CN109499495A - A kind of zinc oxide/hydroxide aeroge and preparation method thereof - Google Patents
A kind of zinc oxide/hydroxide aeroge and preparation method thereof Download PDFInfo
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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Abstract
A kind of zinc oxide/hydroxide aeroge and preparation method thereof, belongs to aeroge preparation technical field.The present invention uses hydro-thermal method using soluble zinc salt, alkaline slow releasing agent as raw material, pattern uniform zinc oxide/hydroxide nanometer sheet is synthesized under the influence of anionic surfactant and hydroxide ion, and loose porous zinc oxide/hydroxide aeroge is then prepared using the active force between hydrone and lamella using ice template method.The zinc oxide/hydroxide aeroge preparation method that the purpose is to probe into a kind of simple possible, be conducive to promote and apply on a large scale.Zinc oxide/hydroxide aeroge preparation method proposed by the invention has the characteristics that reaction is easy, easy to operate, the means of production and time cost are cheap, yield is high, zinc oxide/hydroxide aerogel structure obtained is uniform, density very little, specific surface area and porosity with higher.
Description
Technical field
The invention belongs to aeroge preparation technical fields, and in particular to a kind of to induce nanometer sheet self assembly system by ice template
The method of standby zinc oxide/hydroxide aeroge, the zinc oxide/hydroxide aeroge of preparation can be widely applied to battery, pass
The fields such as sense, catalysis.
Background technique
Photocatalytic cleavage water hydrogen is considered as a kind of very promising method for obtaining clean energy resource, to alleviate
Fossil energy increasingly short bring energy crisis.This method, can convert cleaning for almost limitless solar energy can deposit
The chemical energy source of storage.In the art, solar conversion efficiency can be significantly improved by introducing semiconductor light-catalyst.Therefore honest and clean
Valence, efficient, stable semiconductor material are considered as very potential photocatalyst material.Some semiconductor materials, such as
TiO2、ZnO、Fe2O3、WO3Hydrogen field is prepared in photocatalytic cleavage water etc. being widely used.These materials can pass through water
Thermally grown method or electrodeposition process simply and economically prepare environmental-friendly photochemical catalyst.However since perveance is low, expands
Dissipate that length is short, the charge-conduction between reagent and photochemical catalyst is poor, the efficiency of light energy utilization is low and surface Precipitation Kinetics characteristic is poor
Etc. factors, limit solar energy-Hydrogen Energy transfer efficiency of these catalyst.To avoid these deficiencies, in addition to changing catalyst material
Expect other than material composition itself, existing catalyst structure can also be improved, such as is some special to the imparting of these materials
Structure further increases the catalytic performance of material by the synergistic effect of structure and material.These special structures enable to
The contact interface of catalyst increases, and reduces Carrier recombination, charge transfer rate and the efficiency of light energy utilization improve, to answer in photocatalysis
Good performance is shown with field.
Zinc oxide has resourceful, cheap, environmental-friendly and operating voltage window as transition metal oxide
Wider, the features such as chemical property is good, be exactly the favorite of photoelectric material and electrode material field all the time.In addition, zinc oxide
With good ion exchange and Molecular Adsorption performance, the fields such as molecular sieve and catalyst material also show it is wide before
Scape has received widespread attention in recent years.It is well known that the factors difference journey such as the crystal form of nanoparticle, size, pattern and dimension
Affect the performances such as optics, electricity and the magnetics of nano material to degree.It is existing research shows that Zinc oxide particles size, shape
Looks, specific surface area and pore-size distribution determine the Maximum Contact face between the diffusion length and solid electrode/solution interface of ion,
To improve chemical property and and catalytic performance be of great significance.Therefore, control the size of nano zinc oxide material, composition,
Crystalline structure or even package assembly, the relationship between architectural characteristic and physical and chemical performance for furtheing investigate nano zinc oxide material
And the performance for finally improving nano material is of great significance.
