CN108130574A - A kind of method of oxygen auxiliary cathode deposited metal organic framework material - Google Patents
A kind of method of oxygen auxiliary cathode deposited metal organic framework material Download PDFInfo
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- CN108130574A CN108130574A CN201810003797.9A CN201810003797A CN108130574A CN 108130574 A CN108130574 A CN 108130574A CN 201810003797 A CN201810003797 A CN 201810003797A CN 108130574 A CN108130574 A CN 108130574A
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Abstract
The present invention provides a kind of methods of oxygen auxiliary cathode deposited metal organic framework material, include the following steps：（1）Reaction precursor liquid solution is prepared, the precursor solution is by the source metal of 5 ~ 50mM, organic ligand and the organic solvent composition of 10 ~ 250mM；（2）Using constant voltage method or cyclic voltammetry, electrochemical deposition is carried out on cathode conductive substrates surface to obtain the final product.The method of the present invention will not cause to corrode to depositing electrode, conductive substrates range of choice is wide, the patterns of prepared MOF materials, size and thickness are adjustable on nanoscale, material is pure, supporting electrolyte need not be added, at low cost, synthesis only needs a step, method and easy to operate, is easy to implement industrialized production.
Description
Technical field
Electrochemical method the invention belongs to metal-organic framework materials synthesizes field, and in particular to a kind of oxygen auxiliary cathode
The method of deposited metal organic framework material.
Background technology
Metal organic framework (Metal-Organic frameworks, abbreviation MOFs) material is by metal ion（Or gold
Belong to ion cluster）A kind of porous crystalline material with three-dimensional net structure formed with organoligand coordination.Due to MOFs
With big specific surface area, uniform adjustable aperture and it is unique chemistry, physical property, make its gas storage, separation and
The traditional fields such as heterocatalysis have very big potential application, and MOF film materials are prepared in conductive substrates makes its application latent
The fields such as energy storage and conversion, sensing and electronics can be further extended to.In all kinds of methods for preparing MOF film layers,
Electrochemical deposition because reaction condition is mild, the reaction time is short, reactive group bottom need not especially processing and pattern thickness it is controllable this
A little advantages and receive favor.
The electrochemistry preparation of MOFs is divided into cathode deposition and anodic deposition.In anodic deposition method, by aoxidizing various anodes
Metal generates corresponding metal ion and is deposited on anode surface with the ligands formation MOF materials in electrolyte.Cathode deposits
Rule is the specific reactant probase of reduction（Such as：Nitrate anion or triethylamine ion）Increase the pH value near cathode, from
And promote the deprotonation of ligand, therefore MOF is deposited in cathode surface.
Relative to Zn (II), Co (II), the common metal ions of Cu (II) these MOF, probase has higher reduction
Overpotential, therefore, along with the plating of metal in the cathode run of these MOF, such as Li Minjuan etc. are in document：
J. Am. Chem. Soc., 133 (2011), 12926-12929 pages, Campagnol etc. J. Mater. Chem. A.,
4 (2016), 3914-3925 pages reported.Although the regulation and control during the reaction that theoretically electrochemical deposition can be more flexible
The growth of MOF, such as Al-Kutubi etc., ChemElectroChem, 2 (2015), 462-474, Wei-Jin Li etc., J.
Mater. Chem. A., 4 (2016), 12356-12369 are reported, but in terms of the accuracy controlling of the pattern of MOF and thickness still
Not by developmental research, and the regulation and control of the two are extremely important in the application of optics and electronic device.In addition to this, before
In report, cathode deposition need to be under anaerobic environment and containing carrying out under conditions of supporting electrolyte, supporting electrolyte（Particularly
Organic bath）Price it is higher, therefore synthesis cost is higher.
The electrochemical reduction of oxygen is critically important during the conversion and storage of energy, and in some and superoxipe ion
Relevant bioprocess（For example superoxide dismutase catalysis causes the disproportionation of superoxipe ion）Also important role is play,
Therefore, the electrochemical reduction of oxygen has obtained extensive research.Compared to those probase, the reduction potential of molecular oxygen is more
It is low, and in special metal ion（Zn (II), Co (II), Fe (II), Mn (II) and Cd (II)）In the presence of, starting
Current potential can also reduce.As the electrochemical reduction product of molecular oxygen, superoxipe ion and many substances（Such as water, acids and gold
Belong to ion etc.）Between exist very high reactivity.
Invention content
Technical problems to be solved：The present invention is corroded for present in current electrochemical method deposited metal framework material
Depositing electrode needs that the material for being deposited, being prepared under anaerobic is impure, thickness is unable to the technical problems such as control accurate,
A kind of method of oxygen auxiliary cathode deposited metal organic framework material is provided, this method is at low cost, and synthesis only needs a step, side
Method and easy to operate, is easy to implement industrialized production.
