics and preparation method and application thereof |
| CN114762826A (en) * | 2021-07-21 | 2022-07-19 | 天津科技大学 | High index crystal plane Cu2Preparation method and application of O photocatalyst |
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| CN105152199A (en) * | 2015-08-06 | 2015-12-16 | 上海应用技术学院 | Preparation method of tetradecahedral cuprous oxide nanoparticle |
| CN105621473A (en) * | 2014-11-06 | 2016-06-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nanometer cuprous oxide particle, and morphology and particle size controlling method |
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| CN102583499A (en) * | 2012-01-11 | 2012-07-18 | 哈尔滨工业大学 | Preparation method for cuprous oxide micron/nano crystal with controllable morphology |
| CN105621473A (en) * | 2014-11-06 | 2016-06-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nanometer cuprous oxide particle, and morphology and particle size controlling method |
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| CN110227457A (en) * | 2019-06-26 | 2019-09-13 | 成都理工大学 | A kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst |
| CN114762826A (en) * | 2021-07-21 | 2022-07-19 | 天津科技大学 | High index crystal plane Cu2Preparation method and application of O photocatalyst |
| CN113856704A (en) * | 2021-11-16 | 2021-12-31 | 四川轻化工大学 | Photocatalyst for efficiently degrading antibiotics and preparation method and application thereof |
| CN113856704B (en) * | 2021-11-16 | 2023-04-07 | 四川轻化工大学 | Photocatalyst for efficiently degrading antibiotics and preparation method and application thereof |
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