CN105110423B - Carbon-aerogel-carried bimetal organic framework electro-Fenton cathode and preparation method thereof - Google Patents
Carbon-aerogel-carried bimetal organic framework electro-Fenton cathode and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carbon-aerogel-carried bimetal organic framework electro-Fenton cathode and a preparation method thereof. The preparation method comprises the following steps: by using a block carbon aerogel as a substrate electrode, carrying out hydrothermal reaction to load a bimetal organic framework onto the substrate electrode, filtering, washing, and carrying out vacuum drying to obtain the carbon-aerogel-carried bimetal organic framework electro-Fenton cathode, wherein the bimetal organic framework is a Fe/Co bimetal organic framework. Compared with the prior art, by combining the photocatalytic technique and electro-Fenton, the carbon-aerogel-carried bimetal organic framework electro-Fenton cathode can degrade organic pollutants by using the higher-efficiency low-energy-consumption advanced oxidation technique, thereby providing a new way for using the electro-Fenton cathode in the photocatalytic/electro-Fenton combined technique for treating nondegradable organic pollutants. The carbon-aerogel-carried bimetal organic framework electro-Fenton cathode has the advantages of simple technical operation, energy saving and high efficiency, and has very wide application range in the field of actual water treatment.
Description
Technical field
The invention belongs to water-treatment technology field, be related to carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode and its
Preparation method.
Background technology
Global water pollution and water quality deterioration already turn into an environmental problem for sternness of face of mankind nowadays.People couple
The active demand of clean water promotes water technology to be increasingly subject to extensive concern.At present, it is applied to the side in water pollution control
Method mainly has：Physical, chemical method and microbial method, in these techniques, high-level oxidation technology (Advanced Oxidation
Processes abbreviation AOP), including Fenton technology, photocatalysis, ozone oxidation and they be combined with each other etc., it is efficient with its
Degradation capability, simple and convenient and product greenization the features such as get the attention and pay attention to.High-level oxidation technology is most aobvious
The characteristics of work is as primary oxidizers, due to reactivity OH high and non-selective degraded with hydroxyl radical free radical (OH)
It is difficult to by biodegradable pollutant.And OH is mainly by decomposing H2O2Produce, so electric Fenton arises.
Electric Fenton technology can be in negative electrode generation H in situ2O2, overcome transport and storage H2O2The shortcoming of inconvenience, therefore suffers from extensive
Using.In fact, the H that electric Fenton is produced2O2In transition metal ions (Fe2+, Fe3+, Cu+, Cr6+Deng), ultra violet lamp and
OH is readily available under the catalytic action of ultrasound, however, these homogeneous electricity Fenton methods use narrow range to the pH of solution, is held
The continuous time is long and constantly requires the expenditure of energy.In order to solve the above problems, the research of out-phase electricity Fenton technology causes gradually
The interest of scientist.These researchs are based primarily upon the out-phase electricity fenton catalyst of iron, such as nano zero valence iron (nZVI), Fe2O3,
Fe3O4, alpha-feooh, BiFeO4, FeVO4, CuFe2O4, CuFe-MC, Fe alginates and Fe-ZSM-5 molecular sieves etc..Certainly also have
Research finds that some semiconductor light-catalysts also can under visible light activate H2O2, such as 3DOM-Fe2O3, TiO2, BiVO4, WO3, g-
C3N4, ZnFe2O4, K3PW12O40Deng.Therefore, efficiently out-phase electricity Fenton agent activation H is constructed2O2It is to realize efficiently drop to produce OH
Solve the key of pollutant.
Metal-organic framework compound (MOFs) is assembled with oxygen-containing or nitrogen organic ligand by transition metal ions
The class zeolitic material with tridimensional network.It is a kind of new porous material, because its prepare it is simple, porous, compare table
The advantages of big its structure of area is adjustable, MOFs is widely used for the neck such as gas absorption, separation, catalysis, sensor, drug delivery
Domain.But, recent research indicate that some of which MOFs shows semiconductor property, it is meant that it has extensively as photochemical catalyst
General application prospect.Compared to the system of more traditional conductor photocatalysis, the advantage of the photocatalytic system of MOF is more effective
Using solar energy, also just because of its regulatable avtive spot (i.e. metal carboxyl cluster and organic ligand), preferable porosity
MOF photocatalytic systems are not only enabled reasonably to be designed on a molecular scale and assembled with specific surface area high, and
Can quickly transmit and store guest molecule.In a word, MOFs captures luminous energy carries out the research of photocatalysis degradation organic contaminant
It is a significantly problem.
