CN107987279A - Utilize the method for the Janus microballoons of ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame ZIF-8 - Google Patents
Utilize the method for the Janus microballoons of ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame ZIF-8 Download PDFInfo
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Abstract
The present invention discloses a kind of method of the Janus microballoons using ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame (MOFs) ZIF 8.2 methylimidazole of organic molecules-ligands is dissolved in ionic liquid first, it is placed in again in bi-polar electrochemical synth sink, bipolar electrode is used as using zinc ball, zinc ion is produced in zinc ball anode surface by bi-polar electrochemical method, zinc ion and 2 methylimidazoles are combined into 8 films of metal organic frame ZIF with petal shape so as to fulfill Janus microballoons are prepared.Relative to traditional direct electrosynthesis method, the present invention can arbitrarily select the electro-deposition point on micro-sphere material surface to realize the controllable preparation to Janus micro-sphere materials, and the adverse effect that preparation process produces MOFs films without evolving hydrogen reaction.The present invention has that cost is low, and device is simple, and operation is simple, highly controllable, without using toxic reagent in preparation process, it is environmentally friendly the advantages that.
Description
Technical field
The present invention relates to the preparation method of Janus section bar material, and in particular to one kind utilizes ionic liquid bi-polar electrochemical
The method for synthesizing the Janus microballoons of petal-shaped Metal-organic frame ZIF-8.
Background technology
De Gennes professors describe to contain in same structure with Janus first in Nobel Prize award-giving meeting within 1991
There are unsymmetric structure (the De Gennes, P.G.Angew. of two kinds of different chemical compositions or opposed polarity
Chem.Int.Edit.1992,31,842.), this word of present Janus is used for describing the feature of asymmetric particle.This Janus
Particle has unique physicochemical properties, has recently become the research hotspot of new function type Material Field.Two-sidedness
Janus particles are conveyed in electronic console, heterogeneous catalysis, anti-reflection coating, nano-motor, medicine or gene, emulsion stabilizer
And the field such as the more complicated superparticle of 26S Proteasome Structure and Function or device has a wide range of applications (Walther, A.and
A.H.E.Müller.Chemical Reviews,2013,113, 5194.)。
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) are a kind of by metal ion and more
The crystalline material for the periodicity net structure that functional group's organoligand coordination forms.Metal-organic frame ZIF-8 (Zn
(Hmim)2, Hmim=2- methylimidazoles) be skeleton structure of zeolite MOFs materials Typical Representative.ZIF-8 both has MOFs materials
Expect high porosity and big specific surface area and adjustability of structure, and with the high stability of inorganic zeolite.Therefore, ZIF-8
Store with separating in gas, heterocatalysis, chemical sensor, many aspects such as biomedical imaging and drug delivery are with potential
Application value.Janus section bars material is combined to form a kind of Janus types Metal-organic frame ZIF-8 materials with ZIF-8
So as to extend Janus type materials applications.At present Janus section bars material mainly using phase separation method, Semi-shielded method, layer by layer from
The preparation methods such as construction from part (Walther, A.and A.H.E.M ü ller.Chemical Reviews, 2013,113,
5194.).Bi-polar electrochemical synthesis Janus type MATERIALS METHODSs are a kind of new synthetic methods that nearest researcher is found
(Fosdick,S.E.,K.N.Knust,et al.Angewandte Chemie International Edition,2013,
52,10438.).Bi-polar electrochemical device mainly by DC power supply and the driving electrodes being connected on DC power supply and its is immersed in
Electric conductor (i.e. bipolar electrode) composition in solution.Under power on condition, the driving electrodes shape that is connected on DC power supply
Into electric field, soak the bipolar electrode not contacted directly with driving electrodes in the solution and produce polarization potential under electric field action,
One section close to driving electrodes anode produces polarization negative potential so as to form bipolar electrode cathode, close to one section of driving electrodes cathode
Polarization positive potential is produced so as to forming bipolar electrode anode, therefore, this leaching in the solution there is cathodic polarization potential and anode
Electrochemical reaction can also occur on the conductor bipolar electrode surface of polarization potential.Bi-polar electrochemical is of low cost, device is simple
It is single, operation is simple, the advantages of being controlled from region.In addition, relative to aqueous solution, ionic liquid has electrochemical window mouth width, steams
Vapour pressure is low, heat-resisting, nonflammable, advantages of environment protection, and conductor bipolar electrode, which is immersed in ionic liquid, to be electrochemically reacted,
The interference of water can be avoided, is conducive to the reaction of bipolarity electro synthesis.Have no at present and bipolarity is used under ionic liquid reaction condition
Electro synthesis method prepares the research report of the Janus type microballoons of surface one end covering Metal-organic frame ZIF-8, especially spends
The Metal-organic frame ZIF-8 of lobed shape.The present invention provides one kind to utilize ionic liquid bi-polar electrochemical synthesis petal
The method of the Janus microballoons of shape Metal-organic frame ZIF-8.
