CN105731609B - A kind of porous carbon electrodes based on metal-organic framework materials and preparation method thereof - Google Patents
A kind of porous carbon electrodes based on metal-organic framework materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of novel porous carbon electrode based on metal-organic framework materials and preparation method thereof, belong to field of water treatment technology application.Described porous carbon electrodes are that high-temperature calcination under metal-organic framework materials vacuum state first is obtained into porous carbon, and then porous carbon is well mixed with binding agent, is laid on graphite paper, is dried, finally binding agent is carbonized and is made.Compared with common active carbon electrode, the porous carbon electrodes specific surface area obtained is big, good hydrophilic property, and desalination rate is high during capacitive deionization, and regenerability is excellent, is a kind of promising electrode suitable for capacitive deionization technology.
Description
Technical field
The present invention relates to a kind of novel porous carbon electrode based on metal-organic framework materials and preparation method thereof, the electrode
It is mainly used in capacitive deionization desalting process, belongs to the application field of water technology, particularly belongs to salt water desalting technology field.
Background technology
While economy constantly grows continuously and fast, China is faced with the situation of freshwater resources critical shortage.In order to full
The sufficient demand to pure water, people start to carry out desalt processing to salt water.Traditional desalination method master available for desalination
There are distillation, ion exchange, electrodialysis, counter-infiltration etc..But the shortcomings that these traditional methods have its each, distillation need to grow
Time heats, high energy consumption；A large amount of strong acid and highly basic are needed during ion exchange resin regeneration, easily produce secondary pollution；Electrodialysis
Expensive with the permeable membrane of counter-infiltration, cost is high.
Electro Sorb technology（EST, Electro-Sorption Technology）, also known as capacitive deionization（CDI,
Capacitive Deionization）, be utilize charged electrode surface adsorption water in carry opposite charges ion, and by its
It is strapped in the electric double layer of electrode surface formation, so as to realize a kind of new water technology of Water warfare/desalination.When electrode is inhaled
It is attached reach saturation after, removing extra electric field or will be released to electrode reversal connection, the ion of absorption in solution, and electrode obtains again
Raw, the electrode after regeneration can be put back into.Any chemical agent is not required to during CDI, the discharged strong brine of regeneration comes
From raw water, system does not produce new emission in itself, avoids secondary pollution problem.Therefore, should compared with traditional desalination technology
Technology not only eliminates concentrated acid, the transport of concentrated base, storage and operational trouble, and energy consumption is low, and investment is small, without secondary dirt
Dye, it is a kind of both economic, and effective desalination technology.
Electrode material is the most important factor for influenceing CDI desalination effects, it is necessary to possesses sufficiently large surface area and good
Electric conductivity, therefore electrode material is often the carbon material with high-specific surface area used by CDI, as activated carbon, activated carbon are fine
Dimension, CNT, carbon aerogels etc..But metal-organic framework materials carbonization is prepared into porous carbon, there is no as CDI electrode materials
Document report.
Metal organic framework（Metal Organic Frameworks）Material has inorganic and organic functional material comprehensive
Characteristic is closed, novel porous carbon material can be obtained after calcining, it is notable to have that specific surface area is big, resistance is low, preparation technology is simple etc.
Advantage, it can be used as excellent CDI electrode materials.Therefore, the present invention is prepared for being based on novel metal organic framework material
MOF-66, and metal-organic framework materials MOF-5, ZIF-8 porous carbon, and shaping porous carbon electrodes are prepared into respectively, study
Such electrode capacitance deionization desalination performance.
The content of the invention
It is an object of the invention to provide a kind of porous carbon electrodes based on metal-organic framework materials and preparation method thereof,
And this novel porous carbon electrode is applied to capacitive deionization desalination field, compare table using porous carbon electrodes made from the material
Area is big, good hydrophilic property, and desalination rate is high during capacitive deionization, and regenerability is excellent.
