CN110172709A - The preparation method and application of MOFs char-forming material electrochemical cathode based on metal ion and organic matter absorption - Google Patents
The preparation method and application of MOFs char-forming material electrochemical cathode based on metal ion and organic matter absorption Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of MOFs char-forming material electrochemical cathode based on metal ion and organic matter absorption, comprising the following steps: 1) carbonization of the MOFs of adsorption saturation；2) preparation of electrochemical cathode.The invention also discloses the electrochemical cathode and its applications.The electrochemical cathode can be used for electro-catalysis PMS, electrochemistry/O3Equal water treatment systems.The preparation method expands the utilization field of MOFs material, realize the secondary use of resource, it is abundant to have porous structure, transition metal oxide for material after carbonization, catalytic activity is excellent, the dioxygen outlet capacity in situ that generates is strong, the electrochemical cathode stable structure, and electro catalytic activity is high, continuous performance is excellent, fluoroquinolone antibiotic in energy efficient mineralization water.
Description
Technical field
The invention belongs to water process deep purifying fields, are related to a kind of MOFs carbon based on metal ion and organic matter absorption
Change the preparation method and application of material electrochemical cathode.
Background technique
In in recent years, preparing carbon-based material as precursor using MOFs becomes new hot topic.Contain in MOFs material
Organic ligand provides carbon source for carbonization, can also be carbonized in the case where no additional carbon as carbon-based material either carbon
Base-metal nano material, during heating in vacuum, old pore structure can change, and form new pore structure.If
It is to be heated under aerobic environment, then metal center can aoxidize, and obtain being that precursor-derived porous metals are aoxidized with MOFs
Object can derive porous mixed metal oxide in addition, heating to the MOFs material for having more than one metallic sites.
Fluoquinolone is the antibiotic of a kind of pair of resisting gram-positive bacteria and Gram-negative bacteria, is caused to the DNA of bacterium
Irreversible damage, replicates bacterium no longer, and due to its has a broad antifungal spectrum, cheap, side effect is light, is widely used in mankind doctor
The fields such as treatment, Animal Medicine are also used as growth accelerator in cultivation industry.Fluoquinolone mostly come from medical waste water,
Pharmacy waste water can will also be metabolized incomplete pharmaceutical intermediate and bring into if the excreta that livestock generates is not appropriately processed
In environment, if pharmaceutical intermediate maintains the active group of quinolone, pharmacological action will not disappear.Fluoquinolone can interfere micro-
Biological activity, traditional sludge water purification can not effectively be degraded, and the sewage for largely having fluoquinolone is caused to be discharged into water ring
Border, and long-term preservation in water, the fluoquinolone in water can apply directional selection pressure to the bacterium in water body, promote anti-medicine base
It is spread in the water body of cause, accelerates to cultivate infecting both domestic animals and human and the bacterium with drug resistance, in addition, fluoquinolone can be through animal ingestion
Into in food chain, concentration increases step by step in food chain, if the mankind eat this group food by mistake, the efficiency of body cell duplication be will receive
It influences, will be unable to be effective against fungus attack.In view of above-mentioned various reasons, it is necessary to design a kind of efficient, cleaning
Method degradation water in fluoquinolone.
Electrochemistry and ozone coupling technique are electrolysed the ozone in water, and it is free to generate the extremely strong hydroxyl of oxidability
Most organic pollutant can be degraded to inorganic matter by base, and electrochemistry/ozone system has a series of advantages, such as
Good degrading effect, energy consumption be small, it is clean, secondary pollution will not be generated etc..Have multiple studies have shown that the system can have
Effect handles medical waste water, and pre-processes to antibiotic, and pretreated intermediate product can be gone completely through sludge water purification workshop section
It removes.Electrode is electrochemistry/ozone system important component, and carbonization MOFs material has flourishing three dimensional pore structures, is obtained
To char-forming material be used to prepare electrode, this system can efficient degradation water pollutant, realize the thorough mine of Organic substance in water
Change, realizes the good control to water quality.