Since finding graphene, it is prepared for a large amount of two-dimensional material, such as nitride, sulfide, selenides, tellurium
Compound etc..It is an important step for developing 2D material that the stratified material of high quality, which how is mass produced,.It prepares at present mesoporous
A kind of higher method of cost-effectiveness of zinc oxide is that stratiform zinc hydroxide decomposes at high temperature.However, layer structure after calcining
It is destroyed, photocatalysis performance is similar to nano zine oxide.Therefore, how two-dimensional material and the advantage of zinc oxide further to be played
Out, the zinc oxide material for preparing similar two-dimensional material, is a significantly research hotspot.And in nanotechnology
In, in order to obtain macroscopically novel structure and function, need to carry out the microcosmic upper nano material unit with special nature
Assembling.Aeroge is that a kind of light porous property for the structure-controllable for mutually being coalesced by colloidal particle or the high-polymer molecule and being constituted is consolidated
State material.Microcosmos network structure has hole abundant in aeroge, provides big specific surface area, it has wide application
Prospect, have been used for acoustic impedance coupling material, catalyst or catalyst carrier, adsorbent, filtering material, high temperature insulating material and
In high-performance cell material.Therefore, size, composition, crystal structure or even the package assembly of nano zinc oxide material are controlled,
The relationship between architectural characteristic and physical and chemical performance for furtheing investigate nano zinc oxide material and finally raising nano material
Performance is of great significance.
In the case for preparing aeroge in the past, scientist mainly uses sol-gel method and template-directing method.The former can
To synthesize in batches, but poor controllability；The latter can generate orderly structure, but depend on the size and fine structure of template, difficult
Largely to prepare.Zinc oxide wet gel is usually prepared in the preparation for the zinc oxide aeroge reported at present, then by overcritical
Drying process prepares aeroge.However, the research report in relation to zinc oxide wet gel is very limited, this is mainly due to aeroges
The interaction of crystal grain is weaker in zinc oxide material in structure.Up to the present, the relevant report of zinc oxide aeroge is also
Seldom.Old thumb prestige is using zinc salt and polyacrylic acid, propylene oxide as presoma, by supercritical drying, through height under protective atmosphere
Temperature, which makes annealing treatment, is made zinc oxide aeroge (Journal of Mianyang Normal University 2012,31,28).Author is using X-ray diffraction to the gas
The zincite crystal structure of gel has carried out detailed analysis, and when finding annealing temperature difference, the crystallographic system of zinc oxide can be three
Tiltedly change between monocline.Sebastian Polarz is passed through using organic zinc salt (methyl zinc and alkoxy zinc) as presoma
The collosol and gel of organic zinc salt acts on and the hydrolysis of organic zinc salt is prepared for zinc oxide aeroge
(Chem.Mater.2010,22,5129).Djamel Djouadi et al. using solvent to the influence of sol-gel process,
System research forms the solvent effect (Eur.Phys.J.Appl.Phys.2014,66,10402) of aerogel process.Due to oxygen
The crystal structure of itself limitation for changing zinc, it is relatively simple to construct zinc oxide aeroge by the way of hydridization.Sun Litao etc. is with stone
Black alkene is skeleton, and zinc oxide nano-particle is that active ingredient is prepared for zinc oxide/redox graphene hybrid aerogel (patent
Application number: 201610086811.7)；Yang Zhuoshu etc. into inorfil, passes through the gel permeation containing zinc oxide and germanium oxide
The method for crossing gel aging and supercritical drying is prepared for hybrid aerogel (number of patent application: 201610067340.5).
Du Yi etc. prepares sheet by low temperature water-bath on this skeleton structure and receives using native cellulose as skeleton structure
Rice zinc oxide, to construct zinc oxide aeroge (number of patent application: 201710366441.7).The oxidation of these methods preparation
Zinc aeroge is all to be grown in the material surface that other are capable of forming aeroge to constitute, and that reports at present prepares zinc oxide gas
The problem of generally existing zinc oxide reactant precursor of the method for gel, mould material or organic decoration molecule remain, limits oxygen
Change the extensive use of zinc aeroge.Therefore, it is a kind of it is low in cost, easy to operate, be readily produced amplification prepare zinc oxide airsetting
The method of glue is urgently developed.
Summary of the invention
The purpose of the present invention is to provide a kind of zinc oxide/hydroxide aeroges and preparation method thereof.Used in the present invention
Vacuum freeze-drying method there is easy to operate, mild condition, low in cost and technique compared to traditional supercritical drying
It is easy to the advantages of amplifying.Zinc oxide/hydroxide aeroge prepared by the present invention is by buergerite zinc oxide/hydroxide nanometer sheet
It is self-assembly of, crystal form purity is good, solves and produces complexity present in the zinc oxide aeroge preparation method reported at present
Problem.And a process for preparing aeroge have the characteristics that high-specific surface area, high porosity so that its surface catalysis make
There is fairly good application prospect with field.