Technical solution：A kind of method of oxygen auxiliary cathode deposited metal organic framework material, includes the following steps：
（1）Prepare reaction precursor liquid solution, the precursor solution by 5 ~ 50mM source metal, the organic ligand of 10 ~ 250mM and
Organic solvent forms；
（2）Using constant voltage method or cyclic voltammetry, electrochemical deposition is carried out on cathode conductive substrates surface to obtain the final product.
It is further preferred that the source metal include Zn (II), Co (II), Cd (II), Cu (II), Mn (II), Ni (II),
Fe (II) or Fe (III), specifically the compound using Zn (II) as source metal is anhydrous ZnCl2, using Co (II) as metal
The compound in source is anhydrous CoCl2。
It is further preferred that the step（1）Later, 30min high pure airs or oxygen are passed through into precursor solution.
It is further preferred that the organic ligand includes 2-methylimidazole, 4,5- dichloro-imidazoles and the miaow containing difunctional
Azole derivative, benzoic acid, terephthalic acid (TPA) or trimesic acid and its derivative.
It is further preferred that the organic solvent includes methanol, ethyl alcohol, n,N-Dimethylformamide or acetonitrile.
It is further preferred that the conductive substrates include indium tin oxide target, fluorine doped tin oxide, carbon fiber, highly directional pyrolysis stone
Ink, copper, gold, platinum electrode.
It is further preferred that the voltage of the constant voltage method is 0V ~ -2.5V, the time is 2min ~ for 24 hours.
It is further preferred that voltage range is -2.5V ~ 0V, sweep speed 100mV/s in the cyclic voltammetry, sink
The product time is 10min ~ for 24 hours.
It is further preferred that the step（2）Middle depositing temperature is 20 ~ 120 DEG C.
Metal-organic framework materials prepared by method of the present invention.
Oxygen auxiliary cathode deposits the mechanism study of ZIF film layers
Prepare the ammonium hexafluorophosphate of the tetrabutyl containing 100mM (NBu4)PF6) methanol solution as background solution, prepare contain respectively
The methanol solution of 20mM methylimidazoles (HmiM), ZnCl containing 10mM2Methanol solution and ZnCl containing 10mM2And 20mM
The mixed solution of HmiM, the (NBu containing 100mM in each solution4)PF6As electrolyte.Before the test of Ar gas saturations, to treating
It surveys in solution and leads to 30 min of high-purity Ar gas to remove molecular oxygen, before the test of oxygen auxiliary cathode deposition, lead into solution to be measured
30 min of high pure air.
Working electrode-glass-carbon electrode（GCE）Processing：New glassy carbon electrode surface is cleaner, and the solid not deposited is miscellaneous
Matter before use, takes the aluminum oxide polishing powder of a small amount of 0.5mm on chamois leather, polishing powder is drenched for beating with deionized water
Grind glass-carbon electrode（The polishing time is too short, and to be not easy polishing clean）, then cleaned with deionized water, ultrasound, deionized water cleaning,
Use N2Drying examines the whether bright free from admixture of glassy carbon electrode surface, if any impurity, then needs to repeat the above steps；If
There is no apparent impurity then to carry out in next step, passing through multiple cyclic voltammetric with prepared dilution heat of sulfuric acid（CV）To clean electricity
Pole, cleaning 15min or so.
To electrode-platinum filament（Pt）Processing：Platinum filament needs to impregnate 30 min in dilute hydrochloric acid solution before use, removes electricity
The non-organic property impurity of some of pole surface is cleaned multiple times with deionized water after being taken out from dilute hydrochloric acid, uses N2Air-blowing is done, Ran Hou
It burns to aglow under flame, with deionized water ultrasound after cooling, can be used after drying.
The processing of reference electrode-Ag/AgCl electrodes：It is carried out after being taken out from the saturated solution of potassium chloride with deionized water
It repeatedly rinses, uses N2It should be at once put into solution to be measured after drying.
Electrochemical workstation model C HI660（Shanghai Chen Hua Instrument Ltd.）, joined by connecting a computer regulating
Number and collection data.Preliminary sweep is scanned from 0V to negative sense, sweep speed 100mV/s（Except special proposition scanning direction）.
Cyclic voltammetry is tested（CV）：CV tests carry out in ternary electrochemical cell, and the glass-carbon electrode of a diameter 3mm is made
For working electrode, Pt are used as to electrode, and Ag/AgCl (in the KCl aqueous solutions of 3M) is as reference electrode.The work in electrolytic cell
Make electrode with being separated to electrode by inner matter, connected between reference electrode and electrolytic cell by salt bridge.
