CN108940255A - A kind of zinc oxide catalysis material and the preparation method and application thereof - Google Patents
A kind of zinc oxide catalysis material and the preparation method and application thereof Download PDFInfo
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- CN108940255A CN108940255A CN201810796981.3A CN201810796981A CN108940255A CN 108940255 A CN108940255 A CN 108940255A CN 201810796981 A CN201810796981 A CN 201810796981A CN 108940255 A CN108940255 A CN 108940255A
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- zinc oxide
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- oxide catalysis
- zinc
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims description 16
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 3
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 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 description 13
- 229940043267 rhodamine b Drugs 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 9
- 239000011701 zinc Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- 241000257465 Echinoidea Species 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- UHJBUYLXLTVQRO-UHFFFAOYSA-M sodium;acetate;dihydrate Chemical compound O.O.[Na+].CC([O-])=O UHJBUYLXLTVQRO-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- B01J35/33—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
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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
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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
- 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
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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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention provides a kind of preparation methods of zinc oxide catalysis material, belong to nano-functional material technical field.Preparation method of the invention obtains precursor solution the following steps are included: zinc acetate dihydrate aqueous solution is mixed with hexa；Precursor solution is subjected to hydro-thermal reaction, obtains the zinc oxide catalysis material；The molar ratio of the zinc acetate dihydrate and hexa is 1:1.5~2.5.Zinc oxide catalysis material of the invention includes dumbbell shaped zinc oxide, and is attached to the Zinc oxide nano sheet of dumbbell shaped zinc oxide surface；With plane homogeneity junction structure, the separation of photo-generated carrier is effectively promoted, simultaneously because Zinc oxide nano sheet itself has higher reactivity and more active exposed sites, greatly improves the photoelectrocatalysis efficiency of zinc oxide catalysis material.
Description
Technical field
The present invention relates to technical field of function materials more particularly to a kind of zinc oxide catalysis material and preparation method thereof with answer
With.
Background technique
With the economic high speed development with science and technology, living standards of the people and quality of life are also adjoint while being improved
The appearance of problems.Such as: fossil energy rapidly depletes caused energy crisis, vehicle exhaust and work after the industrial revolution
A large amount of discharges of factory's exhaust gas lead to the sharply decline of air quality, the development of textile industry and insecticide, surfactant
Abuse all causes serious resource and environmental crisis to pollution of water resource etc..The above problem causes the production and living of people
Huge puzzlement.Thus, finding cleaning, sustainable energy and exploitation has low in cost, efficient and without secondary pollution ring
Border processing technique becomes the urgent need of people.Traditional method for governing pollution mainly has: physisorphtion, chemistry redox
Method, biological degradation method and landfill incineration method.But there is at high cost, low efficiency and processing step in these technologies to varying degrees
The defects of rapid cumbersome, it is difficult to fundamentally solve pollution problem, or be the generation of by-product and lead to secondary pollution, it is difficult to is big
The industrial applications of scale.
Photocatalysis oxidation technique can utilize the nature sun as a kind of emerging technology with great potential
This inherent advantage of light can not only alleviate the energy crisis being becoming tight day, while in photocatalytically degradating organic dye and resist
Remarkable result is shown in terms of the bio-refractories substances such as raw element.Thus, preparing has partly leading for high-efficiency solar utilization efficiency
Body material becomes current scientific research hot spot.ZnO is as a kind of common broad-band gap nano semiconductor material, because its is excellent
Photoelectric properties, efficient photocatalytic activity, photosensitive property and good biocompatibility obtain extensive concern and development.
The appearance structure of ZnO has strong influence to photocatalytic activity.Currently, thering is researcher to pass through hydro-thermal method both at home and abroad
It is prepared sea urchin shape ZnO, but simple sea urchin shape ZnO absorbs it only in ultraviolet region due to its wide band gap, and
Too fast electron-hole pair recombination rate seriously hinders its application and development in photocatalysis field.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of zinc oxide catalysis materials and the preparation method and application thereof.