From preparation zinc oxide/hydroxide nanometer sheet dispersion liquid, ice crystal template when by freezing lures the present invention
Nanometer sheet self assembly is led, then carries out vacuum freeze drying, conveniently and efficiently prepares low-density zinc oxide/hydroxide airsetting
Glue.Zinc oxide/hydroxide aeroge prepared by the present invention can be widely applied to the fields such as battery, sensing, catalysis.
A kind of method preparing zinc oxide/hydroxide aeroge of the present invention, its step are as follows:
1) preparation of zinc oxide/hydroxide nanometer sheet
Take aqueous surfactant solution 1~4mL, the 100~200mM alkaline slow releasing agent aqueous solution 4 of 200~300mM~
4~8mL of soluble Zn saline solution of 8mL, 100~200mM are add to deionized water, and make total capacity 100mL, then upwards
It states and the pH value that 10~20mg alkali solid adjusts solution is added in mixed liquor, sufficiently dissolution mixes and is placed on 90 DEG C~110 DEG C
At a temperature of react 1~3h, be sufficiently stirred, finally obtained rich in zinc oxide/hydroxide nanometer sheet suspension during reaction,
It is centrifuged 3~10min with the centrifugal rotational speed of 3000rpm~7000rpm, sediment fraction is isolated, obtains zinc oxide/hydroxide and receive
Rice piece；
2) preparation of zinc oxide/hydroxide nanometer sheet dispersion liquid
By the zinc oxide/hydroxide nanometer pellet that step 1) is prepared spend ionized water repeatedly clean carry out it is pure
Change, be then then added in deionized water, obtained suspension is stood into 12h or more, zinc oxide/hydroxide nanometer sheet is made to exist
Natural subsidence is in cotton-shaped in water, removes supernatant liquid, obtains zinc oxide/hydroxide nanometer sheet dispersion liquid；
3) preparation of zinc oxide/hydroxide aeroge
The zinc oxide/hydroxide nanometer sheet dispersion liquid that step 2) is prepared carries out cryogenic freezing, to thoroughly solidify
Afterwards, vacuum freeze drying is used, so that zinc oxide/hydroxide aeroge be prepared.
Surfactant used in step 1) be lauryl sodium sulfate, positive decyl sodium sulphate, dodecyl sulphate potassium,
The mixture of one or more of sodium tetradecyl sulfate, dodecyl polyoxy ether sulfate or ammonium lauryl sulfate.
Alkaline slow releasing agent is hexamethylenetetramine or urea.
Soluble zinc salt is one of zinc nitrate, zinc bromide, zinc chloride, zinc acetate or zinc sulfate.
It is worth noting that the ratio between the alkaline slow releasing agent being added and mole dosage of soluble zinc salt should keep 1:1.
The alkali solid for adjusting mother liquor pH value can be sodium hydroxide, sodium carbonate or potassium hydroxide；Mixing speed be 150~
300rpm。
The concentration of zinc oxide/hydroxide nanometer sheet suspension is 0.1~0.2mg/mL made from step 1).
The concentration of step 2) zinc oxide/hydroxide nanometer sheet dispersion liquid obtained after purification is 1~2mg/mL.
Cryogenic temperature described in step 3) is -20 DEG C~-80 DEG C, and the time is 12~24 hours.
Vacuum freeze drying temperature described in step 3) is -50 DEG C~-80 DEG C, and the time is 24~48 hours.
The equipment that the method for preparation zinc oxide/hydroxide aeroge of the present invention uses is simple, mild condition, used
Chemical reagent is cheap and easy to get.The density of aeroge can be by changing zinc oxide/hydroxide dispersion liquid concentration side when freezing
Just it is finely adjusted.Microcosmic three-dimensional porous structure is presented in the zinc oxide/hydroxide aeroge of preparation, after curling interconnection
The micropore very abundant that is separated into of zinc oxide/hydroxide nanometer sheet (thickness 100nm or less), communicate with one another between micropore.
The shape of vessel used when the volume and freezing of cotton-shaped dispersion liquid when furthermore the volume and shape of aeroge can pass through freezing
Adjusting easily and effectively is carried out, zinc oxide/hydroxide nanometer sheet dispersion liquid is such as concentrated into 4mL and is placed on the freezing of 5mL beaker
It is 2.25cm that volume, which can be made, in drying3Cylindric zinc oxide/hydroxide aeroge.Zinc oxide/hydrogen prepared by the present invention
Zinc oxide aeroge has sizable specific surface area and lower density, in capacitor, catalysis, biosensor, lithium ion
The fields such as battery will have broad application prospects.
