CN110215922A - Core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material preparation method - Google Patents
Core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material preparation method Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 43
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229920001577 copolymer Polymers 0.000 title claims abstract description 23
- 239000011258 core-shell material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000002086 nanomaterial Substances 0.000 claims abstract description 50
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 10
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 78
- 230000015572 biosynthetic process Effects 0.000 claims description 31
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 8
- 238000005297 material degradation process Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 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 description 9
- 229940012189 methyl orange Drugs 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000033001 locomotion Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- -1 2- methyl Imidazoles zinc salt Chemical class 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- SBNQJAHLGZCHCA-UHFFFAOYSA-N [Co].CC=1NC=CN1 Chemical compound [Co].CC=1NC=CN1 SBNQJAHLGZCHCA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000002910 structure generation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B01J35/39—
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- B01J35/396—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material preparation method, is related to a kind of preparation method of nano material.It is the ZnO/Co of existing method preparation to be solved3O4The problem of material degradation effect difference.Zinc nitrate hexahydrate: one, being dissolved in methanol and form solution A by method, and 2-methylimidazole is dissolved in methanol and forms solution B, and solution A and B mixing are placed in aging in baking oven, washing precipitating, dry ZIF8 nano material;Two, it disperses ZIF8 nano material in methanol and forms solution C, cobalt chloride is dissolved in methanol and forms solution D, 2-methylimidazole is dissolved in methanol and forms solution E, solution C, D and E mixing, are placed in aging in baking oven, obtain solidliquid mixture, washing precipitating, dry 67 nano material of ZIF8@;Three, it takes 67 nano material of ZIF8@to calcine, obtains ZnO/Co3O4Nano material.The present invention is used for field of nanometer material technology.
Description
Technical field
The present invention relates to a kind of preparation methods of nano material.
Background technique
In Environmental Chemistry field, photocatalytic pollutant degradation is always hot spot concerned by people, is generally approved by people and grinds
The catalyst studied carefully mainly has ZnO, TiO2、CdS、ZnS、MoS2Deng.Preparation method mainly includes sol-gel method, ion exchange
Method, the microwave-assisted precipitation method, electrochemical deposition method, hydro-thermal method and solvent-thermal method and heat treating process.It is applied to pollutant at present
Have the defects that on the material structure of degradation it is universal, such as someone it has been reported that the inhomogenous ZnO/Co of pattern3O4Material is deposited
It is too small in specific surface area, and then electron-hole recombinations are too fast, on the other hand orient without the channel supplied for electronic hole of uniform rule
Migration, all substantially reduces photocatalysis efficiency, degradation effect is unsatisfactory.
Summary of the invention
The present invention is to solve the ZnO/Co of existing method preparation3O4The problem of material degradation effect difference, provides a seed nucleus-
Shell bilayer ZnO/Co3O4The preparation method of nano material.
The preparation method of core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material of the present invention, comprising the following steps:
One, the synthesis of ZIF8 material:
By zinc nitrate hexahydrate (Zn (NO3)2·6H2O it) is dissolved in methanol and forms solution A, 2-methylimidazole is dissolved in methanol
Middle formation solution B while magnetic stirrer solution A, is slowly added to solution B and continuing and stirs 5-10min, formation it is mixed
It closes solution to be transferred in reaction kettle, be placed in baking oven, the aging 12-14h under the conditions of 100-120 DEG C obtains solidliquid mixture, uses
Methanol centrifuge washing solid precipitates three times, and under the conditions of 70-80 DEG C, dry 8-12h obtains the ZIF8 nanometer of granatohedron
Material;
Two, the synthesis of ZIF8@ZIF67 material:
It disperses ZIF8 nano material ultrasound 30-60min in methanol and forms solution C, cobalt chloride is dissolved in shape in methanol
At solution D, 2-methylimidazole is dissolved in methanol and forms solution E, while magnetic stirrer solution C, successively slowly plus
Enter solution D and solution E, and continue to stir 5-10min, the mixed solution of formation is transferred in reaction kettle, is placed in baking oven, 100-
Aging 12-14h, obtains solidliquid mixture under the conditions of 120 DEG C, three times with methanol centrifuge washing solid precipitating, in 70-80 DEG C of condition
Under, dry 8-12h obtains 67 nano material of ZIF8@of core-shell structure copolymer two-tier rhombic dodecahedron;
Three, ZnO/Co3O4The synthesis of nano material:
It takes 67 nano material of ZIF8@to be placed in porcelain boat, in air atmosphere, is placed in Muffle furnace, is warming up to 350-370
DEG C calcining 2-3h, heating rate be 1-1.5 DEG C/min, obtain regular appearance, uniform ZnO/Co3O4Nano material.