Include dumbbell shaped zinc oxide using zinc oxide catalysis material prepared by method of the invention, and is attached to dumbbell shaped zinc oxide surface
Zinc oxide nano sheet；The diameter of the zinc oxide catalysis material is 3~6 μm, and length is 15~18 μm, has plane homojunction
Structure is effectively facilitated the separation of photo-generated carrier, can be improved photoelectrocatalysis efficiency, it is organic to be widely used in bio-refractory
Object processing, dye-sensitized solar cells and photo catalytic reduction CO2Field.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of zinc oxide catalysis material, comprising the following steps:
Zinc acetate dihydrate aqueous solution is mixed with hexa, obtains precursor solution；
Precursor solution is subjected to hydro-thermal reaction, obtains the zinc oxide catalysis material；
The molar ratio of the zinc acetate dihydrate and hexa is 1:1.5~2.5.
Preferably, the mass concentration of the zinc acetate dihydrate aqueous solution is 15~30mg/mL.
Preferably, the temperature of the hydro-thermal reaction is 70~120 DEG C.
Preferably, the time of the hydro-thermal reaction is 7~12h.
Preferably, the pressure of the hydro-thermal reaction is 100~275KPa.
The present invention also provides the zinc oxide catalysis material that preparation method described in above-mentioned technical proposal obtains, feature exists
In, including dumbbell shaped zinc oxide, and it is attached to the Zinc oxide nano sheet of dumbbell shaped zinc oxide surface；The zinc oxide catalysis material
Diameter be 3~6 μm, length be 15~18 μm.
Preferably, the Zinc oxide nano sheet is supported on (101) crystal face of dumbbell shaped zinc oxide.
The present invention also provides the answering in catalyzing organic degradation field of zinc oxide catalysis material described in above-mentioned technical proposal
With.
The present invention also provides zinc oxide catalysis materials described in above-mentioned technical proposal in field of dye-sensitized solar cells
Application.
The present invention also provides zinc oxide catalysis materials described in above-mentioned technical proposal in photocatalytic reduction of carbon oxide field
Application.
The present invention provides a kind of preparation methods of zinc oxide catalysis material, comprising the following steps: by zinc acetate dihydrate water
Solution is mixed with hexa, obtains precursor solution；Precursor solution is subjected to hydro-thermal reaction, obtains the zinc oxide
Catalysis material；The molar ratio of the zinc acetate dihydrate and hexa is 1:1.5~2.5.The present invention passes through two water of control
The molar ratio of zinc acetate and hexa obtains six prismatics matrix by nucleus growth by hydro-thermal reaction, and wherein Zn is sudden and violent
Show up positively charged, O exposure is negatively charged, combines under the action of electrostatic attraction and forms dumbbell shaped zinc oxide, and reaction obtains
Including dumbbell shaped zinc oxide, and it is attached to the zinc oxide catalysis material of the Zinc oxide nano sheet of dumbbell shaped zinc oxide surface.This hair
Bright zinc oxide catalysis material has plane homogeneity junction structure, the separation of photo-generated carrier is effectively promoted, simultaneously because oxygen
Changing zinc nanometer sheet itself has higher reactivity and more active exposed sites, greatly improves catalysis material
Photoelectrocatalysis efficiency can be widely applied to the processing of bio-refractory organic matter, dye-sensitized solar cells and photocatalysis also
Former CO2Equal fields.From embodiment as can be seen that zinc oxide catalysis material reaches 88.8% to the degradation efficiency of rhodamine B.
Detailed description of the invention
Fig. 1 is the scanning electron microscope spectrogram for the zinc oxide catalysis material that embodiment 1 obtains；
Fig. 2 is the transmission electron microscope spectrogram for the zinc oxide catalysis material that embodiment 1 obtains；
Fig. 3 is the X-ray diffraction spectrogram for the zinc oxide catalysis material that embodiment 1 obtains；
Fig. 4 is rhodamine B surplus versus time curve after the zinc oxide catalysis material that embodiment 1 obtains is added；
Fig. 5 is rhodamine B surplus versus time curve after the zinc oxide catalysis material that embodiment 2 obtains is added；
Fig. 6 is rhodamine B surplus versus time curve after the zinc oxide catalysis material that embodiment 3 obtains is added.
Specific embodiment
The present invention provides a kind of preparation methods of zinc oxide catalysis material, comprising the following steps:
Zinc acetate dihydrate aqueous solution is mixed with hexa, obtains precursor solution；
The precursor solution is subjected to hydro-thermal reaction, obtains the zinc oxide catalysis material；
The molar ratio of the zinc acetate dihydrate and hexa is 1:1.5~2.5.