Detailed description of the invention
Fig. 1: the optical photograph of the cylindrical zinc oxide/hydroxide aeroge for the different volumes that embodiment 1 is prepared；
Fig. 2: the electron scanning micrograph for the zinc oxide/hydroxide aeroge that embodiment 1 is prepared；
Fig. 3: the X-ray diffraction spectrogram for the zinc oxide/hydroxide aeroge that embodiment 1 is prepared；
Fig. 4: the zinc oxide/hydroxide aeroge that embodiment 1 is prepared is used for photocatalytically degradating organic dye (Luo Dan
It is bright) experimental result；
Fig. 5: the electron scanning micrograph and optics for the zinc oxide/hydroxide aeroge that embodiment 2 is prepared
Photo (illustration).
Specific embodiment
More detailed description is done to technical solution of the present invention with specific embodiment below, but the example is not constituted to this
The limitation of invention.
Embodiment 1
1) preparation of zinc oxide/hydroxide nanometer sheet:
Take the nitric acid of hexamethylenetetramine the solution 4mL, 100mM of the sodium dodecyl sulfate solution 1mL, 100mM of 200mM
Zinc solution 4mL is added in 91mL deionized water and is added the NaOH solid adjusting solution ph of 10mg, is uniformly mixed and is placed on
2h is reacted at a temperature of 90 DEG C, is during which sufficiently stirred, and mixing speed 200rpm is finally obtained rich in zinc oxide/hydrogen-oxygen
Change the suspension of zinc nanometer sheet.After taking-up hangs cooling at room temperature, which is centrifuged under the revolving speed of 3000rpm, is taken
Precipitating is cleaned 5 times repeatedly with deionized water out, is finally distributed in 10mL deionized water, is stood and is removed residue after supernatant
The cotton-shaped zinc oxide/hydroxide nanometer sheet dispersion liquid of 5mL.The dispersion liquid is contained in 5mL beaker and is freezed in -20 DEG C of refrigerators
12h, being subsequently placed into vacuum freeze drier the drying at -50 DEG C, for 24 hours, obtaining volume respectively may be about 2.7cm3、2.3cm3、
3.6cm3、2.2cm3Zinc oxide/hydroxide aeroge.It is respectively with the quality that precision balance accurate weighing goes out them
17.9mg, 14.8mg, 19.1mg, 12.6mg, it is about 6.6mg/cm that corresponding aeroge density, which is calculated,3、6.4mg/cm3、
5.3mg/cm3、5.7mg/cm3。
The optical photograph of the zinc oxide/hydroxide aeroge of different shape, volume that attached drawing 1 is.
The electron scanning micrograph for the zinc oxide/hydroxide aeroge that attached drawing 2 is.As shown, material
Three-dimensional loose and porous structure is all presented in very big range, the curling of zinc oxide/hydroxide nanometer sheet, which is coupled to be formed, to be enriched
Cavity, the size of cavity is mostly at 30 μm hereinafter, form is fluffy and uniform, zinc oxide/hydroxide nanometer sheet thickness in figure
At 0.1 μm or less.
The X-ray diffraction spectrogram for the zinc oxide/hydroxide aeroge that attached drawing 3 is.Buergerite oxidation as shown in the figure
(100) of zinc, (002), (101), (102), (110), (103) and (112) diffractive features peak is high-visible, illustrates the gas of preparation
Zinc oxide component in gel is wurtzite phase.(004) of zinc hydroxide simultaneously, (005), (006) and (007) diffraction maximum
(add * and zinc oxide to distinguish) peak type is distinct, illustrates to contain a certain amount of zinc hydroxide component in material.
The zinc oxide/hydroxide aeroge photocatalytically degradating organic dye (rhodamine, for simulating that attached drawing 4 is
Organic pollutants) absorption change over time curve.As shown, obtained zinc oxide aeroge will in 3 hours
The complete catalytic degradation of rhodamine illustrates obtained zinc oxide/hydroxide aeroge in photocatalysis degradation organic contaminant side
Face is with good performance.