Further, the mass concentration of zinc nitrate hexahydrate is 29-30g/L in step 1 solution A.
Further, the mass concentration of 2-methylimidazole is 49-50g/L in step 1 solution B.
Further, the volume ratio of solution A and solution B is 3:(2-2.5 in step 1).
Further, the mass volume ratio of ZIF8 nano material and methanol is (0.14-0.16) g in step 2 solution C:
20mL。
Further, the mass concentration of cobalt chloride is 5.00g/L~22.62g/L in step 2 solution D.
Further, the mass concentration of 2-methylimidazole is 25.50g/L~114.37g/L in step 2 solution E.
Further, the volume ratio of step 2 component solution C, solution D and solution E is 10:(3-6): (3-6).
Further, it dries described in step 1 and step 2 as vacuum drying.
Beneficial effects of the present invention:
Present invention employs regular appearance and the very big ZIF67 (2-methylimidazole cobalt salt) of specific surface area, ZIF8 (2- methyl
Imidazoles zinc salt) material be presoma, pass through solvent structure core-shell structure copolymer ZIF67 nanometers of materials of bilayer ZIF8 simple to operation
Material, using being heat-treated under air atmosphere, has obtained the core-shell structure copolymer bilayer ZnO/Co of regular appearance, large specific surface area3O4Nanometer material
Material.Since ZnO is n-type semiconductor, Co3O4P-type semiconductor, formed p-n junction material be more favorable for electrons and holes separation and
Diffusion movement, to improve photocatalytic activity.
Synthetic method of the present invention is simply easily realized, is not necessarily to high-end professional equipment, synthesis temperature is not high, and energy consumption is small, at low cost
It is honest and clean.The morphological rules that obtains after calcining, uniform core-shell structure copolymer two-tier rhombic dodecahedron form p-n junction heterojunction structure ZnO/Co3O4
Nano material.Firstly, material maintains the porous regular pattern of ZIF8@ZIF67, remains big specific surface area and provide more
Active site, to reach better catalytic efficiency;Second, it is fixed to be conducive to electrons and holes for regular cellular structure
To diffusion motion, electrons and holes separating capacity is increased;Third, the formation of p-n junction profile material can effectively inhibit electronics empty
The probability of recombination in cave can reach better photocatalysis effect naturally.Experiment shows this special regular p-n junction profile material
It is 50 μm of olL in methyl orange initial concentration by taking the degradation of methyl orange as an example applied to contaminant degradation-1When, after 6h, methyl
The degradation rate of orange can reach 96.36%, and photocatalytic degradation effect is significant.
Detailed description of the invention
Fig. 1 is 67 nano material SEM of the ZIF8@figure for amplifying 50000 times;
Fig. 2 is 67 nano material SEM of the ZIF8@figure for amplifying 100000 times;
Fig. 3 is the ZnO/Co for amplifying 50000 times3O4Nano material SEM figure;
Fig. 4 is the ZnO/Co for amplifying 150000 times3O4Nano material SEM figure;
Fig. 5 is ZnO/Co3O4The XPS of nano material schemes;
Fig. 6 is ZnO/Co3O4The Mott-Schottky curve of nano material at different frequencies;
Fig. 7 is the photoelectricity flow graph comparison of calcining front and back material;
Fig. 8 is ZnO/Co3O4Nano material degradation methyl orange UV-vis figure.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: present embodiment core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material preparation side
Method, comprising the following steps:
One, the synthesis of ZIF8 material:
By zinc nitrate hexahydrate (Zn (NO3)2·6H2O it) is dissolved in methanol and forms solution A, 2-methylimidazole is dissolved in methanol
Middle formation solution B while magnetic stirrer solution A, is slowly added to solution B and continuing and stirs 5-10min, formation it is mixed
It closes solution to be transferred in reaction kettle, be placed in baking oven, the aging 12-14h under the conditions of 100-120 DEG C obtains solidliquid mixture, uses
Methanol centrifuge washing solid precipitates three times, and under the conditions of 70-80 DEG C, dry 8-12h obtains the ZIF8 nanometer of granatohedron
Material;
Two, the synthesis of ZIF8@ZIF67 material:
Dispersing formation solution C in methanol for ZIF8 nano material ultrasound 30-60min, (it is more uniform suspended to disperse
Liquid, ZIF8 nano material can precipitate after standing), cobalt chloride is dissolved in methanol and forms solution D, 2-methylimidazole is dissolved in methanol
Middle formation solution E while magnetic stirrer solution C, is successively slowly added to solution D and solution E, and continues to stir 5-
The mixed solution of 10min, formation are transferred in reaction kettle, are placed in baking oven, and aging 12-14h under the conditions of 100-120 DEG C is obtained
Solidliquid mixture, three times with methanol centrifuge washing solid precipitating, under the conditions of 70-80 DEG C, dry 8-12h obtains core-shell structure copolymer bilayer
67 nano material of ZIF8@of granatohedron;
Wherein core of the ZIF8 nano material as final material in solution C is added cobalt ions (solution D), adds 2-
Methylimidazole can grow one layer of ZIF67 on the surface ZIF8, form the granatohedron structural material of ZIF8@ZIF67.