The cathode deposition of ZIF materials occurs at room temperature in the present invention, and reaction solution is containing ZnCl2（Or CoCl2）And imidazoles
The methanol solution of ligand.According to hsab theory principle (HSAB), Zn (II)/Co (II) (boundary acid) and Cl（Boundary
Alkali）In the presence of very strong interaction, therefore, metal ion drives before the reaction can be with the shape of free ion and a variety of complexs in liquid
Formula exists, [M (II) (imidazole)nClm] (solvent molecule of coordination omits herein).The precursor solution at room temperature can be with
It is stabilized more days, has no solid product.The understanding of ZIF-8 is deposited to increase oxygen auxiliary cathode, has individually prepared ZnCl2
(10mM), 2-methylimidazole (HmiM, 20mM）And ZnCl2The methanol of (10mM) and 2-methylimidazole (HmiM, 20mM)
Mixed solution, and with tetrabutyl ammonium hexafluorophosphate ((NBu)4PF6, 100mM) and as electrolyte, to contain (NBu)4PF6
The methanol solution of (100mM) is followed on glass-carbon electrode (GCE) with the sweep speed of 100mV/s respectively as background solution
Ring voltammetry (CV) studies respective electrochemical behavior.
CV curves in Fig. 2 a for each solution after removing molecular oxygen.Methanol background solution shows without any volt-ampere of response
Methanol is in research voltage range -1.2V-1.0V（With Ag/AgCl（3M KCl）For reference electrode）It is electrochemically stable.Containing with
The background solution of body HmiM until -1.2V is stable, but when voltage is higher than 0.75V, will occur in cathode in anode
Oxidation.Relative to ZnCl2Reduction takes place in -1.08V in solution, Zn (II), and in ZnCl2With Zn in the mixed solution of HmiM
(II) it is because ligand HmiM and Zn (II) coordination form complex Zn (II) that reduction, which needs higher reduction overpotential,
(HmiM)nClm, so as to reduce the concentration of metal free ion.
Such as Fig. 2 b, when being passed through high pure air in these methanol solutions（Oxygen concentration in methanol solution is about 2mM）, then its
Electrochemical behavior then occurs substantially to change.For background solution, the visible cathodic reduction peak at -0.85V, in starting -0.4V
Peak, this corresponds to electrode surface O2It is reduced into O2 -：
O2 + e- → O2 -
It would generally be in non-protonic solvent（Such as dimethyl sulfoxide (DMSO) (MDSO), n,N-Dimethylformamide（DMF）, acetonitrile
（MeCN）In the anode back reaction O that will appear2 -It is oxidized to O2, do not occur during counter sweep, show in protonic solvent
O2 -Rapid disproportionation occurs.Anode peak appears in 0.82V, is attributed to the oxidation of methoxide, and methoxide comes from the O of proton initiation2 -'s
Disproportionation：
2O2 - + 2CH3OH → H2O2 + 2CH3O- + O2
It adds in the methanol background solution of HmiM, then negative sense is moved to -0.89V at the cathodic reduction peak of molecular oxygen, and anode peak occurs
In 0.77V and intensity enhancing.The acidity of both imidazole ligands and methanol is compared, it is presumed that the anode peak comes from deprotonation
Imidazole ligands oxidation.PKa value of the methanol in water or DMSO solution is respectively 15.5 or 29, and HmiM ligands are corresponding
PKa value in two kinds of solution is respectively 14.2 or 18.8, and acidity is better than methanol, therefore is easier as O2 -Disproportionation provide matter
Son：
2O2 - + 2HmiM → H2O2 + 2miM- + O2
Contain ZnCl2Methanol background solution in, oxygen molecule reduction rise peak position forward direction movement, originate in -0.16V, electric current
It substantially reduces, shows to occur and Zn (II) relevant O2 -Disproportionation.Before research shows that, Zn (II) can be used as lewis acid
Promote O2 -Between electronics transfer generation O2[Zn (II) O2 2-].The Zn (II) of peroxidating can be with water, organic substrate or even electricity
Pole surface reacts, therefore guesses that the Zn (II) of peroxidating is reacted with methanol and generate hydrogen peroxide and methoxide：
Zn(II) + O2 - → [Zn(II)O2 -]
[Zn(II)O2 -] + O2 - → [Zn(II)(O2 -)2]
[Zn(II)(O2 -)2] → [Zn(II)O2 2-] + O2
[Zn(II)O2 2-] + 2CH3OH → Zn(II) + H2O2 + 2CH3O-
Add in ZnCl2In the methanol background solution of HmiM, there are two cathode peaks in -0.77V and -1.0V in first lap scanning,
Current strength is decreased obviously compared with first three solution, the two peak cathode current intensity are also continued in next scanning under stablizing
The petition of surrender is bright to have material to be deposited on electrode surface.The two cathode peaks occurred in first lap scanning, -0.77V places should be attributed to O2
In the reduction of electrode surface, and film layer causes resistance to become larger in electrode surface deposition, so -1.0V places should be attributed to O2It is depositing