Summary of the invention
In order to solve the above technical problems in background technology, the present invention provides a kind of generation dioxygen water energys in situ
Power is strong, the electrochemical cathode stable structure, and electro catalytic activity is high, and continuous performance is excellent, fluorine quinoline promise in energy efficient mineralization water
The preparation method and application of the MOFs char-forming material electrochemical cathode based on metal ion and organic matter absorption of ketone antibiotic.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of the MOFs char-forming material electrochemical cathode based on metal ion and organic matter absorption, the side
Method the following steps are included:
1) the metal organic framework compound MOFs for being adsorbed with metal ion or organic matter centrifuge separation is placed on tubular type
In electric furnace, high-temperature roasting under inert gas protection is ground after cooling, obtains carbonization MOFs material；
2) carbonization MOFs material and rush that step 1) is prepared are led into agent, pore creating material and dehydrated alcohol or polyethylene glycol is mixed
Ultrasound after conjunction object is added after binder and stirs under water bath with thermostatic control to rubberlike mixture；Rubberlike mixture is wrapped up
In nickel foam, compression moulding after ethyl alcohol is added, is then roasted under conditions of inert gas shielding, then washed with 80-100 DEG C
It washs, the electrochemical cathode of carbonization MOFs material is obtained after natural air drying.
Preferably, step 1) metal ion of the present invention is copper ion, iron ion, manganese ion and cobalt ions
One of or a variety of combinations；The organic matter is POPs or PPCPs.
Preferably, used maturing temperature is 600-900 when high-temperature roasting in step 1) of the present invention
DEG C, electric tube furnace heating rate is 5-10 DEG C per minute, and the high-temperature roasting time is 1-3h；The inert gas is nitrogen or argon
Gas；Further included the steps that 300 mesh screens after the grinding.
Preferably, the mass ratio that rush of the present invention leads agent, pore creating material, binder and the MOFs material that is carbonized is
(10~20): (15~35): (250~450): 100.
Preferably, it is acetylene black that the step 2) rush of the present invention, which leads agent,；The pore creating material be sodium sulphate or/
And sodium bicarbonate；The binder is polytetrafluoroethylene (PTFE).
Preferably, the thickness of the electrochemical cathode of carbonization MOFs material of the present invention is 1-3mm；Be carbonized MOFs
Each side length of the electrochemical cathode of material is 1-5cm；H can be generated in situ per minute by being passed through in the case of oxygen2O2 5-10mg/L。
Preferably, the MOFs char-forming material electrochemistry yin of the present invention based on metal ion and organic matter absorption
The MOFs char-forming material electrochemical cathode based on metal ion and organic matter absorption that the preparation method of pole is prepared.
Preferably, the MOFs char-forming material electrochemistry yin of the present invention based on metal ion and organic matter absorption
Pole generates application when hydrogen peroxide in situ.
Preferably, the MOFs char-forming material electrochemistry yin of the present invention based on metal ion and organic matter absorption
Application of the pole in terms of electro-catalysis PMS (persulfate) degrades fluoroquinolone antibiotic.
Preferably, the MOFs char-forming material electrochemistry yin of the present invention based on metal ion and organic matter absorption
Application of the pole in terms of electrochemical couple ozone degradation fluoroquinolone antibiotic.