Three, ZnO/Co3O4The synthesis of nano material:
It takes 67 nano material of ZIF8@to be placed in porcelain boat, in air atmosphere, is placed in Muffle furnace, is warming up to 350-370
DEG C calcining 2-3h, heating rate be 1-1.5 DEG C/min, obtain regular appearance, uniform ZnO/Co3O4Nano material.
Present embodiment synthetic method is simply easily realized, high-end professional equipment is not necessarily to, and synthesis temperature is not high, and energy consumption is small, at
This is cheap.The morphological rules that obtains after calcining, uniform core-shell structure copolymer two-tier rhombic dodecahedron form p-n junction heterojunction structure ZnO/
Co3O4Nano material.Firstly, material maintains the porous regular pattern of ZIF8@ZIF67, remains big specific surface area and provide
More active sites, to reach better catalytic efficiency;Second, regular cellular structure is conducive to electronics and sky
Cave orients diffusion motion, increases electrons and holes separating capacity;Third, the formation of p-n junction profile material can effectively inhibit electricity
The probability of recombination in sub- hole can reach better photocatalysis effect naturally.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: six hydration in step 1 solution A
The mass concentration of zinc nitrate is 29-30g/L.It is other same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: 2- in step 1 solution B
The mass concentration of methylimidazole is 49-50g/L.It is other the same as one or two specific embodiments.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: molten in step 1
The volume ratio of liquid A and solution B is 3:(2-2.5).It is other identical as one of specific embodiment one to three.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: step 2 solution C
The mass volume ratio of middle ZIF8 nano material and methanol is (0.14-0.16) g:20mL.Other and specific embodiment one to four
One of it is identical.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: step 2 solution D
The mass concentration of middle cobalt chloride is 5.00g/L~22.62g/L.It is other identical as one of specific embodiment one to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: step 2 solution E
The mass concentration of middle 2-methylimidazole is 25.50g/L~114.37g/L.It is other identical as one of specific embodiment one to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: step 2 component
The volume ratio of solution C, solution D and solution E is 10:(3-6): (3-6).It is other identical as one of specific embodiment one to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: step 1 and step
It is dry for vacuum drying described in rapid two.It is other identical as one of specific embodiment one to eight.
Vacuum drying can preferably avoid sample oxidation by air in slightly higher temperature, while be easier to obtain moisture drying
More thoroughly, convenient for storage.
Elaborate below to the embodiment of the present invention, following embodiment under the premise of the technical scheme of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment 1:
One, the synthesis of ZIF8 material:
By 0.892g zinc nitrate hexahydrate (Zn (NO3)2·6H2O it) is dissolved in 30ml methanol and forms solution A, by 0.985g's
2-methylimidazole, which is dissolved in 20ml methanol, forms solution B, while magnetic stirrer solution A, be slowly added to solution B and after
Continuous stirring 5min, the mixed solution of formation are transferred in reaction kettle, are placed in baking oven, aging 12h under the conditions of 100 DEG C.Use methanol
Centrifuge washing precipitates three times, under the conditions of 70 DEG C, is dried in vacuo 8h, obtains the ZIF8 nano material of granatohedron.