The purpose of the present invention can be achieved through the following technical solutions：The porous carbon electrodes are that synthesis uses the organic bone of metal
High-temperature calcination obtains porous carbon to frame material under vacuum conditions, then porous carbon is mixed with binding agent, is laid on graphite paper, does
It is dry, finally binding agent is carbonized, is prepared into porous carbon electrodes.
Described metal-organic framework materials are new MOF materials [Cd (OTADDB) C2H5OH·2DMF·H2O]n
(OTADDB=3,3′-[(6-oxbydrl-1,3,5-triazine-2,4-diyl)diimino]dibenzoic acid)（This is specially
The sharp new MOF materials are referred to as MOF-66）.
This method comprises the following steps：
（1）, new MOF materials MOF-66 preparation：1. 1.08g 5- amino isophthalic acids are added to 20mL pure water
In, magnetic agitation is to being completely dissolved, then 0.36g NaOH and 0.552g NaHCO are slowly added into solution3, continue magnetic force and stir
Mix to NaOH and NaHCO3It is completely dissolved acquisition solution A；2. 0.6g Cyanuric Chlorides are added in 5.0mL Isosorbide-5-Nitraes-dioxane,
Magnetic agitation is to being completely dissolved acquisition solution B；3. at ambient temperature, solution B is added dropwise in solution A, magnetic agitation
12h, the pH value for adjusting solution with the HCl that mass concentration is 20% filter to 3, obtain ligand L；4. by 0.024g Cd（NO3）2With
0.018g ligand Ls are added in 4mL DMFs, and 1mL 2mol/L HNO is added dropwise3, dissolve and shake up, will be upper
State solution to be placed in vial, seal, be placed in baking oven at 85 DEG C and react 3 days, taken out after naturally cooling to room temperature, filter, obtain
Pale yellow crystals are obtained, then washed with DMF, filter the pale yellow crystals, repeatedly twice, will be light yellow after filter
Crystal is put into baking oven, and 1h is dried at 50 DEG C, obtains new MOF materials MOF-66.
（2）, using new MOF materials MOF-66 prepare porous carbon：
Will（1）In obtained new MOF materials MOF-66 be placed in vacuum Muffle furnace, under vacuum state, in 900 DEG C calcining
2h, taken out after naturally cooling to room temperature, obtain the porous carbon based on new MOF materials MOF-66.
（3）, binding agent prepare：
It is respectively 2.0% acrylic acid, 0.3% methyl acrylate and 0.0125% azodiisobutyronitrile by mass concentration
The aqueous solution be well mixed, be placed in 60 DEG C of thermostat water bath, under 150r/min rotating speeds constant temperature mechanical agitation 4h obtain just colloid,
First colloid is taken out from thermostat water bath, naturally cools to room temperature, the tetraethylene glycol that mass concentration is 0.7% is added, uses glass
Rod stirs, and obtains binding agent.
（4）, prepare porous carbon electrodes：
By step（2）The porous carbon and step based on new MOF materials MOF-66 of middle preparation（3）The binding agent of middle preparation
In mass ratio 5:5 mixing, stir, take 1.0g mixtures to be laid on 5cm × 3cm graphite paper, put in an oven in 120
10-30min is dried at DEG C, then is placed in vacuum Muffle furnace vacuum calcining 1-3h at 650-900 DEG C, is taken after naturally cooling to room temperature
Go out, obtain the porous carbon electrodes based on new MOF materials MOF-66.
It is described a kind of to be gone based on the porous carbon electrodes of metal-organic framework materials carrying out desalt processing electric capacity to salt water
Application in terms of ion desalination, it is specific as follows：
20mL 500mg/L NaCl solution is taken to be placed in capacitive deionization container, by step（4）In it is obtained more than two
Hole carbon electrode is close to container wall and is placed on face-to-face in capacitive deionization container, and spacing is 1.5 cm between two electrodes, uses wire
Electrode is connected with D.C. regulated power supply, applies 1.2V voltages, the electrical conductivity of a solution is surveyed every 10min, until electrical conductivity
Be worth it is constant untill, now electrode reaches saturation state.By electrode regeneration after saturation, i.e., by electrode reversal connection 10min, then power off
20min, so complete a capacitive deionization/regeneration cycle.Solution is changed to the NaCl solution that concentration is 500mg/L again,
Repeat the above steps and carry out next circulation.