Embodiment 2
Such as each step operation of embodiment 1, six methines of the sodium dodecyl sulfate solution 4mL, 200mM of 300mM are taken
The zinc nitrate solution 8mL of four amine aqueous solution 8mL, 200mM is added in 80mL deionized water, then is adjusted with 20mg sodium hydrate solid
PH value obtains the zinc oxide/hydroxide nanometer pellet that quality is about 40mg.Oxygen is further prepared using identical method
Change zinc/zinc hydroxide aeroge, the zinc oxide/hydroxide aeroge of preparation is cylindrical, and volume is 4.8cm3, density is
7.7mg/cm3。
Attached drawing 5 is the electron scanning micrograph and optical photograph for the zinc oxide/hydroxide aeroge that this example obtains
(illustration).Three-dimensional porous structure is all presented in very big range as shown in the figure, hole wall is rolled up by zinc oxide/hydroxide nanometer sheet
Qu Lianjie is formed, and lamellar spacing is at 0.1 μm or less.
Embodiment 3
Such as each step operation of embodiment 1, using dodecyl sulphate potassium sulfate；Further prepared using identical method
Zinc oxide/hydroxide aeroge.The zinc oxide/hydroxide aeroge prepared is cylindrical, volume 3.0cm3, quality
For 19.5mg, density is 6.5mg/cm3。
Embodiment 4
Such as each step operation of embodiment 1, zinc oxide/hydroxide nanometer sheet is dispersed in 20mL deionized water, dense
Degree is about 0.5mg/mL；Zinc oxide/hydroxide aeroge is further prepared using identical method.Zinc oxide/hydrogen obtained
Zinc oxide aeroge is cylindrical, volume 3.7cm3, quality 16.2mg, density 4.4mg/cm3。
Embodiment 5
Such as each step operation of embodiment 1, the temperature of freezing is -80 DEG C, and cooling time is for 24 hours, further using identical
Method prepare zinc oxide/hydroxide aeroge.The zinc oxide/hydroxide aeroge of preparation be it is cylindrical, volume is
3.1cm3, density is 5.3mg/cm3, micropore is abundant.
Embodiment 6
Such as each step operation of embodiment 1, vacuum freeze drying temperature is -80 DEG C, sublimation drying 48h, into one
Step prepares zinc oxide/hydroxide aeroge using identical method.The zinc oxide/hydroxide aeroge of preparation is in cylinder
Shape, volume are 3.3cm3, density is 6.0mg/cm3, the connection of zinc oxide/hydroxide nanometer sheet is close, and cavity is abundant.
Embodiment 7
As embodiment 1 each step operate, reaction temperature is 110 DEG C, further using identical method prepare zinc oxide/
Zinc hydroxide aeroge.The zinc oxide/hydroxide aeroge of preparation is cylindrical, and volume is 3.3cm3, density is 6.6mg/
cm3。
It should be understood that the above-mentioned description for preferred embodiment is more detailed, can not therefore be considered to this
The limitation of invention patent protection range, those skilled in the art under the inspiration of the present invention, are not departing from power of the present invention
Benefit requires that the various deformations such as replacement, simple combination can also be made, of the invention is claimed model under protected ambit
Enclosing should be determined by the appended claims.
Claims (10)
1. a kind of method for preparing zinc oxide/hydroxide aeroge, its step are as follows:
1) preparation of zinc oxide/hydroxide nanometer sheet
Take aqueous surfactant solution 1~4mL, 100~200mM alkaline slow releasing agent aqueous solution 4~8mL of 200~300mM, 100
4~8mL of soluble Zn saline solution of~200mM is add to deionized water, and makes total capacity 100mL, then to above-mentioned mixing
The pH value that 10~20mg alkali solid adjusts solution is added in liquid, sufficiently dissolution is mixed and is placed at a temperature of 90 DEG C~110 DEG C
1~3h is reacted, is sufficiently stirred during reaction, is finally obtained rich in zinc oxide/hydroxide nanometer sheet suspension, with
The centrifugal rotational speed of 3000rpm~7000rpm is centrifuged 3~10min, isolates sediment fraction, obtains zinc oxide/hydroxide nanometer
Piece；
2) preparation of zinc oxide/hydroxide nanometer sheet dispersion liquid
It the zinc oxide/hydroxide nanometer pellet that step 1) is prepared is spent into ionized water cleans repeatedly and purify, so
After be then added in deionized water, by obtained suspension stand 12h or more, make zinc oxide/hydroxide nanometer sheet in water
Natural subsidence removes supernatant liquid, obtains zinc oxide/hydroxide nanometer sheet dispersion liquid in cotton-shaped；
3) preparation of zinc oxide/hydroxide aeroge
The zinc oxide/hydroxide nanometer sheet dispersion liquid that step 2) is prepared is carried out cryogenic freezing to adopt after thoroughly solidifying
With vacuum freeze drying, so that zinc oxide/hydroxide aeroge be prepared.