The beneficial effects of the present invention are:
The present invention provides a kind of systems of MOFs char-forming material electrochemical cathode based on metal ion and organic matter absorption
Preparation Method, the preparation method expand the utilization field of MOFs material, realize the secondary use of resource, material has more after carbonization
Pore structure, transition metal oxide are abundant, and catalytic activity is excellent, and the dioxygen outlet capacity in situ that generates is strong, the electrochemical cathode structure
Stablize, electro catalytic activity is high, and continuous performance is excellent, which can be used for electro-catalysis PMS, electrochemical couple ozone
Wait water treatment systems, fluoroquinolone antibiotic in energy efficient mineralization water, specifically, compared with prior art, of the invention is excellent
Point is:
1) carbonization treatment can be carried out to the MOFs material that absorption is complete or fails, realizes secondary use, expands it and answer
With field and range；The reusing of MOFs char-forming material electrochemical cathode 2) based on metal ion and organic matter absorption,
Stability, catalytic performance are all significantly improved, can the different types of emerging pollutant of efficient degradation, have a wide range of application, be discharged
Water quality is high；3) based on metal ion and organic matter adsorb complete MOFs char-forming material electrochemical cathode can by rush lead agent,
The composition proportion of pore creating material, binder and carbonization MOFs etc. optimize selection, can efficiently generate hydrogen peroxide in situ；4) it is carbonized
MOFs new pore structure and derivative porous metal oxide, can not only provide reaction compartment, can also provide for electron transmission logical
Road accelerates electron transport rate；5) electrochemical cathode can be applied simultaneously in the water process body such as PMS and electrochemical couple ozone
System.
Detailed description of the invention
Fig. 1 is the MOFs char-forming material transmission electron microscope picture of metal ion and organic matter absorption.
Fig. 2 is the MOFs char-forming material magnetic characterization figure of metal ion and organic matter absorption.
Fig. 3 is electrochemical couple ozone degradation fluoroquinolone antibiotic process ration situation.
Fig. 4 is the removal efficiency histogram of different fluoquinolones.
Fig. 5 is different POPs removal rate histograms.
Specific embodiment
Below by specific embodiment, the present invention is further described, it is noted that for the ordinary skill of this field
For personnel, without departing from the principle of the present invention, several variations and modifications can also be made, these also should be regarded as belonging to
Protection scope of the present invention.
Embodiment 1 is prepared based on the MOFs char-forming material electrochemical cathode of metal ion and organic matter absorption
The preparation of MOFs: weighing Fe(NO3)39H2O 14.43g using assay balance, be dissolved in the UP water of 36mL, and stirring is equal
After even, 5.04g trimesic acid is added, magneton, after being sealed with preservative film, magnetic agitation 1h is added.It will mixing after stirring
Liquid is transferred in autoclave, 120 DEG C of reaction 12h in baking oven.After reaction, the cooling reaction kettle in cold water, wait react
After kettle is cooling, the solidliquid mixture in liner is taken out completely, is transferred among clean beaker, ultrapure water cleaning, cup is added
Mouth is sealed with preservative film, and magnetic agitation 3h is centrifuged solution after stirring, gives up liquid portion, and what reservation centrifugation obtained consolidates
Solid is transferred in another clean beaker by body, and dehydrated alcohol is added and is cleaned, rim of a cup is sealed with preservative film, magnetic agitation
3h is centrifuged again after stirring, and the solid that dry centrifugation obtains is ground into uniform powder.
The carbonization of the MOFs of adsorption saturation: the above-mentioned MOFs of precise 1g is placed in 1L beaker, is added into round-bottomed flask
The copper nitrate and 100mg/L (initial concentration of substance before reacting) Tetracyclines of 100mg/L (initial concentration of substance before reacting)
Above-mentioned round-bottomed flask ultrasound is mixed 1h after absorption 2 days later and is centrifugated drying by antibiotic solution；It is placed in 750 in porcelain boat
DEG C with 5 DEG C of heatings, roasting 2h make material be carbonized under nitrogen protection, and it is stand-by to cross 300 mesh screens after grinding after cooling sufficiently.