The new MOF materials MOF-66 of high-temperature calcination prepares carbon material to the present invention under vacuum conditions, has using the carbon material
There is the characteristics of 3 D stereo loose structure and big specific surface area, novel capacitor deionization electrode prepared as electrode material,
Show good capacitive deionization performance.Compared with traditional activated carbon electrode, advantages of the present invention and effect are：
1st, the porous carbon based on new MOF materials MOF-66 prepared by the present invention has three-dimensional porous structure, compares surface
Product is big, up to 1850m2/g。
2nd, the porous carbon electrodes based on new MOF materials MOF-66 prepared by the present invention, which have, is substantially better than activated carbon electricity
The hydrophily of pole, be advantageous to solution and quickly reach electrode interior, improve capacitive deionization speed.
3rd, the porous carbon electrodes based on new MOF materials MOF-66 prepared by the present invention, are removed during capacitive deionization
Salt rate can reach 61.8%, be 2.30 times of active carbon electrode（The desalination rate of active carbon electrode is only 26.9%）, and 20 circulations
The capacitive deionization desalination rate of electrode is not decreased obviously afterwards, has good reproducibility.
Brief description of the drawings
Fig. 1 is the stereoscan photograph figure of activated carbon and porous carbon [in figure：（a）Activated carbon；（b）Based on new MOF materials
MOF-66 porous carbon；（c）Porous carbon based on MOF-5；（d）Porous carbon based on ZIF-8].
Fig. 2 is the hydrophilic angle photo figure of active carbon electrode and porous carbon electrodes [in figure：（a）Active carbon electrode；（b）It is based on
New MOF materials MOF-66 porous carbon electrodes；（c）Porous carbon electrodes based on MOF-5；（d）Porous carbon electricity based on ZIF-8
Pole].
Fig. 3 is electrical conductivity of solution change curve during active carbon electrode and porous carbon electrodes capacitive deionization.
Fig. 4 is new MOF materials MOF-66 in [100] direction（a）[010] direction（b）Pore passage structure.
Embodiment
First, the preparation of active carbon electrode：
For the ease of the comparison of product of the present invention, we are prepared for active carbon electrode, and specific preparation method is as follows：
（1）, activated carbon is washed with deionized repeatedly, is filtered, until electrical conductivity is less than 10us/cm, be placed in baking oven
1h is dried at 100 DEG C, clean activated carbon is obtained, such as accompanying drawing 1（a）.
（2）, by mass concentration be respectively that 2.0% acrylic acid, 0.3% methyl acrylate and 0.0125% azo two are different
The aqueous solution of butyronitrile is well mixed, and is placed in 60 DEG C of thermostat water bath, and constant temperature mechanical agitation 4h is obtained just under 150r/min rotating speeds
Colloid, first colloid is taken out from thermostat water bath, naturally cools to room temperature, add the tetraethylene glycol that mass concentration is 0.7%,
Stirred with glass bar, obtain binding agent.
（3）, by step（1）The clean activated carbon and step of middle acquisition（2）The binding agent of middle preparation is using mass ratio as 5:5
Mixing, stirs, takes 1.0g mixtures to be laid on 5cm × 3cm graphite paper, puts and is dried in an oven at 120 DEG C
20min, then vacuum calcining 2h at 850 DEG C is placed in vacuum Muffle furnace, taken out after naturally cooling to room temperature, obtain activated carbon electricity
Pole.
Utilize the hydrophily of contact angle instrument measure active carbon electrode：Because the hydrophily of electrode prepared by the present invention is special
Not good, when dropwise addition thing is water, water droplet is encountered electrode surface and absorbed immediately, can not capture water droplet at the hydrophilic angle of electrode surface
Photo, so thing, which is added dropwise, is changed to glycerine, its hydrophilic angle photo, such as accompanying drawing 2（a）, hydrophilic angle is 100 °.