Two, the synthesis of ZIF8@ZIF67 material:
It disperses 0.16g ZIF8 nano material ultrasound 30min in 20ml methanol and forms solution C, by 0.136g cobalt chloride
(CoCl2) be dissolved in 6ml methanol and form solution D, the 2-methylimidazole of 0.686g is dissolved in 6ml methanol and forms solution E, magnetic force
While blender agitating solution C, it is successively slowly added to solution D and solution E, and continues to stir 5min, the mixed solution of formation
It is transferred in reaction kettle, is placed in baking oven, aging 12h under the conditions of 100 DEG C.Three times with methanol centrifuge washing precipitating, in 70 DEG C of items
Under part, it is dried in vacuo 8h, obtains 67 nano material of ZIF8@of core-shell structure copolymer two-tier rhombic dodecahedron.
Three, ZnO/Co3O4The synthesis of nano material:
It takes 67 nano material of ZIF8@of 60mg in porcelain boat, in air atmosphere, is placed in Muffle furnace, is warming up to 350
DEG C calcining 2h, heating rate be 1 DEG C/min, by SEM, XPS characterization can determine to have obtained regular appearance, uniform ZnO/Co3O4
Nano material.
Scheme to can be seen that the sample size synthesized is uniform by SEM, about 500nm, the ZnO/Co formed after calcining3O4Retain
The granatohedron pattern of ZIF8@67, does not collapse, surface becomes coarse formation porous structure.
(1) XPS is tested
XPS test result confirms ZnO and Co3O4The formation of two kinds of substances, and sample size in test result is summarized in
Following table:
(2) Mott-Schottky curve
This experiment uses Shanghai Chen Hua CHI660D electrochemical workstation, is to electrode, Ag/ with Pt under three-electrode system
AgCl is reference electrode, the ZnO/Co of preparation3O4Nanomaterial loadings are in, as working electrode, electrolyte used is on ITO
The Na of 0.1M2SO4Solution.In M-S curve graph, positive and negative according to the corresponding slope of curve of depletion layer can determine whether that oxidation film is partly led
The type of body.If slope is positive value, expression oxidation film is n-type semiconductor;If slope is negative value, for p-type semiconductor.Figure
Curve a indicates that 1000Hz, curve b indicate that 1200Hz, curve c indicate 1500Hz in 6.
It will be appreciated from fig. 6 that current potential is in -0.2V~0.4V, slope is positive, and embodies n-type semiconductor feature, and current potential is located at
When 0.4V~0.85V, slope is negative, and shows p-type semiconductor feature, thus obviously can be concluded that ZnO/Co3O4In nano material
There is the formation of p-n junction, this has great advantage for the diffusion motion of the two kinds of carriers in hole and electronics and separation, further mentions
Highlight catalytic active.
(3) photoelectricity current test
This experiment uses Shanghai Chen Hua CHI660D electrochemical workstation, is to electrode, Ag/ with Pt under three-electrode system
AgCl is reference electrode, the ZnO/Co of preparation3O4Nanomaterial loadings are in, as working electrode, electrolyte used is on ITO
The KOH solution of 0.1M applies the rate of departure that 0.3V bias promotes photo-generated carrier.
The changing value size of photoelectric current and the PhotoelectrocatalytiPerformance Performance of material have close and directly contact.As seen from Figure 7, it forges
ZnO/Co after burning3O4Nano material photocurrent variations value improves octuple up to 8 μ A compared to photoelectric current before calcining.
Curve 1 is ZIF8@ZIF67 in Fig. 7, and curve 2 is ZnO/Co3O4Nano material.
(4) Photodegradation of Methyl Orange is tested
Configuration concentration is 50 μm of olL first-1Methyl orange solution, and weigh 50mg ZnO/Co3O4Catalyst sample,
The two mixing is placed in quartz reactor (capacity 100mL), stirs 2h under dark-state environment in the hope of reaching adsorption-desorption balance.
The xenon lamp for mooring luxuriant and rich with fragrance Lay PLS-SXE300SUV is light source, is equipped with 365nm ultraviolet filter, and irradiation level is 5 μ w/cm2Stone is irradiated in position
English reactor, and 5mL is sampled at interval of 1h, supernatant is taken after centrifuge separation, tests to obtain map using ultraviolet specrophotometer.