In the reduction of the film surface on electrode.Anode reaction, which disappears, to be illustrated not generating metal Zn, methoxide during cathodic scan
With the ligand (miM of free-moving deprotonation-).Zn (II) can exist in a variety of forms in the solution, [Zn (II)
(HmiM)n]2+(n=0-4) this form is most beneficial for the intermediate for forming super oxygen Zn (II), [Zn (II) (HmiM)n
(O2 -)2] as lewis acid catalysis O2 -Disproportionation, promote superoxipe ion between electronics transfer：
[Zn(II)(HmiM)n]2++ 2O2- → [Zn(II)(HmiM)nO2 2-]+ O2
Imidazoles and metal are coordinated the complex to be formed（PKa=10.3 in aqueous solution) than free HmiM（PKa in aqueous solution
=14.2）And methanol（PKa=15.5 in aqueous solution）It is acid stronger, thus speculate, peroxidating Zn (II) intermediate products [Zn
(II)(HmiM)nO2 2-] be intended to and [Zn (II) (HmiM)nClm] reaction（Possibly even peroxidating Zn (II) intermediate product
Between react to each other）Hydrogen peroxide and the Imidazole complex of deprotonation are generated, and the Imidazole complex of deprotonation is in the case where connecing
To form ZIF-8 ([Zn (II) (miM) by ligand exchange, nucleation and growth2]x)。
[Zn(II)(HmiM)nO2 2-] + [Zn(II)(HmiM)nClm] → [Zn(II)(miM)2(HmiM)n-2Clm] +
[Zn(II)(HmiM)n] + H2O2
x[Zn(II)(miM)2(HmiM)n-2Clm] → [Zn(II)(miM)2]x
Advantageous effect：A kind of method of oxygen auxiliary cathode deposited metal organic framework material of the present invention, first, it is sunk using cathode
Area method relative to anodic dissolution process, will not cause to corrode to depositing electrode, meanwhile, cathode deposition expand significantly depositing electrode,
The selectivity of source metal and organic ligand；Second, the pattern of MOF film materials that is prepared using the method for the present invention, size and
Thickness is adjustable on nanoscale；Third using the relatively low reduction potential of oxygen, is effectively prevented from the deposition process of MOF
Metal deposit, and react and be also deposited without other dephasigns, obtain pure MOF；4th, the present invention in oxygen assist
Cathode deposition can carry out under conditions of no supporting electrolyte, directly avoid electrolyte in this way and be embedded in material when MOF is deposited
Possibility in the pore structure of material, due to electrolyte（Particularly organic bath）Higher price, therefore the present invention is also significantly
Reduce synthesis cost；5th, the method for the invention realizes a variety of MOF alternating deposits, to prepare orderly controllable hydridization MOF
Material provides method；6th, three-electrode system, which had both may be used, in method of the invention can also use two electrode systems；The
Seven, it reacts in of the invention and carries out at ambient temperature, reaction condition is mild, and oxygen needed for reaction can arise directly from sky
Gas, almost cost free, is easy to get and cleanliness without any pollution, synthesis only needs a step, method and easy to operate and above-mentioned each advantage, make
It is of the invention in MOF cathode deposition methods be applicable not only to laboratory preparation, equally also allow for realize industrialized production.
Description of the drawings
Fig. 1 deposits ZIF-8 schematic diagrames for oxygen auxiliary cathode, in the electrochemical reaction for forming ZIF-8, in methanol precursor liquid
O2O is electrochemically reduced near electrode surface2-, next chemical reaction is related to Zn (II)-Imidazole complex and promotes to surpass
Between oxygen radical ion electronics transfer, Zn (II)-Imidazole complex deprotonation and pass through ligand exchange, nucleation and growth
Form ZIF-8.
A in Fig. 2, b are respectively in Ar saturations（Not molecule-containing keto）And the saturation of the air（Molecule-containing keto）Under conditions of followed
Ring volt-ampere tests (100mV/s),Representing methanol background solution, (methanol of 100mM tetrabutyl ammonium hexafluorophosphates is molten
Liquid),Represent 2-methylimidazole（20mM）With the mixed solution of background solution,Represent ZnCl2(10mM) and background are molten
The mixed solution of liquid,Represent 2-methylimidazole (20mM), ZnCl2The mixed solution of (10mM) and background solution.
Fig. 3 is the SM figures of the film of embodiment 1, and wherein a, b, c is respectively deposition 2h (a), 6h under -0.7V voltages
(b), 12h (c)；E, f are respectively -0.9V (e), and 2h is deposited under -1.0V (f) voltages；D be simulation ZIF-8, HOPG bases
Bottom and figure a, the corresponding XRD comparison diagrams of b, c.
SEM planes and corresponding sectional view of a for embodiment 2 (- 0.8 ~ 0 V, 100 mV/s) film, b in Fig. 4
It is 2 thin film deposition thickness of embodiment with the change curve of sedimentation time.
Fig. 5 is that the XRD of embodiment 2 (- 0.8V ~ 0V, 100mA/s) film schemes.