The content of the invention
There is machine frame using ionic liquid bi-polar electrochemical synthesis petal-shaped metal it is an object of the invention to provide one kind
The method of the Janus microballoons of frame thing ZIF-8.
The present invention realizes that the technical solution of above-mentioned purpose is specially：
A kind of Janus microballoons using ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame ZIF-8
Method, include the following steps：
(1) a kind of device of bi-polar electrochemical synthetic system is built：The device of bi-polar electrochemical synthetic system includes
Direct current driving power supply, driving electrodes, bipolar electrode, membrane and polytetrafluoroethylene (PTFE) square groove, by inert electrode platinized platinum or graphite
Piece makees driving electrodes, and the anode of driving electrodes connects direct current driving power supply cathode and anode, driving electricity with conducting wire respectively with cathode
The anode and cathode of pole are respectively placed in the both ends in polytetrafluoroethylene (PTFE) square groove, driving electrodes anode and driving electrodes cathode at the same time
The distance between be 2.5cm；Bipolar electrode zinc microballoon is positioned between the anode of driving electrodes and cathode, while with perfluor sulphur
Acid ion isolation film keeps apart the anode of driving electrodes and cathode with bipolar electrode zinc sphere physical；Such polytetrafluoroethylene (PTFE)
Square groove forms the space segment of three isolation, and it is micro- that polytetrafluoroethylene (PTFE) square groove center section forms zinc containing bipolar electrode
The electro synthesis room of ball, the insulating space at polytetrafluoroethylene (PTFE) square groove both ends form respectively the anode containing driving electrodes anode chamber and
The cathode chamber of the cathode containing driving electrodes；
(2) ionic liquid is prepared：Choline chloride and ethylene glycol be uniformly mixed to (molar ratio of choline chloride and ethylene glycol is excellent
Select 1~4:100) transparent ionic liquid is formed；
(3) 2-methylimidazole is dissolved in ionic liquid obtained by step (2), stirring makes it fully dissolve, and controls 2- first
Concentration of the base imidazoles in ionic liquid is 0.3~3.0mol/L, is subsequently added into 1,4-benzoquinone, stirring makes it fully dissolve, to benzene
Concentration of the quinone in ionic liquid is 0.005~0.015mol/L, finally obtains transparent weak yellow liquid；
(4) weak yellow liquid obtained by step (3) is poured into the electro synthesis room in step (1), by obtained by step (2) from
Sub- liquid pours into anode chamber and cathode chamber in step (1) respectively；
(5) preparation of the Janus microballoons of petal-like Metal-organic frame ZIF-8：Control the electricity of direct current driving power supply
Press as 10v~30v, one electric field of formation between driving electrodes, under electric field action, bipolar electrode zinc microballoon (zinc microballoon
Before the use with 1.0~1.5mol/L salt acid soak 15~30 minutes) both ends form polarization anode and polarization cathode, close to driving
The zinc microsphere surface of moving electrode anode one end forms polarization cathode, and the zinc microsphere surface close to driving electrodes cathode one end forms pole
Change anode, the polarization anode surface electro-deposition of the bipolar electrode zinc microballoon in ionic liquid, which goes out petal-like metal, machine frame
Frame thing ZIF-8 films, and the polarization cathode surface of bipolar electrode zinc microballoon only occur the oxidation reaction of 1,4-benzoquinone without
ZIF-8 is deposited, therefore prepares the Janus microballoons of petal-like Metal-organic frame ZIF-8 films.The present invention participates in reaction
Reagent be analysis it is pure, it is commercially available.
The beneficial effects of the present invention are：
(1) present invention carries out the petal-like Metal-organic frame ZIF-8 of electro-deposition using bi-polar electrochemical method,
Products obtained therefrom has very special pattern, is petal-shaped.The bi-polar electrochemical method of the present invention can be realized irregular
Arbitrarily selection saltation point carries out the petal-like Metal-organic frame ZIF-8 of electro-deposition on the conductive material surface of shape.