Electrochemical cathode preparation: accurately weighing above-mentioned carbonization MOFs 0.6g, anhydrous sodium sulfate 0.9g, acetylene black 0.66g,
PTFE 0.777mL is pipetted using liquid-transfering gun, is mixed with 5mL dehydrated alcohol, hand operated mixing is allowed to uniformly, and ultrasonic 20min is by PTFE
It is diffused into system, then magnetic agitation 10min promotes mixing, heating and magnetic agitation 20min in magnetic force heated water bath pot steam
Ethyl alcohol out makes electrode material at rubber shape；Nickel foam is cut, electrode material is wrapped in foam nickel surface, and axis is pressed into piece, to the greatest extent
Amount not expose the edge of nickel foam.The electrode slice wrapped is suppressed with small-sized press, pressure 2t, suppresses 2min, after
It is sent into tube furnace, the lower 350 DEG C of firings 1h of nitrogen protection, 90 DEG C of water-bath 1h after cooling taking-up wash out the sodium sulphate in electrode.
Embodiment 2 is prepared based on the MOFs char-forming material electrochemical cathode of metal ion and organic matter absorption
The preparation of MOFs: by 1.428g COCl2·6H2After the mixing of O and 0.996g terephthalic acid (TPA), 210mL is added
DMF.Then it is respectively added slowly to 15mL second alcohol and water, magneton, after being sealed with preservative film, magnetic agitation 1h is added.After stirring
Mixed liquor is transferred in autoclave, 120 DEG C of reaction 12h in baking oven.After reaction, the cooling reaction kettle in cold water,
After reaction kettle cooling, the solidliquid mixture in liner is taken out completely, is transferred among clean beaker, it is clear that ultrapure water is added
It washes, rim of a cup is sealed with preservative film, and magnetic agitation 3h is centrifuged solution after stirring, gives up liquid portion, is retained centrifugation and is obtained
Solid, solid is transferred in another clean beaker, be added dehydrated alcohol cleaned, rim of a cup is sealed with preservative film, magnetic force
3h is stirred, is centrifuged again after stirring, the solid that dry centrifugation obtains is ground into uniform powder.
The carbonization of the MOFs of adsorption saturation: the above-mentioned MOFs of precise 1g is placed in 1L beaker, is added into round-bottomed flask
The cobalt nitrate and 150mg/L (initial concentration of substance before reacting) polycyclic aromatic hydrocarbon of 150mg/L (initial concentration of substance before reacting)
Above-mentioned round-bottomed flask ultrasound is mixed 1h after absorption 2 days later and is centrifugated drying by class POPs mixed solution；It is placed in porcelain boat
600 DEG C with 5 DEG C of heatings, roasting 1h makes material be carbonized under nitrogen protection, and it is stand-by to cross 300 mesh screens after grinding after cooling sufficiently.
Electrochemical cathode preparation: accurately weighing above-mentioned carbonization MOFs 0.6g, anhydrous sodium sulfate 0.9g, acetylene black 0.66g,
PTFE 0.777mL is pipetted using liquid-transfering gun, is mixed with 5mL dehydrated alcohol, hand operated mixing is allowed to uniformly, and ultrasonic 20min is by PTFE
It is diffused into system, then magnetic agitation 10min promotes mixing, heating and magnetic agitation 20min in magnetic force heated water bath pot steam
Ethyl alcohol out makes electrode material at rubber shape；Nickel foam is cut, electrode material is wrapped in foam nickel surface, and axis is pressed into piece, to the greatest extent
Amount not expose the edge of nickel foam.The electrode slice wrapped is suppressed with small-sized press, pressure 2t, suppresses 2min, after
It is sent into tube furnace, the lower 350 DEG C of firings 1h of nitrogen protection, 80 DEG C of water-bath 1h after cooling taking-up wash out the sodium sulphate in electrode.