Capacitive deionization desalination is carried out using this electrode：20mL 500mg/L NaCl solution is taken to be placed in capacitive deionization appearance
In device, two active carbon electrodes are close to container wall and are placed on face-to-face in capacitive deionization container, the spacing of two electrodes is
1.5cm, electrode is connected with D.C. regulated power supply with wire, applies 1.2V voltages, the conductance of a solution is surveyed every 10min
Rate, the conductivity variations of solution are as shown in curve 1 in Fig. 3, and desalination rate reaches 26.9% after 180min.Electrode after 20 circulations
Desalination rate still can reach 25.7%.
2nd, the preparation of porous carbon electrodes of the present invention：
The preparation method of porous carbon electrodes based on new MOF materials MOF-66.Described method specifically includes following step
Suddenly：
（1）First 1.08g 5- amino isophthalic acids are added in 20mL pure water, magnetic agitation to being completely dissolved, then to
0.36g NaOH and 0.552g NaHCO are slowly added in solution3, continue magnetic agitation to NaOH and NaHCO3It is completely dissolved acquisition
Solution A.Then 0.6g Cyanuric Chlorides are added to 5.0mL Isosorbide-5-Nitraes-dioxane, magnetic agitation is to being completely dissolved acquisition solution B.
Again at ambient temperature, solution B is added dropwise in solution A, magnetic agitation 12h, adjusted with the HCl that mass concentration is 20%
The pH value of solution filters to 3, obtains ligand L.Take 0.024g Cd（NO3）24mL N, N- diformazans are added to 0.018g ligand Ls
In base formamide, the mol/L HNO of 1 mL 2 are added dropwise3, dissolve and shake up, above-mentioned solution is placed in vial, seal, be placed in
React 3 days at 85 DEG C in baking oven, taken out after naturally cooling to room temperature, filter, obtain pale yellow crystals, then with N, N- dimethyl methyls
Acid amides washing, the pale yellow crystals are filtered, repeatedly twice, pale yellow crystals after filter are put into baking oven, 1h is dried at 50 DEG C, is obtained
To new MOF materials MOF-66, the crystal belongs to tetragonal crystal system,I4 (1) md space groups, cell parameter a=22.1003 (5),
b = 22.1003(5) Å, c = 31.9370(15) Å, α = β = γ = 90º, V = 15598.8(9) Å3, Z =
8, there is tridimensional network, penetrating pore passage structure is shown on [100] direction and [010] direction, as shown in figure 4, duct
Size is 8 × 102。
（2）By step（1）In obtained new MOF materials MOF-66 be placed in vacuum Muffle furnace, under vacuum state, in
900 DEG C of h of high-temperature calcination 2, take out after naturally cooling to room temperature, obtain the porous carbon based on new MOF materials MOF-66, such as attached
Fig. 1（b）.
（3）, by mass concentration be respectively that 2.0% acrylic acid, 0.3% methyl acrylate and 0.0125% azo two are different
The aqueous solution of butyronitrile is well mixed, and is placed in 60 DEG C of thermostat water bath, and constant temperature mechanical agitation 4h is obtained just under 150r/min rotating speeds
Colloid, first colloid is taken out from thermostat water bath, naturally cools to room temperature, add the tetraethylene glycol that mass concentration is 0.7%,
Stirred with glass bar, obtain binding agent.
（4）Step（2）The porous carbon and step based on new MOF materials MOF-66 of middle preparation（3）The bonding of middle preparation
Agent is using mass ratio as 5:5 mixing, stir, take 1.0g mixtures to be laid on 5cm × 3cm graphite paper, put in an oven
20min is dried at 120 DEG C, then is placed in vacuum Muffle furnace vacuum calcining 2h at 850 DEG C, is taken out after naturally cooling to room temperature,
Obtain the porous carbon electrodes based on new MOF materials MOF-66.