This experiment is using for typical pollutant methyl orange, it was demonstrated that the light degradation dyestuff effect of material.Methyl orange
50 μm of olL of initial concentration-1, as seen from Figure 8 after 6h, the characteristic peak of methyl orange disappears substantially, and the orange of solution gradually disappears
It moves back, or even already close to transparent.It is computed, when 6h, degradation rate reaches 96.36%.
Methyl orange solution initial concentration is 5 μm of olL-1, after methyl orange concentration reduces, same reaction conditions, illumination 1h, first
Base orange, that is, degradable complete.
The porous core-shell structure copolymer ZnO/Co of granatohedron3O4The dyestuff degradation effect of nano material is excellent, there is great development
Prospect.
Embodiment 2:
The present embodiment is unlike the first embodiment: when step 2 configures solution D, the quality of cobalt chloride is 0.030g, configuration
When solution E, the quality of 2-methylimidazole is 0.153g,
As a result: increasing Co in sample3O4Ratio, photoelectric current declined, it was demonstrated that ZnO has catalyst system prior
Contribution.
Embodiment 3:
The present embodiment is unlike the first embodiment: step 3 450 DEG C of calcining 2h in Muffle furnace,
As a result: 450 DEG C of calcinings, about 40% sample granatohedron structure generation collapsing is damaged, under corresponding photoelectric current
Drop, methyl orange degradation required time lengthen.
Claims (9)
1. core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material preparation method, it is characterised in that this method includes following step
It is rapid:
One, the synthesis of ZIF8 material:
Zinc nitrate hexahydrate is dissolved in methanol and forms solution A, 2-methylimidazole is dissolved in methanol and forms solution B, is stirred molten
While liquid A, solution B being added and continues to stir 5-10min, the mixed solution of formation is transferred in reaction kettle, is placed in baking oven,
The aging 12-14h under the conditions of 100-120 DEG C, obtains solidliquid mixture, three times with methanol centrifuge washing solid precipitating, in 70-80
Under the conditions of DEG C, dry 8-12h obtains the ZIF8 nano material of granatohedron;
Two, the synthesis of ZIF8@ZIF67 material:
Disperse ZIF8 nano material ultrasound 30-60min in methanol and form solution C, cobalt chloride is dissolved in methanol formed it is molten
Liquid D, 2-methylimidazole is dissolved in methanol and forms solution E, while agitating solution C, sequentially adds solution D and solution E, and after
Continuous stirring 5-10min, the mixed solution of formation are transferred in reaction kettle, are placed in baking oven, aging 12- under the conditions of 100-120 DEG C
14h obtains solidliquid mixture, and three times with methanol centrifuge washing solid precipitating, under the conditions of 70-80 DEG C, dry 8-12h is obtained
67 nano material of ZIF8@of core-shell structure copolymer two-tier rhombic dodecahedron;
Three, ZnO/Co3O4The synthesis of nano material:
It takes 67 nano material of ZIF8@to be placed in porcelain boat, in air atmosphere, is placed in Muffle furnace, be warming up to 350-370 DEG C and forge
2-3h is burnt, heating rate is 1-1.5 DEG C/min, obtains regular appearance, uniform ZnO/Co3O4Nano material.
2. the preparation method of core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material according to claim 1, feature
The mass concentration for being zinc nitrate hexahydrate in step 1 solution A is 29-30g/L.
3. the preparation method of core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material according to claim 1 or 2, special
Sign is that the mass concentration of 2-methylimidazole in step 1 solution B is 49-50g/L.
4. the preparation method of core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material according to claim 3, feature
It is in step 1 that the volume ratio of solution A and solution B is 3:(2-2.5).
5. the preparation method of core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material according to claim 1,2 or 4,
It is characterized in that in step 2 solution C that the mass volume ratio of ZIF8 nano material and methanol is (0.14-0.16) g:20mL.
6. the preparation method of core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material according to claim 5, feature
The mass concentration for being cobalt chloride in step 2 solution D is 5.00g/L~22.62g/L.
7. the preparation method of core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material according to claim 6, feature
The mass concentration for being 2-methylimidazole in step 2 solution E is 25.50g/L~114.37g/L.
8. the preparation method of core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material according to claim 7, feature
The volume ratio for being step 2 component solution C, solution D and solution E is 10:(3-6): (3-6).
9. the preparation method of core-shell structure copolymer layer zinc oxide/Co3O4 nanometer material according to claim 8, feature
It is dry for vacuum drying described in step 1 and step 2.
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