CN106986555A - A kind of ZIF 8/ZnO nano-stick array thin film materials and preparation method thereof - Google Patents
A kind of ZIF 8/ZnO nano-stick array thin film materials and preparation method thereof Download PDFInfo
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- CN106986555A CN106986555A CN201710278456.8A CN201710278456A CN106986555A CN 106986555 A CN106986555 A CN 106986555A CN 201710278456 A CN201710278456 A CN 201710278456A CN 106986555 A CN106986555 A CN 106986555A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/211—SnO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/216—ZnO
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/24—Doped oxides
- C03C2217/241—Doped oxides with halides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
Abstract
The present invention relates to a kind of ZIF 8/ZnO nano-stick array thin film materials and preparation method thereof, the thin-film material is obtained by length for 13 μm of the vertical intensive proper alignment of ZIF 8/ZnO nanometer rods in substrate.Preparation method is as follows：1) ZnO crystal seed layers are prepared in FTO conductive glass surfaces；2) aqueous solution of zinc acetate and hexa is prepared, then FTO electro-conductive glass is put into the aqueous solution and carries out hydro-thermal reaction, then cleans and is heat-treated, obtain ZnO nano-rod array；3) methanol solution of 2 methylimidazoles is prepared, FTO electro-conductive glass is put into progress hydro-thermal reaction in methanol solution obtains ZIF 8/ZnO nano-stick array thin film materials.The ZIF 8/ZnO nano-stick array thin film materials that the present invention is provided possess loose structure and form the array of rule, and the absorption to organic matter and catalytic decomposition have larger application potential in the treatment of waste water.
Description
Technical field
The present invention relates to field of material technology, and in particular to a kind of ZIF-8/ZnO nano-stick array thin films material and its system
Preparation Method.
Background technology
Zinc oxide is used as the semiconductor material with wide forbidden band that a kind of energy gap is 3.37eV, at room temperature gain of light coefficient
(300cm-1) and electron excitation combine can (60meV) it is all higher, therefore have good electricity, catalysis, spectrochemical property；
And chemical property is stable, preparation method is simple and easy to apply and cost is not high, very big concern is received, as photochemical catalyst quilt
It is extensively studied.Nano structure of zinc oxide has a variety of, and wherein nanometic zinc oxide rod array is a kind of critically important one-dimension zinc oxide
Nanostructured, compared with common zinc oxide nanosphere, nanometic zinc oxide rod array has bigger specific surface area, quantum size
Effect is also more obvious, but nanometic zinc oxide rod array is typically mono-crystalline structures and surface is smooth, it is impossible to sufficient adsorbance
Sub- point, dyestuff and pollutant.In addition, the roughness of material surface, crystallinity, hydroxy radical content etc. also contribute to surface absorption and
Electron-hole it is compound, and then influence the activity of catalyst.Based on these problems, it is necessary to take certain method to change oxidation
The surface topography of zinc nanometer stick array improves its performance.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of catalytic for above shortcomings in the prior art
ZIF-8/ZnO nano-stick array thin film materials that can be good and preparation method thereof.
In order to solve the above technical problems, the technical scheme that the present invention is provided is：
There is provided a kind of ZIF-8/ZnO nano-stick array thin films material, the thin-film material is by ZIF-8/ that length is 1-3 μm
The vertical intensive proper alignment of ZnO nanorod is obtained in substrate.
Present invention additionally comprises the preparation method of above-mentioned ZIF-8/ZnO nano-stick array thin films material, its step is as follows：
1) preparation of ZnO crystal seed layers：It is the molten of 0.5-1mol/L Zinc diacetate dihydrate to be added to concentration is obtained in methanol
Liquid, is stirring evenly and then adding into monoethanolamine at room temperature, and the monoethanolamine is 1 with Zinc diacetate dihydrate mol ratio:1-3, is stirred for
Stood after even and obtain colloidal sol, be film-made with gained colloidal sol on clean FTO electro-conductive glass, then made annealing treatment in the conductive glass of FTO
Glass surface obtains ZnO crystal seed layers；
2) preparation of ZnO nano-rod array：Prepare the aqueous solution of zinc acetate and hexa (HMTA), wherein acetic acid
Zinc is 3 with hexa mol ratio:1, then by step 1) the gained surface FTO electro-conductive glass with ZnO crystal seed layers puts
Enter and home position polymerization reaction is carried out in the aqueous solution, reaction is cleaned and is heat-treated after terminating, and is obtained in FTO conductive glass surfaces
ZnO nano-rod array；
3) preparation of ZIF-8/ZnO nanometer stick arrays：Prepare 2-methylimidazole methanol solution, by step 2) obtained by table
Face there is the FTO electro-conductive glass of ZnO nano-rod array to be put into the methanol solution carry out hydro-thermal reaction, and reaction is spent after terminating
Ionized water is cleaned repeatedly obtains ZIF-8/ZnO nano-stick array thin film materials.