(2) present invention using ionic liquid is solvent, avoids interference of the aqueous solvent in electrode surface, in preparation process not
It is environmentally friendly using toxic reagent.
(3) present invention has the advantages that cost is low, and device is simple, and operation is simple, highly controllable.
Brief description of the drawings
Fig. 1 is the SEM figures of zinc microballoon before embodiment 1 is reacted.
Fig. 2 is the SEM figures of zinc microballoon after embodiment 1 is reacted.
Fig. 3 is the Metal-organic frame ZIF-8 materials that zinc microsphere surface made from embodiment 1 has petal shape
SEM schemes.
Fig. 4 is the XRD diagram of the Metal-organic frame ZIF-8 materials of petal shape made from embodiment 1.
Embodiment
In order to be better understood from the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
(1) a kind of device of bi-polar electrochemical synthetic system is built：The device of bi-polar electrochemical synthetic system is by straight
Flow driving power, graphite flake driving electrodes, bipolar electrode zinc microballoon, perfluorosulfonic acid ion membrane and polytetrafluoroethylene (PTFE) square groove
Composition.The anode of driving electrodes connects direct current driving power supply cathode and anode, graphite flake driving electrodes with conducting wire respectively with cathode
Anode and cathode be respectively placed in both ends in polytetrafluoroethylene (PTFE) square groove at the same time, graphite flake driving electrodes anode and graphite flake drive
The distance between moving electrode cathode is 2.5cm；Bipolar electrode zinc microballoon is positioned between the anode of driving electrodes and cathode, together
When the anode of graphite flake driving electrodes and cathode are kept apart with bipolar electrode zinc sphere physical with perfluorosulfonic acid ion membrane；
So polytetrafluoroethylene (PTFE) square groove forms the space segment of three isolation, and polytetrafluoroethylene (PTFE) square groove center section, which forms, to be contained
The electro synthesis room of bipolar electrode zinc microballoon, the insulating space at polytetrafluoroethylene (PTFE) square groove both ends form respectively containing driving electrodes
The anode chamber of anode and the cathode chamber of the cathode containing driving electrodes.
(2) ionic liquid is prepared：By choline chloride (98% purity) and ethylene glycol (AR) by mole the ratio between 1：100 mixing are equal
It is even to form transparent ionic liquid；
(3) 2-methylimidazole (99% purity) is dissolved in ionic liquid obtained by step (2), stirring makes it fully molten
Solution, it is 0.3mol/L to make its concentration；Followed by 1,4-benzoquinone (99% purity) is added, stirring makes it fully dissolve, 1,4-benzoquinone is existed
Concentration in ionic liquid is 0.005mol/L, finally obtains transparent weak yellow liquid；
(4) transparent weak yellow liquid prepared by step (3) is poured into the bipolar electrode electro synthesis room in step (1)
In, prepare another ionic liquid according still further to step (2) and pour into anode chamber and cathode chamber in step (1) respectively；
(5) preparation of the Janus microballoons of petal-like Metal-organic frame ZIF-8：Control the electricity of direct current driving power supply
Press as 20v, zinc microballoon (4mm diameters, 99.999% tenor) before the use with 1.0 mol/L salt acid soak 20 minutes,
Bipolar electrode zinc microballoon both ends form polarization anode and polarization cathode, the zinc microsphere surface shape close to driving electrodes anode one end
Polarization cathode, the zinc microsphere surface close to driving electrodes cathode one end form polarization anode.Bipolarity in ionic liquid
The polarization anode surface electro-deposition of electrode zinc microballoon obtains petal-like Metal-organic frame ZIF-8 films, and bipolarity is electric
The oxidation reaction that 1,4-benzoquinone only occurs for the polarization cathode surface of pole zinc microballoon is generated without ZIF-8, therefore prepares petal-shaped
Metal-organic frame ZIF-8 films Janus micro-sphere materials.
Fig. 1 is the SEM figures of zinc microballoon before embodiment 1 is reacted, and zinc microballoon does not have any thing before reacting as can be seen from Figure 1
Matter, surface are gloomy.