The present invention mixes zinc acetate dihydrate aqueous solution with hexa, obtains precursor solution.The present invention is to institute
The preparation method for stating zinc acetate dihydrate aqueous solution does not have special restriction, is prepared using aqueous solution well known to those skilled in the art
Method；Specifically, as the following steps are included: in the case where magnetic agitation, zinc acetate dihydrate is soluble in water, obtain two
Water acetic acid zinc aqueous solution.In the present invention, the mass concentration of the zinc acetate dihydrate aqueous solution is preferably 15~30mg/mL, more
Preferably 18~28mg/mL, most preferably 20~25mg/mL.In the present invention, the zinc acetate dihydrate and hexa
Molar ratio be 1:1.5~2.5, preferably 1.8~2.3, most preferably 1.9~2.1.
The present invention does not have special restriction to the mixed mode, using hybrid mode well known to those skilled in the art
, specifically, as stirred.In the present invention, the revolving speed of the stirring is preferably 500~1000r/min, and more preferably 600
~900r/min, most preferably 700~800r/min.In the present invention, the time of the stirring is preferably 10~20min, more
Preferably 12~18min, most preferably 14~16min.In the present invention, in the precursor solution, acetate dihydrate sodium and six
Methenamine is fully dispersed to be dissolved in water, and uniform and stable precursor solution is formed.
After obtaining precursor solution, precursor solution is carried out hydro-thermal reaction by the present invention, obtains the zinc oxide catalysis material
Material.In the present invention, the temperature of the hydro-thermal reaction is preferably 70~120 DEG C, more preferably 80~110 DEG C, most preferably 90
~100 DEG C.In the present invention, the time of the hydro-thermal reaction is preferably 7~12h, more preferably 8~11h, most preferably 9~
10h.In the present invention, the pressure of the hydro-thermal reaction is preferably 100~275KPa, more preferably 125~250KPa, most preferably
For 150~200KPa.
After hydro-thermal reaction, the present invention preferably by hydro-thermal reaction product cooled to room temperature, is then separated by solid-liquid separation, obtains
To white precipitate；By white precipitate cleaning, drying, the zinc oxide catalysis material is obtained.In the present invention, the medicine of the cleaning
Agent is preferably deionized water.In the present invention, the mode of the drying is preferably freeze-day with constant temperature.In the present invention, the drying
Temperature be preferably 60~80 DEG C, more preferably 65~75 DEG C.In the present invention, the drying time is preferably 2~5h, more excellent
It is selected as 3~4h.The present invention does not have special restriction to the equipment of the drying, dry using constant temperature well known to those skilled in the art
Dry case.
In the present invention, precursor solution is under the thermal and hydric environment of high temperature and pressure, zinc hydroxide and hexa network
Symphysis is at dumbbell shaped zinc oxide, and with the increase in reaction time, surface defect is reduced, and dumbbell shaped zinc oxide surface state becomes light
Sliding, the appearance of simultaneous Zinc oxide nano sheet is self-supported on dumbbell shaped zinc oxide crystal face.
The present invention also provides the zinc oxide catalysis material that preparation method described in above-mentioned technical proposal obtains, the zinc oxide
Catalysis material includes dumbbell shaped zinc oxide, and is attached to the Zinc oxide nano sheet of dumbbell shaped zinc oxide surface；The zinc oxide nano
Rice piece is supported on (101) crystal face of dumbbell shaped zinc oxide；The diameter of the zinc oxide catalysis material is 3~6 μm, length 15
~18 μm.
The present invention also provides the answering in catalyzing organic degradation field of zinc oxide catalysis material described in above-mentioned technical proposal
With.
The present invention also provides zinc oxide catalysis materials described in above-mentioned technical proposal in field of dye-sensitized solar cells
Application.
The present invention also provides zinc oxide catalysis materials described in above-mentioned technical proposal in photocatalytic reduction of carbon oxide field
Application.
Zinc oxide catalysis material provided by the invention and the preparation method and application thereof is carried out below with reference to embodiment detailed
Explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) 3mmol zinc acetate dihydrate water is mixed with 30mL deionized water, forms zinc acetate dihydrate aqueous solution；It will
Zinc acetate dihydrate aqueous solution is mixed with 6mmol hexa, and it is molten to obtain presoma by stirring 15min under 800r/min revolving speed
Liquid；
(2) precursor solution for obtaining the step (1) hydro-thermal reaction 10h at 95 DEG C, after hydro-thermal reaction, water
The filtering of thermal response product, obtained white precipitate is cleaned with deionized water, in 60 DEG C of dry 3h, obtains the zinc oxide catalysis
Material.