By such scheme, step 1) method of the film is：By FTO electro-conductive glass be placed on pulling machine Best-Effort request into
Film, dip time is 1-2min minutes, and pull rate is 40-60mm/min, then will lift obtained wet film room in atmosphere
Temperature is dried 2 minutes, is then heated 10-60 minutes at 300-350 DEG C, and lifting number of times is 3-5 times.
By such scheme, step 1) the annealing condition is：1-1.5h is incubated at 350-450 DEG C.
Preferably, step 2) zinc acetate and hexa the aqueous solution in acetic acid zinc concentration be 0.02-
0.05mol/L。
By such scheme, step 2) the home position polymerization reaction condition is：Growth temperature is 80-90 DEG C, and growth time is
2-4 hours, growth number of times was 2-3 times.
By such scheme, step 2) heat treatment condition is：1-1.5h is incubated at 350-450 DEG C.
By such scheme, step 3) mass concentration of 2-methylimidazole is 2- in the methanol solution of the 2-methylimidazole
10%.
By such scheme, step 2) hydrothermal reaction condition is：12-36h is reacted at 90-110 DEG C.
Zeolitic imidazolate framework material (ZeoliticImidazolate Frameworks, abbreviation ZIFs) is a class with miaow
Azoles or derivatives thereof be part a kind of novel porous materials with skeleton structure of zeolite, its have excellent heat endurance with
The adjustability of structural stability and 26S Proteasome Structure and Function, therefore, ZIF materials are used to adsorb, separated and catalysis aspect as one kind
Have promising material and turn into the focus of research.ZIF-8 is most representational one kind, its specific surface area in ZIF materials
Up to 1400m2/ g, heat endurance is applied to research and has been directed to gas absorption, separation, hydrogen storage and catalysis etc. are more up to 420 DEG C
Individual field, is to study most commonly used class ZIF materials at present.The present invention urges metal-organic framework materials and inorganic semiconductor
Agent is combined, extra specific surface area and hole using organic framework material, absorption, catalytic reaction is combined, in synthesis
The characteristics of stating two kinds of materials each and advantage prepare a kind of new multifunctional composite, would be even more beneficial to the wide of catalytic reaction
General application.
The beneficial effects of the present invention are：1st, the ZIF-8/ZnO nano-stick array thin film materials that the present invention is provided possess many
Pore structure and the array for foring more rule, purity are high, combine the advantage of two kinds of materials of ZnO and ZIF-8, specific surface area
Greatly, pore passage structure is adjustable, is a kind of new multifunctional composite, in the treatment of waste water the absorption to organic matter and catalysis point
Solution has larger application potential；2nd, preparation method of the present invention is simple to operate, and preparation condition is gentle, reproducible, to equipment
It is required that low, cost is low, loose structure ZIF-8/ZnO nano-stick array thin film materials can be prepared on extensive substrate material.