Embodiment 3 is prepared based on the MOFs char-forming material electrochemical cathode of metal ion and organic matter absorption
The preparation of MOFs: 1.8g Al (NO3)3·9H2O is dissolved in the dimethylformamide DMF solution of 28mL, then plus
Enter 5.6mL formic acid, magneton, after being sealed with preservative film, magnetic agitation 1h is added.It is anti-that mixed liquor is transferred to high pressure after stirring 1h
It answers in kettle, 120 DEG C of reaction 12h in baking oven.After reaction, the cooling reaction kettle in cold water will be interior after reaction kettle cooling
Solidliquid mixture in lining takes out completely, is transferred among clean beaker, and ultrapure water cleaning is added, and rim of a cup is sealed with preservative film,
Magnetic agitation 3h, is centrifuged solution after stirring, gives up liquid portion, retains the solid that centrifugation obtains, solid is transferred to
In another clean beaker, dehydrated alcohol is added and is cleaned, rim of a cup is sealed with preservative film, magnetic agitation 3h, after stirring again
Secondary centrifugation, the solid that dry centrifugation obtains, is ground into uniform powder.
The carbonization of the MOFs of adsorption saturation: the above-mentioned MOFs of precise 1g is placed in 1L beaker, is added into round-bottomed flask
The manganese nitrate and 200mg/L (initial concentration of substance before reacting) sulfamido of 200mg/L (initial concentration of substance before reacting) is anti-
Above-mentioned round-bottomed flask ultrasound is mixed 1h after absorption 2 days later and is centrifugated drying by raw element mixed solution；It is placed in porcelain boat
900 DEG C with 10 DEG C of heatings, roasting 1h makes material be carbonized under nitrogen protection, and it is stand-by to cross 300 mesh screens after grinding after cooling sufficiently.
Electrochemical cathode preparation: above-mentioned carbonization MOFs 0.6g, anhydrous sodium sulfate 0.9g, acetylene black are accurately weighed
AB0.66g pipettes PTFE 0.777mL using liquid-transfering gun, mixes with 5mL dehydrated alcohol, and hand operated mixing is allowed to uniformly, ultrasound
PTFE is diffused into system by 20min, then magnetic agitation 10min promotes mixing, heating and magnetic force in magnetic force heated water bath pot
20min is stirred, ethyl alcohol is steamed, makes electrode material at rubber shape；Nickel foam is cut, electrode material is wrapped in foam nickel surface,
And axis is pressed into piece, the edge for exposing nickel foam of trying not.The electrode slice wrapped is suppressed with small-sized press, and pressure is
2t suppresses 2min, rear to be sent into tube furnace, the lower 350 DEG C of firings 1h of nitrogen protection, and 100 DEG C of water-bath 1h after cooling taking-up wash out electricity
Sodium sulphate in extremely.
Application Example 1
Embodiment 1 is efficiently produced in situ based on the MOFs char-forming material electrochemical cathode that metal ion is adsorbed with organic matter
The application of raw hydrogen peroxide.
25 DEG C, under the conditions of pH=7, liquor capacity 1L, sodium sulfate concentration 0.05mol/L, oxygen flow 50mL/
Min, cathode-current density 30mA/cm2, anode is platinized platinum, and cathode is the electrochemical cathode, electrolysis time 10min, using titanium
The concentration of salt Spectrophotometric Determination of Hydrogen Peroxide, hydrogen peroxide yield processing result of the different ratio in 10min are shown in Table 1.
1 different ratio electrochemical cathode hydrogen peroxide yield of table
Note: AB is acetylene black, for conduction.
Hydrogen peroxide producing method, O2+2H++2e-→H2O2, and hydrogen peroxide and ozone reaction can produce hydroxyl radical free radical,
H2O2+2O3→·OH+3O2, while the metallic site after MOFs carbonization can also be catalyzed hydrogen peroxide and generate hydroxyl radical free radical
Mn+H2O2→Mn+1+OH-+·OH；And the yield of hydroxyl radical free radical can measure system degradation capability；
OH+ waste water to be processed → small molecule+H2O；Thus when ozone dosage is excessive, the yield of hydrogen peroxide is direct
Physical performance is polluted in the removal of influence system.The hydrogen peroxide yield for the 10min that the electrode original position of above-mentioned preparation generates is in 45.80-
78.02mg/L (liquor capacity 1L), is above 40mg/L, has excellent performance.