Fig. 2 is the SEM figures of zinc microballoon after embodiment 1 is reacted, as can be seen from Figure 2 zinc microballoon bipolarity in ionic liquid
After electrochemical reaction, the polarization anode surface electro-deposition of bipolar electrode zinc microballoon obtains Metal-organic frame ZIF-8 films
(such as Fig. 2 zinc microballoon left side, color relative zinc microballoon the right will become clear), but the polarization cathode of bipolar electrode zinc microballoon
Surface does not have ZIF-8 films and shows that the ash as zinc initial surface is dark-coloured (such as on the right of Fig. 2 zinc microballoon).So zinc microballoon table
Face forms the Janus microballoons of asymmetric feature of the both sides with different surfaces material.This asymmetric Janus microballoons in surface
There is different chemical property on same particle, therefore have a wide range of applications in fields such as catalyst, photoelectricity and sensors
Prospect.
Fig. 3 is the Metal-organic frame ZIF-8 materials that zinc microsphere surface made from embodiment 1 has petal shape
SEM schemes.From Fig. 3, it is apparent that 1 products obtained therefrom of embodiment is clearly petal-shaped, this flower with fine regularity
The Metal-organic frame ZIF-8 of lobed shape yet there are no relevant report.
Fig. 4 is the XRD diagram of the Metal-organic frame ZIF-8 materials of petal shape made from embodiment 1.The XRD diagram of Fig. 4
Diffraction maximum (011) in spectrum is the most significant characteristic peaks of Metal-organic frame ZIF-8, other diffraction maximums such as (002), (112),
(022), (013) and (222) etc. both correspond to the characteristic peak of Metal-organic frame ZIF-8, these data and relevant research
Report (Venna, Surendar R.Jasinski, Jacek B.Carreon, Moises the A.Journal of that are consistent completely
the American Chemical Society, 2010,132:18030), illustrate successful by bi-polar electrochemical method
It deposited Metal-organic frame ZIF-8 films in one end of zinc microsphere surface.
Embodiment 2
(1) a kind of device of bi-polar electrochemical synthetic system is built：The device of bi-polar electrochemical synthetic system is by straight
Flow driving power, graphite flake driving electrodes, bipolar electrode zinc microballoon, perfluorosulfonic acid ion membrane and polytetrafluoroethylene (PTFE) square groove
Composition.The anode of driving electrodes connects direct current driving power supply cathode and anode, graphite flake driving electrodes with conducting wire respectively with cathode
Anode and cathode be respectively placed in both ends in polytetrafluoroethylene (PTFE) square groove at the same time, graphite flake driving electrodes anode and graphite flake drive
The distance between moving electrode cathode is 2.5cm；Bipolar electrode zinc microballoon is positioned between the anode of driving electrodes and cathode, together
When the anode of graphite flake driving electrodes and cathode are kept apart with bipolar electrode zinc sphere physical with perfluorosulfonic acid ion membrane；
So polytetrafluoroethylene (PTFE) square groove forms the space segment of three isolation, and polytetrafluoroethylene (PTFE) square groove center section, which forms, to be contained
The electro synthesis room of bipolar electrode zinc microballoon, the insulating space at polytetrafluoroethylene (PTFE) square groove both ends form respectively containing driving electrodes
The anode chamber of anode and the cathode chamber of the cathode containing driving electrodes.
(2) ionic liquid is prepared：By choline chloride (98% purity) and ethylene glycol (AR) by mole the ratio between 2：100 mixing
It is formed uniformly transparent ionic liquid；
(3) 2-methylimidazole (99% purity) is dissolved in ionic liquid obtained by step (2), stirring makes it fully molten
Solution, it is 1.5mol/L to make its concentration；Followed by 1,4-benzoquinone (99% purity) is added, stirring makes it fully dissolve, 1,4-benzoquinone is existed
Concentration in ionic liquid is 0.008mol/L, finally obtains transparent weak yellow liquid；
(4) transparent weak yellow liquid prepared by step (3) is poured into the bipolar electrode electro synthesis room in step (1)
In, prepare another ionic liquid according still further to step (2) and pour into anode chamber and cathode chamber in step (1) respectively；
(5) preparation of the Janus microballoons of petal-like Metal-organic frame ZIF-8：Control the electricity of direct current driving power supply
Press as 15v, zinc microballoon (4mm diameters, 99.999% tenor) before the use with 1.0 mol/L salt acid soak 20 minutes,
Bipolar electrode zinc microballoon both ends form polarization anode and polarization cathode, the zinc microsphere surface shape close to driving electrodes anode one end
Polarization cathode, the zinc microsphere surface close to driving electrodes cathode one end form polarization anode.Bipolarity in ionic liquid
The polarization anode surface electro-deposition of electrode zinc microballoon obtains petal-like Metal-organic frame ZIF-8 films, and bipolarity is electric
The oxidation reaction that 1,4-benzoquinone only occurs for the polarization cathode surface of pole zinc microballoon is generated without ZIF-8, therefore prepares petal-shaped
Metal-organic frame ZIF-8 films Janus micro-sphere materials.