Utilize the hydrophily of contact angle instrument measure active carbon electrode：Because the hydrophily of electrode prepared by the present invention is special
Not good, when dropwise addition thing is water, water droplet is encountered electrode surface and absorbed immediately, can not capture water droplet at the hydrophilic angle of electrode surface
Photo, so thing, which is added dropwise, is changed to glycerine, the hydrophilic angle photo of the prepared porous carbon electrodes based on new MOF materials MOF-66
Such as Fig. 2（b）, as seen from the figure, although replacing water droplet with glycerine, due to the perfect hydrophily of electrode, hydrophilic angle is not captured yet
Photo.It can be seen that the hydrophily of the porous carbon electrodes based on new MOF materials MOF-66 will be far superior to active carbon electrode.
Capacitive deionization desalination is carried out using this electrode：20mL 500mg/L NaCl solutions are taken to be placed in capacitive deionization appearance
In device, two porous carbon electrodes are close to container wall and are placed on face-to-face in capacitive deionization container, the spacing of two electrodes is
1.5cm, electrode is connected with D.C. regulated power supply with wire, applies 1.2V voltages, the conductance of a solution is surveyed every 10min
Rate, the conductivity variations of solution are as shown in curve 2 in Fig. 3, and desalination rate reaches 61.8% after 180min, are active carbon electrodes
2.30 times, the desalination rate of electrode still can reach 61.3% after 20 circulations
3rd, desalt processing capacitive deionization desalination is being carried out to salt water based on the porous carbon electrodes of metal-organic framework materials
The application example of aspect：
1st, the preparation method of the porous carbon electrodes based on metal-organic framework materials MOF-5.Described method specifically includes
Following steps：
（1）, first by 2.97g Zn（NO3）2·6H2O and 2.49g terephthalic acid (TPA)s are added to 60mL N,N-dimethylformamides
In, magnetic agitation is to being completely dissolved.Solution is placed in vial again, is sealed, is placed in baking oven and reacts 18h at 85 DEG C, it is natural
Take out, filter after being cooled to room temperature, obtain white crystal, then rinsed with DMF, filter the white crystal, instead
It is multiple that finally white crystal after filter is put into baking oven at 50 DEG C and dries 1h twice, acquisition metal-organic framework materials MOF-5.
（2）, metal-organic framework materials MOF-5 is placed in vacuum Muffle furnace, under vacuum state, forged in 850 DEG C of high temperature
2h is burnt, is taken out after naturally cooling to room temperature, obtains the porous carbon based on metal-organic framework materials MOF-5, such as accompanying drawing 1（c）.
（3）, by mass concentration be respectively that 2.0% acrylic acid, 0.3% methyl acrylate and 0.0125% azo two are different
The aqueous solution of butyronitrile is well mixed, and is placed in 60 DEG C of thermostat water bath, and constant temperature mechanical agitation 4h is obtained just under 150r/min rotating speeds
Colloid, first colloid is taken out from thermostat water bath, naturally cools to room temperature, add the tetraethylene glycol that mass concentration is 0.7%,
Stirred with glass bar, obtain binding agent.
（4）, by step（2）The porous carbon and step based on metal-organic framework materials MOF-5 of middle preparation（3）Middle preparation
Binding agent using mass ratio as 5:5 mixing, stir, take 1.0g mixtures to be laid on 5cm × 3cm graphite paper, be placed on
20min is dried in baking oven at 120 DEG C, then is placed in vacuum Muffle furnace, 2h, natural cooling are calcined in 900 DEG C under vacuum state
Taken out after to room temperature, obtain the porous carbon electrodes based on metal-organic framework materials MOF-5.
Utilize the hydrophily of contact angle instrument measure active carbon electrode：Because the hydrophily of electrode prepared by the present invention is special
Not good, when dropwise addition thing is water, water droplet is encountered electrode surface and absorbed immediately, can not capture water droplet at the hydrophilic angle of electrode surface
Photo, so thing, which is added dropwise, is changed to glycerine, the hydrophilic angle of the prepared porous carbon electrodes based on metal-organic framework materials MOF-5
Photo such as Fig. 2（c）, hydrophilic angle is 18 °, and its hydrophily is substantially better than active carbon electrode.