Application Example 2
MOFs char-forming material electrochemical cathode by embodiment 1 based on metal ion and organic matter absorption is in catalytic electrochemical
Couple the application of ozone degradation fluoroquinolone antibiotic.
At 25 DEG C, under the conditions of pH=7, liquor capacity 1L, fluoroquinolones organic concentration is 40mg/L (fluorine respectively
Quinolones organic matter includes Enrofloxacin, Norfloxacin and Ofloxacin), sodium sulfate concentration 0.05mol/L, foul smell flow
For 100mL/min, gas phase ozone concentration is 50mg/L, cathode-current density 30mA/cm2, anode is platinized platinum, and cathode is the electrification
Cathode is learned, the removal time is 10min.The concentration of fluoquinolone type organic in reaction process is measured using high performance liquid chromatography,
Initial point concentration is Co, and in 0,2,4,6,8,10min point in time sampling, measuring concentration is C.
Transmission electron microscope picture (Fig. 1) illustrates that the MOFs carbonization of metal ion and organic matter absorption is complete, the nano particle of formation
It is evenly dispersed；Magnetic characterization Fig. 2 illustrates that char-forming material generates the magnetic substance of tool；For different process degradation fluoquinolone
Solution afterwards carries out the full spectrum scanning of ultraviolet specrophotometer, shows that the electrochemical cathode removal capacity is superior, hence it is evident that better than single
One technique (Fig. 3)；It is coupled with the MOFs char-forming material electrochemical cathode that organic matter adsorbs in catalytic electrochemical based on metal ion
In ozone degradation Enrofloxacin, Norfloxacin and Ofloxacin system, removal rate respectively 86.3%, 85.6% in 10min
With 87.4%, as shown in Figure 4.
Application Example 3
MOFs char-forming material electrochemical cathode by embodiment 1 based on metal ion and organic matter absorption is in electro-catalysis PMS
Application in terms of degradation organo-chlorine pesticide
At 25 DEG C, under the conditions of pH=7, liquor capacity 1L, be added 5mmol/L persulfate (can be potassium peroxydisulfate or
Person's sodium peroxydisulfate), organo-chlorine pesticide organic concentration be respectively 100mg/L (organo-chlorine pesticide organic matter be 5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfuric ester,
Trans chlordane and 4,4- dichloro-diphenyl-dichlorothane), sodium sulfate concentration 0.05mol/L, oxygen flow 200mL/min, cathode-current density
50mA/cm2, anode is platinized platinum, and cathode is the electrochemical cathode, and the removal time is 30min.It was reacted using gas Chromatographic Determination
The concentration of organic matter in journey, initial point concentration are Co, and in 10min point in time sampling, measuring concentration is C.Based on metal ion
MOFs char-forming material electrochemical cathode with organic matter absorption is in electro-catalysis PMS degradation 5a,6,9,9a-hexahydro-6,9-methano-2,4 sulfuric ester, trans chlordane and 4,4-
In dichloro-diphenyl-dichlorothane system, removal rate respectively 94.1%, 93.2% and 91.6% in 30min, as shown in Figure 5.
It above are only the preferred embodiment of the invention, be not restricted to the present invention.Those skilled in the art is come
It says, other various forms of variations or variation can also be made on the basis of the above description.There is no need and unable to all
Embodiment illustrate.And the obvious changes or variations that thus scheme is extended out are still in protection of the invention
Within the scope of.