Obtained zinc oxide catalysis material is observed under scanning electron microscope, obtained scanning electron microscope spectrogram such as Fig. 1 institute
Show.It will be seen from figure 1 that the zinc oxide catalysis material that the present embodiment obtains has more complete dumbbell shape, specification is neat, table
Face is smooth, and the diameter of dumbbell shaped zinc oxide matrix is 4~5 μm, and length is 16~17 μm；More zinc oxide is observed simultaneously
The self-supported surface at dumbbell shaped Zinc oxide-base bottom of nanometer sheet.Table has been repaired in dissolution and recrystallization process due to zinc oxide structure cell
Planar defect reduces surface electronic hole to the quantity in complex centre, and forming ultra-thin Zinc oxide nano sheet itself has more
High reactivity and more active exposed sites, can effectively adsorb organic pollutant and hydrogen ion, from
And greatly improve the photoelectrocatalysis efficiency of zinc oxide catalysis material.
The zinc oxide catalysis material that the present embodiment obtains is observed using transmission electron microscope, transmission electron microscope spectrogram such as Fig. 2
It is shown.Figure it is seen that it is 0.25nm that zinc oxide catalysis material of the invention, which has orderly spacing of lattice, oxidation is indicated
On self-supported exposure (101) crystal face in dumbbell shaped zinc oxide matrix of zinc nanometer sheet, plane homogeneity junction structure is formed, is promoted
The separation of photo-generated carrier, improves the life time of electron-hole, to enhance the photoelectrocatalysis of zinc oxide catalysis material
Performance.
It is analyzed using structure of the X-ray diffraction to zinc oxide catalysis material, as a result as shown in Figure 3.It can from Fig. 3
Out: 2 θ of diffraction maximum is 31.77 °, 34.42 °, 36.25 °, 47.54 °, 54.60 °, 62.86 °, 66.38 °, 67.96 ° and 69.08 °
Occur (100) of zinc oxide hexagonal wurtzite structure, (002), (101), (102), (110), (103), (200), (112) and
(201) the corresponding diffraction maximum diffraction of crystal face, standard diagram card (the JCPDS CardNo.36- of this and zinc oxide hexagonal wurtzite
1451) it matches, illustrates that the catalysis material of preparation is hexagonal wurtzite zincite crystal.
It is 1 × 10 by 10mg zinc oxide catalysis material and 100mL concentration-5The organic dyestuff rhodamine B of mol/L mixes, and leads to
Cross dark treatment 3h reach adsorption-desorption balance after, use at room temperature power for 300W xenon lamp irradiation, obtain organic dyestuff sieve
Red bright B surplus versus time curve, as a result as shown in Figure 4.As can be seen from Figure 4: zinc oxide catalysis material is after 1h
88.8% is reached to the degradation efficiency of rhodamine B, reaches 2h when the photocatalysis time, rhodamine B almost degrades completely, shows to aoxidize
Zinc catalysis material can effectively inhibit the compound of photo-generated carrier, improve photocatalysis efficiency.
Embodiment 2
(1) 2mmol zinc acetate dihydrate water is mixed with 30mL deionized water, forms zinc acetate dihydrate aqueous solution；It will
Zinc acetate dihydrate aqueous solution is mixed with 5mmol hexa, and it is molten to obtain presoma by stirring 15min under 900r/min revolving speed
Liquid；
(2) precursor solution for obtaining the step (1) hydro-thermal reaction 11h at 90 DEG C, after hydro-thermal reaction, water
The filtering of thermal response product, obtained white precipitate is cleaned with deionized water, in 70 DEG C of dry 2h, obtains the zinc oxide catalysis
Material.
The zinc oxide catalysis material that the present embodiment obtains is scanned Electronic Speculum, transmission electron microscope and X-ray diffraction analysis,
As a result similar to Example 1.
By 10mg zinc oxide catalysis material and 100mL concentration 1 × 10-5The organic dyestuff rhodamine B mixing that mol/L is, leads to
Cross dark treatment 3h reach adsorption-desorption balance after, use at room temperature power for 300W xenon lamp irradiation, obtain organic dyestuff sieve
Red bright B surplus versus time curve, as a result as shown in Figure 5.As can be seen from Figure 5: zinc oxide catalysis material is after 1h
79.8% is reached to the degradation efficiency of rhodamine B, reaches 2h when the photocatalysis time, rhodamine B almost degrades completely, shows to aoxidize
Zinc catalysis material can effectively inhibit the compound of photo-generated carrier, improve photocatalysis efficiency.