Capacitive deionization desalination is carried out using this electrode：20mL 500mg/L NaCl solution is taken to be placed in capacitive deionization appearance
In device, two porous carbon electrodes are close to container wall and are placed on face-to-face in capacitive deionization container, the spacing of two electrodes is
1.5cm, electrode is connected with D.C. regulated power supply with wire, applies 1.2V voltages, the conductance of a solution is surveyed every 10min
Rate, the conductivity variations of solution are as shown in curve 3 in Fig. 3, and desalination rate reaches 46.9% after 180min, are active carbon electrodes
1.74 times, the desalination rate of electrode still can reach 46.2% after 20 circulations
2nd, the preparation method of the porous carbon electrodes based on metal-organic framework materials ZIF-8.Described method specifically includes
Following steps：
（1）, first by 2.97g Zn（NO3）2·6H2O is added in 200mL methanol, and magnetic agitation is prepared to being completely dissolved
Into solution C.3.28g 2-methylimidazoles are added in 200mL methanol again, magnetic agitation is configured to solution D to being completely dissolved.
Then solution C is slowly dropped in solution D, magnetic agitation 2h under room temperature condition, obtains white suspension, by white suspension
Be placed in a centrifuge, centrifuge 10min under 12000 revs/min of rotating speeds, obtain white crystal, then rinsed repeatedly with absolute ethyl alcohol, from
The heart white crystal, white crystal after centrifugation is put into baking oven at 50 DEG C and dries 1h, obtain metal-organic framework materials ZIF-
8。
（2）, metal-organic framework materials ZIF-8 is placed in vacuum Muffle furnace, under vacuum state, 2 are calcined in 900 DEG C
H, taken out after naturally cooling to room temperature, obtain the porous carbon based on metal-organic framework materials ZIF-8, such as accompanying drawing 1（d）.
（3）, by mass concentration be respectively that 2.0% acrylic acid, 0.3% methyl acrylate and 0.0125% azo two are different
The aqueous solution of butyronitrile is well mixed, and is placed in 60 DEG C of thermostat water bath, and constant temperature mechanical agitation 4h is obtained just under 150r/min rotating speeds
Colloid, first colloid is taken out from thermostat water bath, naturally cools to room temperature, add the tetraethylene glycol that mass concentration is 0.7%,
Stirred with glass bar, obtain binding agent.
（4）, by step（2）The porous carbon and step based on metal-organic framework materials ZIF-8 of middle preparation（3）Middle preparation
Binding agent using mass ratio as 5:5 mixing, stir, take 1.0g mixtures to be laid on 5cm × 3cm graphite paper, be placed on
20min is dried in baking oven at 120 DEG C, then is placed in vacuum Muffle furnace, 2h, natural cooling are calcined in 850 DEG C under vacuum state
Taken out after to room temperature, obtain the porous carbon electrodes based on metal-organic framework materials ZIF-8.
Utilize the hydrophily of contact angle instrument measure active carbon electrode：Because the hydrophily of electrode prepared by the present invention is special
Not good, when dropwise addition thing is water, water droplet is encountered electrode surface and absorbed immediately, can not capture water droplet at the hydrophilic angle of electrode surface
Photo, so thing, which is added dropwise, is changed to glycerine, prepared hydrophilic angle photo such as Fig. 2 based on metal-organic framework materials ZIF-8
（d）, hydrophilic angle is 22 °, and its hydrophily is substantially better than active carbon electrode.
Capacitive deionization desalination is carried out using this electrode：20mL 500mg/L NaCl solutions are taken to be placed in capacitive deionization appearance
In device, two porous carbon electrodes are close to container wall and are placed on face-to-face in capacitive deionization container, the spacing of two electrodes is
1.5cm, electrode is connected with D.C. regulated power supply with wire, applies 1.2V voltages, the conductance of a solution is surveyed every 10min
Rate, the conductivity variations of solution are as shown in curve 4 in Fig. 3, and desalination rate reaches 56.7% after 180min, are active carbon electrodes
2.11 times, the desalination rate of electrode still can reach 55.9% after 20 circulations.