Claims (10)
1. a kind of preparation method of the MOFs char-forming material electrochemical cathode based on metal ion and organic matter absorption, feature exist
In: it the described method comprises the following steps:
1) the metal organic framework compound MOFs for being adsorbed with metal ion or organic matter centrifuge separation is placed on electric tube furnace
Interior, high-temperature roasting under inert gas protection is ground after cooling, obtains carbonization MOFs material；
2) carbonization MOFs material and rush that step 1) is prepared are led into agent, pore creating material and dehydrated alcohol or polyethylene glycol mixture
It is ultrasonic afterwards, it is added after binder and stirs under water bath with thermostatic control to rubberlike mixture；Rubberlike mixture is wrapped in bubble
On foam nickel, compression moulding after ethyl alcohol is added, is then roasted under conditions of inert gas shielding, then with 80-100 DEG C of water washing,
The electrochemical cathode of carbonization MOFs material is obtained after natural air drying.
2. the system of the MOFs char-forming material electrochemical cathode according to claim 1 based on metal ion and organic matter absorption
Preparation Method, it is characterised in that: the step 1) metal ion is one of copper ion, iron ion, manganese ion and cobalt ions
Or a variety of combination；The organic matter is POPs or PPCPs.
3. the system of the MOFs char-forming material electrochemical cathode according to claim 2 based on metal ion and organic matter absorption
Preparation Method, it is characterised in that: used maturing temperature is 600-900 DEG C when high-temperature roasting in the step 1), tubular type electricity
Furnace heating rate is 5-10 DEG C per minute, and the high-temperature roasting time is 1-3h；The inert gas is nitrogen or argon gas；It is described to grind
Further included the steps that 300 mesh screens after mill.
4. the MOFs char-forming material electrochemistry yin according to claim 1 or 2 or 3 based on metal ion and organic matter absorption
The preparation method of pole, it is characterised in that: it is described rush lead agent, pore creating material, binder and be carbonized MOFs material mass ratio be (10 ~
20): (15 ~ 35): (250 ~ 450): 100.
5. the system of the MOFs char-forming material electrochemical cathode according to claim 4 based on metal ion and organic matter absorption
Preparation Method, it is characterised in that: it is acetylene black AB that rush, which leads agent, described in the step 2；The pore creating material is sodium sulphate or/and carbonic acid
Hydrogen sodium；The binder is polytetrafluoroethylene (PTFE).
6. the system of the MOFs char-forming material electrochemical cathode according to claim 5 based on metal ion and organic matter absorption
Preparation Method, it is characterised in that: the thickness of the electrochemical cathode of the carbonization MOFs material is 1-3 mm；The electricity of carbonization MOFs material
Each side length of chemical cathode is 1-5 cm；H can be generated in situ per minute by being passed through in the case of oxygen2O2 5-10 mg/L。
7. the MOFs char-forming material described in any claim based on metal ion and organic matter absorption according to claim 1 ~ 6
The MOFs char-forming material electrochemistry yin based on metal ion and organic matter absorption that the preparation method of electrochemical cathode is prepared
Pole.
8. the MOFs char-forming material electrochemical cathode according to claim 7 based on metal ion and organic matter absorption is in original
Position generates application when hydrogen peroxide.
9. the MOFs char-forming material electrochemical cathode according to claim 7 based on metal ion and organic matter absorption is in electricity
Application in terms of chemical Coupling ozone degradation fluoroquinolone antibiotic.