A is the SEM figures of the carbon fiber of blank in Fig. 6, and b is embodiment 3（-1.0V, 2h）The SEM figures of film.
Fig. 7 is the CV curves of embodiment 4 (- 1 ~ 0V, 2h)（A represents (NBu4) of the precursor liquid containing 100mM
PF6, b are represented without (NBu4) PF6).
Fig. 8 is that the SEM of embodiment 4 (- 2V, 2h) schemes, and a is (NBu4) PF6 containing 100mM, and b is without (NBu4)
PF6。
Fig. 9 is embodiment 4 and is deposited the XRD comparison diagrams of ZIF-8 on FTO using binary electrode method.
Figure 10 is that the film SEM of embodiment 5 (- 2V, 6h) schemes.
Figure 11 is the XRD diagram that metal Zn simulates XRD and embodiment 5.
Figure 12 is that the section SEM of embodiment 6 (- 1.5V, 3h) film schemes.
Figure 13 is the XRD diagram that metal Co simulates XRD and embodiment 6.
It is about 5*7cm that a, which is the area of deposition, in Figure 142ZIF-8/ZIF-67 hybridized films optical photograph, b is first deposits
About 100nm thickness ZIF-8 films section SEM figures, c is after deposited 200nm ZIF-67 on 100nm ZIF-8 films
Hybridized film section SEM figure, d be ZIF-8 (~ 100nm)/ZIF-67 (~ 200nm) double layer hybridized film TEM scheme, e for d correspondence
TEM EDX spectrograms.
Specific embodiment
Embodiment 1
Oxygen auxiliary law deposits ZIF-8 on HOPG, includes the following steps：
（1）Prepare ZnCl containing 10mM2, 20mM HmiM and 100mM (NBu4)PF6Methanol solution, be passed through height before deposition
Pure air 30min；
（2）Utilize constant voltage method（Three-electrode system）, carry out electrochemical deposition to obtain the final product on cathode conductive substrates surface, wherein, work
To make electrode as HOPG, be Pt to electrode, reference electrode is Ag/AgCl electrodes, applies different biass and is deposited, respectively-
0.5V, 2h; -0.7V, 2h; 6h, 12h; -0.9V, 2h; -1V, 2h。
The processing of HOPG：Graphite needs are current now to be taken off, and is prevented surface contamination or fracture, is influenced the life of electric conductivity and crystal
It is long.Graphite surface is glued to high temperature resistant is two-sided when needing, gently friction pressing, finally gently takes one layer off and can be used, it
Ensure the continuity of graphite flake, do not need to carry out hydrophilic treated.
To electrode-platinum filament（Pt）Processing：Platinum filament needs to impregnate 30 min in dilute hydrochloric acid solution before use, removes electricity
The non-organic property impurity of some of pole surface is cleaned multiple times with deionized water after being taken out from dilute hydrochloric acid, uses N2Air-blowing is done, Ran Hou
It burns to aglow under flame, with deionized water ultrasound after cooling, can be used after drying.
The processing of reference electrode-Ag/AgCl electrodes：It is carried out after being taken out from the saturated solution of potassium chloride with deionized water
It repeatedly rinses, uses N2It should be at once put into solution to be measured after drying.
Scanning electron microscope (SEM) figure can be observed, the voltage of application -0.5V, by 2 hours, be had no in HOPG substrates apparent
Product.Such as Fig. 3 a, when bias increases to -0.7V, by 2 hours, it is seen that size is in irregular shape between 100-300nm
Grain is distributed on present HOPG, and for time lengthening to 6 hours, these particle sizes increased to 400nm or so, and form distinct
Granatohedron shape（Fig. 3 b）.Reaction time continues to extend to 12 hours, and particle size also continues to become larger to 500-
600nm or so, but generally exist in the form of symbiosis（Fig. 3 c）.The material that x-ray diffraction pattern (XRD) shows to prepare is crystallization
State, peak position is consistent with the XRD peak positions of ZIF-8 at 7.36 °, 10.4 °, 12.74 °, 14.74 ° and 18.08 °.Other peaks
Position is classified as the substrate peak of HOPG.The diffraction peak intensity of ZIF-8 enhances with the growth in reaction time, shows the gradual life of crystal
It is long, it is consistent with SEM results.
The film layer of finer and close symbiosis can then be formed, but particle size generally can be with voltage in film layer by applying more negative voltage
Increase and reduce.As shown in Figure 3 e, application -0.9V voltages formed membrane-coating granules size in 200-300nm or so, and -
The membrane-coating granules size prepared under 1.0V voltages is but in 40-80nm（Fig. 3 f）.The above results show formation and the pattern of ZIF-8
Variation dependent on voltage.Therefore, the voltage of application is high to Zn (the II)-imidazoles cooperation for ensureing the enough deprotonations of generation
Object makes ZIF-8 carry out initial nucleation in electrode surface.On the other hand, higher voltage can promote to be nucleated and make brilliant in film layer
Particle size is generally less than normal.