Claims (3)
- A kind of 1. porous carbon electrodes based on metal-organic framework materials, it is characterised in that：The porous carbon electrodes are to use metal High-temperature calcination obtains porous carbon to organic framework material under vacuum conditions, then porous carbon is mixed with binding agent, is laid in graphite On paper, dry, finally binding agent is carbonized, is prepared into porous carbon electrodes；Described metal-organic framework materials are new MOF materials Expect [Cd (OTADDB) C2H5OH·2DMF·H2O]n,OTADDB=3,3 '-[(6-oxbydrl-1,3,5-triazine-2,4-diyl) diimino] dibenzoic in formula Acid), material designation MOF-66.
- A kind of 2. preparation method of the porous carbon electrodes based on metal-organic framework materials, it is characterised in that：This method include with Lower step：(1), new MOF materials MOF-66 preparation：1. 1.08g 5- amino isophthalic acids are added in 20mL pure water, magnetic Power is stirred to being completely dissolved, then 0.36g NaOH and 0.552g NaHCO are slowly added into solution3, continue magnetic agitation extremely NaOH and NaHCO3It is completely dissolved acquisition solution A；2. 0.6g Cyanuric Chlorides are added in 5.0mL Isosorbide-5-Nitraes-dioxane, magnetic force Stirring is to being completely dissolved acquisition solution B；3. at ambient temperature, solution B is added dropwise in solution A, magnetic agitation 12h, use The HCl that mass concentration is 20% adjusts the pH value of solution to 3, filters, obtains ligand L；4. by 0.024g Cd (NO3)2With 0.018g ligand Ls are added in 4mL DMFs, and 1.0mL 2mol/L HNO is added dropwise3, dissolve and shake up, will Above-mentioned solution is placed in vial, sealing, is placed in baking oven at 85 DEG C and is reacted 3 days, taken out after naturally cooling to room temperature, is filtered, Pale yellow crystals are obtained, then washed with DMF, filter the pale yellow crystals, repeatedly twice, will be pale yellow after filter Color crystal is put into baking oven, and 1h is dried at 50 DEG C, obtains new MOF materials MOF-66；(2), porous carbon is prepared using new MOF materials MOF-66：Obtained new MOF materials MOF-66 in (1) is placed in vacuum Muffle furnace, under vacuum state, calcined at 900 DEG C 2h, taken out after naturally cooling to room temperature, obtain the porous carbon based on new MOF materials MOF-66；(3), prepared by binding agent：It is respectively 2.0% acrylic acid, 0.3% methyl acrylate and 0.0125% azodiisobutyronitrile by mass concentration The aqueous solution is well mixed, and is placed in 60 DEG C of thermostat water bath, and constant temperature mechanical agitation 4h obtains just colloid under 150r/min rotating speeds, will First colloid takes out from thermostat water bath, naturally cools to room temperature, adds the tetraethylene glycol that mass concentration is 0.7%, uses glass Rod stirs, and obtains binding agent；(4) porous carbon electrodes, are prepared：The porous carbon based on new MOF materials MOF-66 prepared in step (2) is pressed into matter with the binding agent prepared in step (3) Measure ratio 5:5 mixing, stir, take 1.0g mixtures to be laid on 5cm × 3cm graphite paper, put in an oven at 120 DEG C 10-30min is dried, then is placed in vacuum Muffle furnace vacuum calcining 1-3h at 650-900 DEG C, is taken out after naturally cooling to room temperature, Obtain the porous carbon electrodes based on new MOF materials MOF-66.
- 3. a kind of porous carbon electrodes based on metal-organic framework materials according to claim 1 are desalinated to salt water Handle the application in terms of capacitive deionization desalination.
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