10. the MOFs char-forming material electrochemical cathode according to claim 7 based on metal ion and organic matter absorption exists
Application in terms of electro-catalysis PMS degradation fluoroquinolone antibiotic.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113998760A (en) * | 2021-10-30 | 2022-02-01 | 北京工业大学 | Copper-cobalt oxide/carbon nanotube/foamed nickel composite electrode for heterogeneous electro-Fenton system and application |
| CN114150333A (en) * | 2021-12-06 | 2022-03-08 | 郑州大学 | Preparation method of iron-doped porous carbon-oxygen reduction catalyst and application of iron-doped porous carbon-oxygen reduction catalyst in electrocatalytic production of hydrogen peroxide |
| CN114539629A (en) * | 2022-02-23 | 2022-05-27 | 中国科学技术大学 | 3D printing biological ink, preparation method thereof, 3D printing biological cathode material, preparation method and application thereof |
| CN115970761A (en) * | 2022-12-14 | 2023-04-18 | 中国五冶集团有限公司 | Synthesis method and test method of catalytic material of alumina reactor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105110423A (en) * | 2015-09-08 | 2015-12-02 | 同济大学 | Carbon-aerogel-carried bimetal organic framework electro-Fenton cathode and preparation method thereof |
| CN106229465A (en) * | 2016-08-18 | 2016-12-14 | 长安大学 | A kind of lithium ion battery negative based on 1,4 naphthalene diacid cobalts and preparation method thereof |
| CN107029789A (en) * | 2017-04-07 | 2017-08-11 | 三峡大学 | A kind of preparation method of water electrolysis hydrogen production electrode material |
| CN108550819A (en) * | 2018-04-23 | 2018-09-18 | 成都新柯力化工科技有限公司 | A kind of lead carbon battery negative material and preparation method |
| CN109019786A (en) * | 2018-09-13 | 2018-12-18 | 南京师范大学常州创新发展研究院 | Preparation method, combination electrode and its application method of MOFs macromolecule combination electrode |
-
2019
- 2019-06-05 CN CN201910489246.2A patent/CN110172709B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105110423A (en) * | 2015-09-08 | 2015-12-02 | 同济大学 | Carbon-aerogel-carried bimetal organic framework electro-Fenton cathode and preparation method thereof |
| CN106229465A (en) * | 2016-08-18 | 2016-12-14 | 长安大学 | A kind of lithium ion battery negative based on 1,4 naphthalene diacid cobalts and preparation method thereof |
| CN107029789A (en) * | 2017-04-07 | 2017-08-11 | 三峡大学 | A kind of preparation method of water electrolysis hydrogen production electrode material |
| CN108550819A (en) * | 2018-04-23 | 2018-09-18 | 成都新柯力化工科技有限公司 | A kind of lead carbon battery negative material and preparation method |
| CN109019786A (en) * | 2018-09-13 | 2018-12-18 | 南京师范大学常州创新发展研究院 | Preparation method, combination electrode and its application method of MOFs macromolecule combination electrode |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113998760A (en) * | 2021-10-30 | 2022-02-01 | 北京工业大学 | Copper-cobalt oxide/carbon nanotube/foamed nickel composite electrode for heterogeneous electro-Fenton system and application |
| CN113998760B (en) * | 2021-10-30 | 2023-09-19 | 北京工业大学 | Copper-cobalt oxide/carbon nano tube/foam nickel composite electrode for heterogeneous electro-Fenton system and application |
| CN114150333A (en) * | 2021-12-06 | 2022-03-08 | 郑州大学 | Preparation method of iron-doped porous carbon-oxygen reduction catalyst and application of iron-doped porous carbon-oxygen reduction catalyst in electrocatalytic production of hydrogen peroxide |
| CN114150333B (en) * | 2021-12-06 | 2023-12-19 | 郑州大学 | Preparation method of iron-doped porous carbon-oxygen reduction catalyst and application of iron-doped porous carbon-oxygen reduction catalyst in electrocatalytic production of hydrogen peroxide |
| CN114539629A (en) * | 2022-02-23 | 2022-05-27 | 中国科学技术大学 | 3D printing biological ink, preparation method thereof, 3D printing biological cathode material, preparation method and application thereof |
| CN114539629B (en) * | 2022-02-23 | 2023-03-14 | 中国科学技术大学 | 3D printing biological ink, preparation method thereof, 3D printing biological cathode material, preparation method and application thereof |
| CN115970761A (en) * | 2022-12-14 | 2023-04-18 | 中国五冶集团有限公司 | Synthesis method and test method of catalytic material of alumina reactor |
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