Embodiment 2
Oxygen auxiliary law deposits ZIF-8 on ITO, includes the following steps：
（1）Prepare ZnCl containing 10mM2, 20mM HmiM and 100mM (NBu4)PF6Methanol solution；
（2）Utilize cyclic voltammetry（Three-electrode system）, carry out electrochemical deposition to obtain the final product on cathode conductive substrates surface, wherein,
Working electrode is ITO, to electrode be Pt, reference electrode be Ag/AgCl electrodes, voltage range -0.8V ~ 0V, sweep speed
100mV/s, sedimentation time are respectively 10 min, 15 min, 30 min, 60 min, 120 min, 240 min.
The processing of ITO：By 100*10 mm2ITO be respectively placed in acetone.Each ultrasonic 15 minutes in ethyl alcohol, deionized water,
It is rinsed well with deionized water, N2Drying, is placed in 1:1:5 H2O2、NH3H2O:、H2In the mixed liquor of O, 90 DEG C are heated 2 hours
Afterwards, deionized water is rinsed well, N2Drying.
The processing method of Pt and Ag/AgCl electrodes is the same as embodiment 1.
Monitored in real time using cyclic voltammetry electrode surface generation electrochemical reaction, experiment condition after optimization,
The thickness and crystallite dimension of ZIF-8 film layers can be regulated simply by control sedimentation time on nanoscale.Such as
Fig. 4 a, using cyclic voltammetry（-0.8-0V）, 15 min are reacted, about 24 nm thickness are prepared on ITO, crystallite dimension is in 15-
The ZIF-8 films of 30 nm.After the deposition of 240 minutes, the crystallite dimensions of ZIF-8 films is about 96 nm, thickness about 86
nm.In entire deposition process, in first 30 minutes, ZIF-8 film layers are thickened rapidly with the speed of about 1.5 nm/min, next
Deposition velocity be reduced to about 0.2 nm/min（Such as Fig. 4 b）, this slack-off is caused by infiltration rate of the reactant in ZIF-8 film layers
's.As shown in figure 5, metal Zn generations are had no in the deposition process of ZIF-8.
Embodiment 3
Oxygen auxiliary law deposits ZIF-8 on carbon fiber, includes the following steps：
（1）It prepares containing 10 mM ZnCl2, 20 mM HmiM and 100 mM (NBu4)PF6Methanol solution, be passed through before deposition
High pure air 30min；
（2）Utilize constant voltage method（Three-electrode system）, carry out electrochemical deposition to obtain the final product on cathode conductive substrates surface, wherein, work
Make electrode as carbon fiber, be Pt to electrode, reference electrode is Ag/AgCl electrodes, and the voltage of application -0.9V deposits 1 h.
The processing of carbon fiber：It is 3 that carbon fiber is immersed in volume ratio:7 H2O2With dense H2SO4Mixed solution in,
70 DEG C of 1 h of heat treatment, then with deionized water are rinsed repeatedly, are finally immersed in spare in clean deionized water, made repeatedly
It is placed in 80 DEG C of baking oven and dried with preceding taking-up, be cooled to room temperature and can be used.
The processing method of Pt and Ag/AgCl electrodes is the same as embodiment 1.
Such as Fig. 6 a, it can be seen that blank carbon fiber surface compares smooth；It is visible in Fig. 6 b to be deposited on carbon fiber
One layer of ZIF-8 film, after depositing one layer of ZIF-8 film, surface becomes relatively rough, it might even be possible to apparent observation
To the large-size crystals for being deposited on film surface, one layer of fine and close ZIF-8 film can be clearly seen that by the illustration for scheming S8b.
Embodiment 4
Oxygen auxiliary law deposits ZIF-8 on FTO, includes the following steps：
（1）Prepare ZnCl containing 10mM2With the methanol solution of 20mM HmiM, separately match portion ZnCl containing 10mM2、20mM HmiM
With 100mM (NBu4)PF6Methanol solution；
（2）Utilize cyclic voltammetry（Three-electrode system）, carry out electrochemical deposition to obtain the final product on cathode conductive substrates surface, wherein,
To electrode be Pt, reference electrode be Ag/AgCl electrodes, working electrode 10*15mm2FTO, in the voltage range of -1 ~ 0V
Lower deposition 2h.
The processing method of FTO is identical with the processing method of the ITO in embodiment 2.
Compare the deposition results participated in and without supporting electrolyte, the reaction precursor liquid phase of electroless matter (Fig. 7 b) for
Containing electrolyte（Fig. 7 a）Reaction precursor liquid electric conductivity reduce, also reduce the electrochemical reaction speed of reducing molecular oxygen, cause
The ZIF-8 membrane-coating granules sizes of preparation add (NBu than before4)PF6The film layer crystal grain of preparation is bigger（Such as Fig. 8）.XRD diagram（Fig. 9）Table
The equal metal phases of ZIF-8 and other miscellaneous generations that bright electroless matter and having deposits under the conditions of two kinds of electrolyte.