Brief description of the drawings
Fig. 1 is the ZIF-8/ZnO nano-stick array thin films material and ZnO nano-rod array prepared by the embodiment of the present invention 1
X-ray diffractogram；
Fig. 2 is that ZnO nano-rod array and ZIF-8/ZnO nano-stick array thin film material sections prepared by embodiment 1 are swept
Retouch electromicroscopic photograph；
Fig. 3 is that ZnO nano-rod array and ZIF-8/ZnO nano-stick array thin film material sections prepared by embodiment 1 are swept
Retouch electromicroscopic photograph；
ZnO nano-rod arrays and ZIF-8/ZnO nano-stick array thin film material of the Fig. 4 prepared by embodiment 1 are to a huge sum of money
Belong to the rate of photocatalytic oxidation curve map of Cr (VI) solution.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Embodiment 1
ZIF-8/ZnO nano-stick array thin film materials are prepared, step is as follows：
1) zinc oxide precursor colloidal sol is prepared：Weigh 5.4876g Zinc diacetate dihydrates and be dissolved in 20 points of stirring in 50mL methanol
Clock, then measures 1.5mL monoethanolamines and adds in above-mentioned solution, and to form transparent homogeneous within 25 minutes molten for stirring on magnetic stirring apparatus
Glue, is made zinc oxide precursor colloidal sol；
2) cleaning of deposition substrate：By the FTO Conducting Glass (SnO of doping fluorine2Transparent conducting glass) use liquid detergent
After cleaning, it is sequentially placed into acetone, absolute ethyl alcohol, deionized water, absolute ethyl alcohol and is cleaned by ultrasonic 30 minutes；
3) deposition substrate Best-Effort request film forming：The folder of pulling machine will be placed on after FTO Conducting Glass drying after cleaning
On son, FTO Conducting Glass is immersed in the zinc oxide precursor colloidal sol prepared, soaked with 50mm/min pull rate
The stain time is 1 minute, after the completion of lifting for the first time, takes out FTO Conducting Glass and first spontaneously dries 2 minutes, then wipes non-
Conducting surface simultaneously places it in heat preservation and dryness 1 hour in 350 DEG C of heating plate, repeats above-mentioned Best-Effort request technique three times, and last two
The drying temperature of secondary FTO Conducting Glass is 300 DEG C, and soaking time is 5 minutes, then cools down FTO Conducting Glass
To room temperature；
4) crystallization of zinc oxide seed layer film：The above-mentioned FTO Conducting Glass handled well is transferred in Muffle furnace,
Annealed 1 hour at 350 DEG C, furnace cooling to room temperature obtains high-purity ZnO crystal seed layers in FTO conductive glass surfaces；
5) growth and cleaning of nanometic zinc oxide rod array：120mL deionized waters are taken, 0.6585g two hydration vinegar are added
Sour zinc is with using magnetic stirrer 15 minutes after 0.1402g hexas, preparation obtains growth solution, and surface is contained
The substrate transverse of ZnO crystal seed layers is put into growth solution, the growth polymerization in 85 DEG C of water-bath, is changed once every 4 hours
Growth solution, changes 2 times and amounts to growth 8 hours, when changing growth solution every time, the glass substrate in growth is taken out and in sky
Dried in gas, be subsequently placed into ultrasound in absolute ethyl alcohol and take out drying after about 5 seconds, to remove the bulky grain of glass substrate surface；It is raw
Glass substrate is taken out after the completion of length and is washed and is dried with deionized water and absolute ethyl alcohol respectively；
6) crystallization of loose structure nanometic zinc oxide rod array：The glass substrate grown is transferred in Muffle furnace, 350
Made annealing treatment 1 hour at DEG C, furnace cooling afterwards to room temperature, i.e., ZnO nano-rod array is made in FTO conductive glass surfaces；
7) weigh 2-methylimidazole add 100mL methanol in prepare obtain mass concentration be 8% methanol solution (Hmim is molten
Liquid), the growth solution that ZIF-8/ZnO nanometer stick arrays are obtained after 10min is stirred at room temperature；Then by step 6) middle preparation
The one side with nanometic zinc oxide rod array be placed on the high-pressure sealed of polytetrafluoroethyllining lining stainless steel outer lining diagonally downward
In reactor, at 100 DEG C, hydro-thermal reaction 24 hours in constant temperature blast drying oven are repeatedly clear with deionized water after completion of the reaction
Wash multiple, dry, obtain ZIF-8/ZnO nano-stick array thin film materials.
ZIF-8/ZnO nano-stick array thin films material manufactured in the present embodiment and ZnO nano are followed successively by Fig. 1 from top to bottom
The XRD of rod array, as can be seen from the figure product ZIF-8/ZnO nano-stick array thin films material contain hexagonal wurtzite structure
ZnO, (002) peak intensity is maximum and peak shape is sharp, illustrates zinc oxide nanocrystalline along c-axis preferential growth, form perpendicular to
The nanometer stick array of substrate, secondly, except ZnO diffraction maximums, remaining peak is fitted well with the ZIF-8 patterns simulated, and illustrates production
Contain two kinds of thing phases of ZnO and ZIF-8 in thing；
Fig. 2, Fig. 3 are the ZnO nano-rod array and ZIF-8/ZnO nano-stick array thin film materials prepared by the embodiment of the present invention
Material profile scanning electromicroscopic photograph (left side is ZnO nano-rod array, and the right is ZIF-8/ZnO nano-stick array thin films material), Fig. 2
About 3 μm of ZIF-8/ZnO nanometer rods average length is can be seen that, nanometer stick array grows perpendicular to substrate direction, and with porous
Structure, matches with XRD analysis result；Fig. 3 then can be seen that ZnO nanorod surface is grown into by the regular hexagon of rule and not advise
Polyhedron then, illustrates that ZnO nanorod surface is covered by ZIF-8 layers substantially.