Embodiment 3
(1) 4mmol zinc acetate dihydrate water is mixed with 30mL deionized water, forms zinc acetate dihydrate aqueous solution；It will
Zinc acetate dihydrate aqueous solution is mixed with 7mmol hexa, and it is molten to obtain presoma by stirring 15min under 900r/min revolving speed
Liquid；
(2) precursor solution for obtaining the step (1) hydro-thermal reaction 9h at 100 DEG C, after hydro-thermal reaction, water
The filtering of thermal response product, obtained white precipitate is cleaned with deionized water, in 80 DEG C of dry 2h, obtains the zinc oxide catalysis
Material.
The zinc oxide catalysis material that the present embodiment obtains is scanned Electronic Speculum, transmission electron microscope and X-ray diffraction analysis,
As a result similar to Example 1.
It is 1 × 10 by 10mg zinc oxide catalysis material and 100mL concentration-5The organic dyestuff rhodamine B of mol/L mixes, and leads to
Cross dark treatment 3h reach adsorption-desorption balance after, use at room temperature power for 300W xenon lamp irradiation, obtain organic dyestuff sieve
Red bright B surplus versus time curve, as a result as shown in Figure 6.As can be seen from Figure 6: zinc oxide catalysis material is after 1h
60.6% is reached to the degradation efficiency of rhodamine B, reaches 3h when the photocatalysis time, rhodamine B almost degrades completely, shows to aoxidize
Zinc catalysis material can effectively inhibit the compound of photo-generated carrier, improve photocatalysis efficiency.
It is from embodiment as can be seen that provided by the invention or prepare zinc oxide catalysis material according to preparation method of the present invention
Diameter is 3~6 μm, and length is 15~18 μm, the performances such as existing high adsorption and the separation of quick electron hole, can be extensive
Applied to the processing of bio-refractory organic matter, dye-sensitized solar cells and photo catalytic reduction CO2Equal fields.The present invention
The preparation method operation of offer is succinct, low in cost, is applicable to large-scale industrial production.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of zinc oxide catalysis material, comprising the following steps:
Zinc acetate dihydrate aqueous solution is mixed with hexa, obtains precursor solution；
The precursor solution is subjected to hydro-thermal reaction, obtains the zinc oxide catalysis material；
The molar ratio of the zinc acetate dihydrate and hexa is 1:1.5~2.5.
2. preparation method according to claim 1, which is characterized in that the mass concentration of the zinc acetate dihydrate aqueous solution is
15~30mg/mL.
3. preparation method according to claim 1, which is characterized in that the temperature of the hydro-thermal reaction is 70~120 DEG C.
4. preparation method according to claim 3, which is characterized in that the time of the hydro-thermal reaction is 7~12h.
5. preparation method according to claim 1 or 3, which is characterized in that the pressure of the hydro-thermal reaction be 100~
275KPa。
6. the zinc oxide catalysis material that any one of Claims 1 to 5 preparation method obtains, including dumbbell shaped zinc oxide and attached
The dumbbell shaped zinc oxide surface Zinc oxide nano sheet；The diameter of the zinc oxide catalysis material is 3~6 μm, length
It is 15~18 μm.
7. zinc oxide catalysis material according to claim 6, which is characterized in that the Zinc oxide nano sheet is supported on dumbbell
On (101) crystal face of shape zinc oxide.
8. application of the zinc oxide catalysis material described in claim 6 or 7 in catalyzing organic degradation field.
9. application of the zinc oxide catalysis material in field of dye-sensitized solar cells described in claim 6 or 7.
10. application of the zinc oxide catalysis material in photocatalytic reduction of carbon oxide field described in claim 6 or 7.
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| CN111001429A (en) * | 2019-12-27 | 2020-04-14 | 吉林师范大学 | Preparation method of nitrogen-doped modified zinc oxide visible-light-driven photocatalyst |
| CN111001429B (en) * | 2019-12-27 | 2022-08-02 | 吉林师范大学 | Preparation method of nitrogen-doped modified zinc oxide visible-light-driven photocatalyst |
| CN117380204A (en) * | 2023-10-11 | 2024-01-12 | 杭州同净环境科技有限公司 | Cuprous oxide-zinc oxide composite photocatalytic material with corn cob structure, preparation method and application thereof |
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