Embodiment 3
(1) a kind of device of bi-polar electrochemical synthetic system is built：The device of bi-polar electrochemical synthetic system is by straight
Flow driving power, graphite flake driving electrodes, bipolar electrode zinc microballoon, perfluorosulfonic acid ion membrane and polytetrafluoroethylene (PTFE) square groove
Composition.The anode of driving electrodes connects direct current driving power supply cathode and anode, graphite flake driving electrodes with conducting wire respectively with cathode
Anode and cathode be respectively placed in both ends in polytetrafluoroethylene (PTFE) square groove at the same time, graphite flake driving electrodes anode and graphite flake drive
The distance between moving electrode cathode is 2.5cm；Bipolar electrode zinc microballoon is positioned between the anode of driving electrodes and cathode, together
When the anode of graphite flake driving electrodes and cathode are kept apart with bipolar electrode zinc sphere physical with perfluorosulfonic acid ion membrane；
So polytetrafluoroethylene (PTFE) square groove forms the space segment of three isolation, and polytetrafluoroethylene (PTFE) square groove center section, which forms, to be contained
The electro synthesis room of bipolar electrode zinc microballoon, the insulating space at polytetrafluoroethylene (PTFE) square groove both ends form respectively containing driving electrodes
The anode chamber of anode and the cathode chamber of the cathode containing driving electrodes.
(2) ionic liquid is prepared：By choline chloride (98% purity) and ethylene glycol (AR) by mole the ratio between 3：100 mixing
It is formed uniformly transparent ionic liquid；
(3) 2-methylimidazole (99% purity) is dissolved in ionic liquid obtained by step (2), stirring makes it fully molten
Solution, it is 2.5mol/L to make its concentration；Followed by 1,4-benzoquinone (99% purity) is added, stirring makes it fully dissolve, 1,4-benzoquinone is existed
Concentration in ionic liquid is 0.010mol/L, finally obtains transparent weak yellow liquid；
(4) transparent weak yellow liquid prepared by step (3) is poured into the bipolar electrode electro synthesis room in step (1)
In, prepare another ionic liquid according still further to step (2) and pour into anode chamber and cathode chamber in step (1) respectively；
(5) preparation of the Janus microballoons of petal-like Metal-organic frame ZIF-8：Control the electricity of direct current driving power supply
Press as 30v, zinc microballoon (4mm diameters, 99.999% tenor) before the use with 1.0 mol/L salt acid soak 20 minutes,
Bipolar electrode zinc microballoon both ends form polarization anode and polarization cathode, the zinc microsphere surface shape close to driving electrodes anode one end
Polarization cathode, the zinc microsphere surface close to driving electrodes cathode one end form polarization anode.Bipolarity in ionic liquid
The polarization anode surface electro-deposition of electrode zinc microballoon obtains petal-like Metal-organic frame ZIF-8 films, and bipolarity is electric
The oxidation reaction that 1,4-benzoquinone only occurs for the polarization cathode surface of pole zinc microballoon is generated without ZIF-8, therefore prepares petal-shaped
Metal-organic frame ZIF-8 films Janus micro-sphere materials.
Claims (8)
1. a kind of Janus microballoons using ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame ZIF-8
Method, it is characterised in that include the following steps：
(1) a kind of structure of bi-polar electrochemical synthetic system：The device of bi-polar electrochemical synthetic system includes DC driven
Power supply, driving electrodes, bipolar electrode and membrane, the positive and negative anodes of direct current driving power supply connect the anode and the moon of driving electrodes respectively
Pole, places bipolar electrode between the anode and cathode of driving electrodes, between bipolar electrode and driving electrodes anode and cathode respectively
Separated with membrane and form cathode chamber respectively, electro synthesis room and anode chamber；
(2) choline chloride and ethylene glycol are uniformly mixed to form transparent ionic liquid；
(3) 2-methylimidazole is dissolved in ionic liquid obtained by step (2), stirring makes it fully dissolve；Add 1,4-benzoquinone,
Stirring makes 1,4-benzoquinone fully dissolve, and obtains transparent weak yellow liquid；
(4) bipolar electrode in using zinc microballoon as step (1), step (1) is poured into by weak yellow liquid prepared by step (3)
In electro synthesis room in, ionic liquid prepared by step (2) is poured into anode chamber and cathode chamber in step (1)；
(5) voltage of direct current driving power supply, the anode surface electro-deposition of the bipolar electrode zinc ball only in ionic liquid are controlled
Petal-like Metal-organic frame ZIF-8 films are obtained, so as to obtain the Janus of petal-shaped Metal-organic frame ZIF-8
Microballoon.