Fig. 4 is ZnO nano-rod array manufactured in the present embodiment and ZIF-8/ZnO nano-stick array thin film material heavy metals
The rate of photocatalytic oxidation curve map of Cr (VI) solution, wherein, a, b represent ZnO nano-rod array and ZIF-8/ZnO nanometers respectively
Rod array film material is to Cr (VI) catalytic degradation rate curve, it can be seen that being received in illumination with ZnO after 8 hours
Rice rod array still retains about 70% for Cr (VI) in Cr (VI) solution of photochemical catalyst；After incorporation ZIF-8, ZIF-8/ZnO
Nano-stick array thin film material sample reduces about 40% and still declined after being irradiated to Cr (VI) at 8 hours, heavy metal is gone
Except efficiency is better than ZnO nano-rod array, good photocatalysis performance is shown.
Claims (9)
1. a kind of ZIF-8/ZnO nano-stick array thin films material, it is characterised in that the thin-film material is 1-3 μm by length
The vertical intensive proper alignment of ZIF-8/ZnO nanometer rods is obtained in substrate.
2. a kind of preparation method of the ZIF-8/ZnO nano-stick array thin film materials described in claim 1, it is characterised in that step
It is rapid as follows：
1) preparation of ZnO crystal seed layers：Zinc diacetate dihydrate is added to the solution for obtaining that concentration is 0.5-1mol/L in methanol, room
Monoethanolamine is stirring evenly and then adding under temperature, the monoethanolamine is 1 with Zinc diacetate dihydrate mol ratio:1-3, is stirred for uniform rear quiet
Put and obtain colloidal sol, be film-made, then made annealing treatment in FTO conductive glass surfaces on clean FTO electro-conductive glass with gained colloidal sol
Obtain ZnO crystal seed layers；
2) preparation of ZnO nano-rod array：Prepare the aqueous solution of zinc acetate and hexa, wherein zinc acetate and six methylenes
Urotropine mol ratio is 3:1, then by step 1) that there is the FTO electro-conductive glass of ZnO crystal seed layers to be put into is described water-soluble on gained surface
Home position polymerization reaction is carried out in liquid, reaction is cleaned and is heat-treated after terminating, ZnO nanorod battle array is obtained in FTO conductive glass surfaces
Row；
3) preparation of ZIF-8/ZnO nanometer stick arrays：Prepare 2-methylimidazole methanol solution, by step 2) obtained by surface tool
The FTO electro-conductive glass for having ZnO nano-rod array, which is put into the methanol solution, carries out hydro-thermal reaction, and reaction uses deionization after terminating
Water is cleaned repeatedly obtains ZIF-8/ZnO nano-stick array thin film materials.
3. preparation method according to claim 2, it is characterised in that step 1) method of the film is：FTO is conductive
Glass is placed in Best-Effort request film forming on pulling machine, and dip time is 1-2min minutes, and pull rate is 40-60mm/min, then
Obtained wet film drying at room temperature 2 minutes in atmosphere will be lifted, is then heated 10-60 minutes at 300-350 DEG C, lifts number of times
For 3-5 times.
4. preparation method according to claim 2, it is characterised in that step 1) the annealing condition is：In 350-
450 DEG C of insulation 1-1.5h.
5. preparation method according to claim 2, it is characterised in that step 2) zinc acetate and hexa
Acetic acid zinc concentration is 0.02-0.05mol/L in the aqueous solution.
6. preparation method according to claim 2, it is characterised in that step 2) the home position polymerization reaction condition is：It is raw
Long temperature is 80-90 DEG C, and growth time is 2-4 hours, and growth number of times is 2-3 times.
7. preparation method according to claim 2, it is characterised in that step 2) heat treatment condition is：In 350-450
DEG C insulation 1-1.5h.
8. preparation method according to claim 2, it is characterised in that step 3) in the methanol solution of the 2-methylimidazole
The mass concentration of 2-methylimidazole is 2-10%.
9. preparation method according to claim 2, it is characterised in that step 2) hydrothermal reaction condition is：90-110
12-36h is reacted at DEG C.