Embodiment 5
Oxygen auxiliary cathode deposits ZIF-71, includes the following steps：
（1）Prepare the ZnCl containing 10mM2With the methanol solution of 4, the 5- dichloro-imidazoles (dclM) of 20mM, high-purity sky is led to before deposition
Gas 30min；
（2）Utilize constant voltage method（Two electrode systems）, carry out electrochemical deposition to obtain the final product on cathode conductive substrates surface, wherein, work
Make electrode and be 10*15mm to electrode2FTO, deposit 6h under the voltage of -2V.
The processing method of FTO is same as Example 4.
It can obtain fine and close ZIF-71 film layers（Figure 10）, XRD show in deposition process without metal Zn generate（Figure 11）, and
ZIF-71 prepared by this method has consistent XRD diffraction maximums with the ZIF-71 of theoretical modeling.
Embodiment 6
Oxygen auxiliary cathode deposits ZIF-67, includes the following steps：
（1）Prepare CoCl containing 10mM2With the methanol solution of 30mM HmiM, high pure air 30min is led to before deposition；
（2）Utilize constant voltage method（Two electrode systems）, carry out electrochemical deposition to obtain the final product on cathode conductive substrates surface, wherein, work
Make electrode and be 10*15mm to electrode2FTO, deposit 3h under -1.5V voltages.
The processing method of FTO is same as Example 4.
Although Co (II) has the reduction potential of corrigendum than Zn (II), before two electrode systems, the reaction of electroless matter
It drives in liquid, fine and close ZIF-67 (Co (miM) is deposited on FTO2) film（Figure 12）.Shown in Figure 13, XRD shows to deposit
It is generated in the process without metal Co, and ZIF-67 prepared by this method has identical diffraction maximum with the XRD of ZIF-67 simulated.
Embodiment 7
Oxygen auxiliary cathode deposits large-sized ZIF-8/ZIF-67 hydridization film layer, includes the following steps：
（1）Prepare precursor liquid-ZnCl containing 10mM of ZIF-82With the methanol solution of 20mM HmiM and the forerunner of ZIF-67
Liquid-CoCl containing 10mM2With the methanol solution of 30mM HmiM；
（2）Utilize cyclic voltammetry（Three-electrode system）, carry out electrochemical deposition to obtain the final product on cathode conductive substrates surface, wherein,
Working electrode is 50*90mm2ITO, be Pt to electrode, reference electrode is Ag/AgCl electrodes, deposits ZIF-8 first, with following
The sweep speed of ring voltammetry -0.8-0V, 100mV/s deposit 2h, obtain the ZIF-8 films of 100nm or so（Figure 14 b）, no water beetle
Alcohol is rinsed well, N2Drying, is subsequently placed in the precursor liquid of ZIF-67, cyclic voltammetry, under -0.8V voltages, 100mV/s's
Sweep speed deposits 2h.
The processing method of ITO is the same as embodiment 2.
The processing method of Pt and Ag/AgCl electrodes is the same as embodiment 1.
It deposited the ZIF-67 of about 200nm thickness in the ZIF-8 film layers of about 100nm, obtained ZIF-8/ZIF-67 hydridization
Film layer（Figure 14 a, c）.Figure 14 d are the TEM figures of the fragment of the hydridization film layer, and Figure 14 e EDX figures suggest the formation of Zn-/Co-MOF
Hydridization film layer.
Claims (10)
- A kind of 1. method of oxygen auxiliary cathode deposited metal organic framework material, it is characterised in that：Include the following steps：（1）Prepare reaction precursor liquid solution, the precursor solution by 5 ~ 50mM source metal, the organic ligand of 10 ~ 250mM and Organic solvent forms；（2）Using constant voltage method or cyclic voltammetry, electrochemical deposition is carried out on cathode conductive substrates surface to obtain the final product.
- 2. a kind of method of oxygen auxiliary cathode deposited metal organic framework material according to claim 1, feature exist In：The source metal includes Zn (II), Co (II), Cd (II), Cu (II), Zr (IV), Mn (II), Ni (II), Fe (II) or Fe (III), specifically the compound using Zn (II) as source metal as anhydrous ZnCl2, using Co (II) as the compound of source metal For anhydrous CoCl2。
- 3. a kind of method of oxygen auxiliary cathode deposited metal organic framework material according to claim 1 or 2, feature exist In：The step（1）Later, 30min high pure airs or oxygen are passed through into precursor solution.
- 4. a kind of method of oxygen auxiliary cathode deposited metal organic framework material according to claim 1, it is characterised in that： The organic ligand includes 2-methylimidazole, 4,5- dichloro-imidazoles and imidazole derivative containing difunctional, benzoic acid, to benzene Dioctyl phthalate or trimesic acid and its derivative.