2. according to claim 1 utilize ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame ZIF-
The method of 8 Janus microballoons, it is characterised in that in step (1), the driving electrodes are inert electrode platinized platinum or graphite flake；Institute
It is metallic conductor zinc microballoon to state bipolar electrode.
3. according to claim 1 utilize ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame ZIF-
The method of 8 Janus microballoons, it is characterised in that the distance between driving electrodes anode and driving electrodes cathode are 2.5cm；Zinc
Microballoon is before the use with the salt acid soak 15~30 minutes of 1.0~1.5mol/L.
4. according to claim 1 utilize ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame ZIF-
The method of 8 Janus microballoons, it is characterised in that in step (1), the membrane is perfluorosulfonic acid ion isolation film.
5. according to claim 1 utilize ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame ZIF-
The method of 8 Janus microballoons, it is characterised in that in step (2), the molar ratio of choline chloride and ethylene glycol mixing is 1~4：
100。
6. according to claim 1 utilize ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame ZIF-
The method of 8 Janus microballoons, it is characterised in that in step (3), 2-methylimidazole is dense in ionic liquid obtained by step (2)
Spend for 0.3~3.0mol/L.
7. according to claim 1 utilize ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame ZIF-
The method of 8 Janus microballoons, it is characterised in that in step (3), concentration of the 1,4-benzoquinone in ionic liquid obtained by step (2) is
0.005~0.015mol/L.
8. according to claim 1 utilize ionic liquid bi-polar electrochemical synthesis petal-shaped Metal-organic frame ZIF-
The method of 8 Janus microballoons, it is characterised in that in step (5), the voltage control of direct current driving power supply is 10v~30v.
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| CN112812316A (en) * | 2020-12-23 | 2021-05-18 | 华南理工大学 | Method for preparing ZIF-8 material under external electric field condition |
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| CN109082685A (en) * | 2018-08-28 | 2018-12-25 | 河南师范大学 | A kind of application of the method that flower-shaped AuPt alloy nano particle is prepared in eutectic solvent and its Electric oxidative synthesis xanthone |
| CN109082685B (en) * | 2018-08-28 | 2020-04-21 | 河南师范大学 | Method for preparing flower-like AuPt alloy nanoparticles in eutectic solvent and application of flower-like AuPt alloy nanoparticles in electrooxidation synthesis of xanthone |
| CN109183063A (en) * | 2018-11-23 | 2019-01-11 | 南京科技职业学院 | A kind of batch electrochemistry formated device of metal-organic framework materials |
| CN110078935A (en) * | 2019-05-17 | 2019-08-02 | 哈尔滨理工大学 | A kind of electrochemistry new method synthesizing metal-organic framework materials DUT-52 |
| CN110144048A (en) * | 2019-05-29 | 2019-08-20 | 哈尔滨理工大学 | A kind of method of electrochemistry rapid synthesis bimetallic Zn/Co-ZIF-8 |
| CN110144048B (en) * | 2019-05-29 | 2021-07-09 | 哈尔滨理工大学 | Method for electrochemically and rapidly synthesizing bimetallic Zn/Co-ZIF-8 |
| CN112812316A (en) * | 2020-12-23 | 2021-05-18 | 华南理工大学 | Method for preparing ZIF-8 material under external electric field condition |
| CN115201295A (en) * | 2022-07-13 | 2022-10-18 | 江汉大学 | Chemically modified electrode for detecting high sweetener NHDC and preparation method thereof |
| CN115201295B (en) * | 2022-07-13 | 2024-04-02 | 江汉大学 | Chemically modified electrode for detecting high-power sweetener NHDC and preparation method |
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