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Cited By (12)
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| CN107867713A (en) * | 2017-11-09 | 2018-04-03 | 扬州大学 | A kind of ZnO sensing electrode material preparation methods of porous nano pie structure |
| CN108545960A (en) * | 2018-05-08 | 2018-09-18 | 武汉理工大学 | A kind of Y doping zinc oxide nanometers stick array preparation method |
| CN108620125A (en) * | 2018-04-26 | 2018-10-09 | 江南大学 | A kind of preparation method of the nitridation carbon complex with high catalytic degradation activity |
| CN109485272A (en) * | 2018-11-21 | 2019-03-19 | 江苏大学 | High reflection infrared energy-conserving compound glass and preparation method thereof |
| CN113457461A (en) * | 2021-06-01 | 2021-10-01 | 四川大学 | Oil-water separation membrane and preparation method thereof |
| CN113842950A (en) * | 2021-08-18 | 2021-12-28 | 中国石油大学(华东) | Application method of metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics |
| CN114053884A (en) * | 2021-11-23 | 2022-02-18 | 浙江机电职业技术学院 | Nanofiltration membrane and preparation method and application thereof |
| CN114369252A (en) * | 2020-10-14 | 2022-04-19 | 中国科学院福建物质结构研究所 | Method for preparing metal-organic framework film based on self-sacrifice metal oxide film template |
| CN114538788A (en) * | 2022-03-08 | 2022-05-27 | 广西大学 | Preparation method of layered double metal hydroxide electrochromic energy storage film |
| CN114768699A (en) * | 2022-05-13 | 2022-07-22 | 昆明学院 | Growth method of Si NWs @ ZIF-8 core-shell structure |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107867713B (en) * | 2017-11-09 | 2019-07-05 | 扬州大学 | A kind of ZnO sensing electrode material preparation method of porous nano pie structure |
| CN107867713A (en) * | 2017-11-09 | 2018-04-03 | 扬州大学 | A kind of ZnO sensing electrode material preparation methods of porous nano pie structure |
| CN108620125A (en) * | 2018-04-26 | 2018-10-09 | 江南大学 | A kind of preparation method of the nitridation carbon complex with high catalytic degradation activity |
| CN108545960A (en) * | 2018-05-08 | 2018-09-18 | 武汉理工大学 | A kind of Y doping zinc oxide nanometers stick array preparation method |
| CN109485272A (en) * | 2018-11-21 | 2019-03-19 | 江苏大学 | High reflection infrared energy-conserving compound glass and preparation method thereof |
| CN109485272B (en) * | 2018-11-21 | 2022-01-11 | 江苏大学 | High-reflection infrared energy-saving composite glass and preparation method thereof |
| CN114369252A (en) * | 2020-10-14 | 2022-04-19 | 中国科学院福建物质结构研究所 | Method for preparing metal-organic framework film based on self-sacrifice metal oxide film template |
| CN113457461B (en) * | 2021-06-01 | 2022-07-19 | 四川大学 | Oil-water separation membrane and preparation method thereof |
| CN113457461A (en) * | 2021-06-01 | 2021-10-01 | 四川大学 | Oil-water separation membrane and preparation method thereof |
| CN113842950A (en) * | 2021-08-18 | 2021-12-28 | 中国石油大学(华东) | Application method of metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics |
| CN114053884A (en) * | 2021-11-23 | 2022-02-18 | 浙江机电职业技术学院 | Nanofiltration membrane and preparation method and application thereof |
| CN114053884B (en) * | 2021-11-23 | 2023-05-26 | 浙江机电职业技术学院 | Nanofiltration membrane and preparation method and application thereof |
| CN114538788A (en) * | 2022-03-08 | 2022-05-27 | 广西大学 | Preparation method of layered double metal hydroxide electrochromic energy storage film |
| CN114538788B (en) * | 2022-03-08 | 2023-07-25 | 广西大学 | Preparation method of layered double hydroxide electrochromic energy storage film |
| CN114768699A (en) * | 2022-05-13 | 2022-07-22 | 昆明学院 | Growth method of Si NWs @ ZIF-8 core-shell structure |
| CN114768699B (en) * | 2022-05-13 | 2023-04-25 | 昆明学院 | Growth method of Si NWs@ZIF-8 core-shell structure |
| CN115260514A (en) * | 2022-08-01 | 2022-11-01 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method of ZIF-8 or derivative film thereof |
| CN115595565A (en) * | 2022-10-26 | 2023-01-13 | 山东胜利通海集团东营天蓝节能科技有限公司（Cn） | Preparation method and application of complex-phase ZnO/ZnS nano array film |
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Application publication date: 20170728 |