- 5. a kind of method of oxygen auxiliary cathode deposited metal organic framework material according to claim 1, it is characterised in that： The organic solvent includes methanol, ethyl alcohol, N,N-dimethylformamide or acetonitrile.
- 6. a kind of method of oxygen auxiliary cathode deposited metal organic framework material according to claim 1, it is characterised in that： The conductive substrates include indium tin oxide target, fluorine doped tin oxide, carbon fiber, highly oriented pyrolytic graphite, nickel, copper, gold, platinum electricity Pole.
- 7. a kind of method of oxygen auxiliary cathode deposited metal organic framework material according to claim 1, feature exist In：The voltage of the constant voltage method is 0V ~ -2.5V, and the time is 2min ~ for 24 hours.
- 8. a kind of method of oxygen auxiliary cathode deposited metal organic framework material according to claim 1, feature exist In：In the cyclic voltammetry voltage range be -2.5V ~ 0V, sweep speed 100mV/s, sedimentation time for 10min ~ 24h。
- 9. a kind of method of oxygen auxiliary cathode deposited metal organic framework material according to claim 1, feature exist In：The step（2）Middle depositing temperature is 20 ~ 120 DEG C.
- 10. the metal-organic framework materials prepared by method described in claim 1-9.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130026029A1 (en) * | 2010-04-08 | 2013-01-31 | Sam Kayaert | Photo-electrochemical cell |
| CN103820850A (en) * | 2014-02-27 | 2014-05-28 | 河南理工大学 | Preparation method of metal organic framework MOF-2 polycrystalline film |
| CN104801341A (en) * | 2015-04-07 | 2015-07-29 | 大连理工大学 | Method for electrochemical synthesis of Cu3 (BTC) 2 as catalyst and NH3-SCR application of Cu3 (BTC) 2 |
| CN105226085A (en) * | 2015-08-26 | 2016-01-06 | 中国科学院福建物质结构研究所 | A kind of MOF thin-film material and preparation and application thereof with high dielectric property |
| CN105369306A (en) * | 2015-11-24 | 2016-03-02 | 北京理工大学 | Method for preparing electrocatalytic water-splitting oxygen production electrode |
| CN106622381A (en) * | 2017-01-05 | 2017-05-10 | 福州大学化肥催化剂国家工程研究中心 | Novel preparation method of Fe-MOF (ferrous-metal oxide framework) catalyst and application thereof in desulfurizing field |
| CN106669432A (en) * | 2016-12-20 | 2017-05-17 | 华南理工大学 | Method for preparing metal organic framework membrane by utilizing stainless steel mesh modified by electro-deposition method |
| CN107151331A (en) * | 2017-06-05 | 2017-09-12 | 北京化工大学 | A kind of method of the quick preparation structure controllable metal organic framework compounds of electrochemical method |
-
2018
- 2018-01-03 CN CN201810003797.9A patent/CN108130574A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130026029A1 (en) * | 2010-04-08 | 2013-01-31 | Sam Kayaert | Photo-electrochemical cell |
| CN103820850A (en) * | 2014-02-27 | 2014-05-28 | 河南理工大学 | Preparation method of metal organic framework MOF-2 polycrystalline film |
| CN104801341A (en) * | 2015-04-07 | 2015-07-29 | 大连理工大学 | Method for electrochemical synthesis of Cu3 (BTC) 2 as catalyst and NH3-SCR application of Cu3 (BTC) 2 |
| CN105226085A (en) * | 2015-08-26 | 2016-01-06 | 中国科学院福建物质结构研究所 | A kind of MOF thin-film material and preparation and application thereof with high dielectric property |
| CN105369306A (en) * | 2015-11-24 | 2016-03-02 | 北京理工大学 | Method for preparing electrocatalytic water-splitting oxygen production electrode |
| CN106669432A (en) * | 2016-12-20 | 2017-05-17 | 华南理工大学 | Method for preparing metal organic framework membrane by utilizing stainless steel mesh modified by electro-deposition method |
| CN106622381A (en) * | 2017-01-05 | 2017-05-10 | 福州大学化肥催化剂国家工程研究中心 | Novel preparation method of Fe-MOF (ferrous-metal oxide framework) catalyst and application thereof in desulfurizing field |
| CN107151331A (en) * | 2017-06-05 | 2017-09-12 | 北京化工大学 | A kind of method of the quick preparation structure controllable metal organic framework compounds of electrochemical method |
Non-Patent Citations (2)
| Title |
|---|
| ADINA MOROZAN 等: "Metal organic frameworks for electrochemical applications", 《ENERGY ENVIRON. SCI.》 * |
| 李莹 等: "MOFs膜的制备方法及其应用研究", 《现代化工》 * |
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