2. a kind of method for preparing zinc oxide/hydroxide aeroge as described in claim 1, it is characterised in that: step 1)
Used in surfactant be lauryl sodium sulfate, positive decyl sodium sulphate, dodecyl sulphate potassium, myristyl sulfate
The mixture of one or more of sodium, dodecyl polyoxy ether sulfate or ammonium lauryl sulfate.
3. a kind of method for preparing zinc oxide/hydroxide aeroge as described in claim 1, it is characterised in that: step 1)
Used in alkaline slow releasing agent be hexamethylenetetramine or urea.
4. a kind of method for preparing zinc oxide/hydroxide aeroge as described in claim 1, it is characterised in that: step 1)
Described in soluble zinc salt be one of zinc nitrate, zinc bromide, zinc chloride, zinc acetate or zinc sulfate.
5. a kind of method for preparing zinc oxide/hydroxide aeroge as described in claim 1, it is characterised in that: step 1)
The ratio between the alkaline slow releasing agent of middle addition and the mole dosage of soluble zinc salt are 1:1.
6. a kind of method for preparing zinc oxide/hydroxide aeroge as described in claim 1, it is characterised in that: step 1)
Described in alkali solid be sodium hydroxide, ammonium hydroxide, sodium carbonate or potassium hydroxide.
7. a kind of method for preparing zinc oxide/hydroxide aeroge as described in claim 1, it is characterised in that: step 1)
In mixing speed be 150~300rpm, the concentration of obtained zinc oxide/hydroxide nanometer sheet suspension is 0.1~
0.2mg/mL。
8. a kind of method for preparing zinc oxide/hydroxide aeroge as described in claim 1, it is characterised in that: step 2)
The concentration of zinc oxide/hydroxide nanometer sheet dispersion liquid obtained is 1~2mg/mL after purification.
9. a kind of method for preparing zinc oxide/hydroxide aeroge as described in claim 1, it is characterised in that: step 3)
The cryogenic temperature is -20 DEG C~-80 DEG C, and the time is 12~24 hours；Vacuum freeze drying temperature is -50 DEG C~-80 DEG C,
Time is 24~48 hours.
10. a kind of zinc oxide/hydroxide aeroge, it is characterised in that: be the side as described in claim 1~9 any one
Method is prepared.
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| CN110212224A (en) * | 2019-05-23 | 2019-09-06 | 上海交通大学 | A method of porous membrane electrode is prepared using ice template method |
| CN112117383A (en) * | 2020-09-11 | 2020-12-22 | 东北师范大学 | Structure-adjustable electron transport layer and preparation method thereof, and solar cell and preparation method thereof |
| CN115057417A (en) * | 2022-06-08 | 2022-09-16 | 安徽大学 | Preparation of copper nitride nanosheet and application of copper nitride nanosheet in formate electrosynthesis |
| WO2022204866A1 (en) * | 2021-03-29 | 2022-10-06 | 中国科学院深圳先进技术研究院 | Aerogel with double-orientation network, preparation method therefor and use thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110212224A (en) * | 2019-05-23 | 2019-09-06 | 上海交通大学 | A method of porous membrane electrode is prepared using ice template method |
| CN112117383A (en) * | 2020-09-11 | 2020-12-22 | 东北师范大学 | Structure-adjustable electron transport layer and preparation method thereof, and solar cell and preparation method thereof |
| CN112117383B (en) * | 2020-09-11 | 2022-07-05 | 东北师范大学 | Structure-adjustable electron transport layer and preparation method thereof, and solar cell and preparation method thereof |
| WO2022204866A1 (en) * | 2021-03-29 | 2022-10-06 | 中国科学院深圳先进技术研究院 | Aerogel with double-orientation network, preparation method therefor and use thereof |
| CN115057417A (en) * | 2022-06-08 | 2022-09-16 | 安徽大学 | Preparation of copper nitride nanosheet and application of copper nitride nanosheet in formate electrosynthesis |
| CN115057417B (en) * | 2022-06-08 | 2023-09-12 | 安徽大学 | Preparation of copper nitride nano-sheet and application of copper nitride nano-sheet in formate electrosynthesis |
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