Certainly, there is researcher that MOFs is applied into photocatalytic pollutant degradation recently.For example, the metal of Zn is organic
Framework compound (MOF-5) is used for electronics and the hole that ultraviolet catalytic is produced, and can be used in the benzene in wastewater by photocatalysis
Phenol；Likewise, also there is researcher that another metallic framework compound (UTSA-38) of Zn is contaminated for visible light photocatalytic degradation
Methyl orange (MO) in material waste water；Also have using Co-MOF ([Co2(C10H8N2)]L2) decline Xie Leima in UV, visible light light irradiation
Azoles light blue；More also meet structure come degradable organic pollutant, such as Fe using what oxide or simple substance and MOF were formed3O4@
MIL-100 (Fe), Cu/ZIF-67, Fe@MIL-100 (Fe) etc..Photocatalysis or out-phase are applied in spite of so many MOF
Fenton degradation of contaminant, but applications of the MOF in electro-catalysis can not be ignored.Current MOF is applied to the main side of electro-catalysis
Face has：Evolving hydrogen reaction, oxygen evolution reaction, oxygen reduction reaction, oxidation of ethanol etc..Such as Babu have studied MOF (Fe) recently
(BasoliteTMF300) cyclic voltammetry curve in acid medium, draws FeII/FeIIIReduction peak occur at 0.48V.
Mao etc. utilizes trimesic acid (1,3,5-BTC) and 2,2 ' two pyridines to be used for as the Cu-btc-bipy that organic ligand is prepared
ORR reacts, and finds that the take-off potential of its generation ORR reactions, in -0.05V, thus illustrates that MOF also has very big in electro-catalysis
Application prospect.But the photocatalysis technology of MOF is rarely reported with the research that electro-catalysis is combined.
The content of the invention
The purpose of the present invention is exactly that one kind is provided for the defect for overcoming above-mentioned prior art to exist under the conditions of pH wide
Possesses carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode of photoelectricity Fenton catalysis activity high and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
Carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode, the electric Fenton negative electrode includes basal electrode and load
Bimetallic organic backbone on basal electrode, wherein, described basal electrode is block carbon aerogels, and described bimetallic has
Machine skeleton is Fe/Co bimetallic organic backbones.
The preparation method of carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode, the method is with block carbon aerogels
As basal electrode, bimetallic organic backbone is supported on basal electrode by hydro-thermal reaction, by filtering, washing, vacuum
Dry, that is, described carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode is obtained.
The preparation method of described carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode, specifically includes following step
Suddenly：
(1) block carbon aerogels (CA) are prepared；
(2) it is 1-3 by the mol ratio that metal Fe salt and metal Co salt press Fe and Co:1 mixing, with organic ligand, hydrofluoric acid
Add together in distilled water, mix 1-2h, be configured to the precursor solution of bimetallic organic framework material, then by bimetallic
The precursor solution of organic framework material is placed in reactor together with block carbon aerogels, sealing, carries out hydro-thermal reaction, treats anti-
After should terminating, reactor naturally cools to room temperature, filtering, then scrubbed treatment, removes unreacted impurity, dry by vacuum
It is dry, that is, described carbon aerogel load bimetallic organic backbone electricity Fenton (i.e. MOF (Fe/Co)/CA) negative electrode is obtained.
The concentration of described HF is 40wt%, its pH value for being mainly used in controlling solution, its pH value is less than 1.
Block carbon aerogels described in step (1) are prepared from using following methods：
By resorcinol, formaldehyde, water and sodium carbonate according to mol ratio be 1：2：17.5：0.0008 is well mixed, and pours into glass
In glass mould, it is then placed in closed container, stands reaction, phenolic resin aerogel obtained by taking out, then it is small with surface tension
Solvent displacement is carried out in the organic reagent of 30mN/m, the time is 5-7 days, and an acetone was changed every 1-2 days, treat solvent displacement knot
Shu Hou, resulting phenolic resin aerogel is dried at room temperature, controls drying time for 5-7 days, in transferring to tube furnace
High-temperature heat treatment is carried out, that is, described block carbon aerogels are obtained.
The condition of described high-temperature heat treatment is：800-950 DEG C, at constant temperature is warming up to the speed of 1.5-3.5 DEG C/min
Reason 3-5h, then room temperature is cooled to the speed of 1.5-3.5 DEG C/min.
Metal Fe salt described in step (2) is Fe (NO3)3、Fe2(SO4)3Or FeCl3In one kind, described metal Co salt
It is CoSO4、CoCl2Or Co (NO3)2In one kind, described organic ligand is 2,2'- bipyridyls, 4,4'- bipyridyls, 1,3,5-
One kind in benzenetricarboxylic acid or 1,4- phthalic acids.
Preferably, described metal Fe salt is Fe (NO3)3, described metal Co salt is CoCl2, described organic ligand is
1,3,5- benzenetricarboxylic acids.
The amount of metal Fe salt described in step (2) and the total material of metal Co salt and organic ligand, the material of hydrofluoric acid
The ratio between amount is 7-8:4-6:2-4.
The condition of the hydro-thermal reaction described in step (3) is：In 150-170 DEG C, isothermal reaction 48-72h；Described washup
The condition of reason is：Prior to cleaning 6h in the 70-90 DEG C of aqueous solution, 6h is then cleaned in 50-70 DEG C of ethanol solution.
The carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode prepared using described preparation method is used for
The reaction temperature of catalyzing oxidizing degrading pollutant is 25-30 DEG C, and pH scopes are 3-9.
In the present invention, organic ligand is selected from 1,3, the 5- benzenetricarboxylic acids with more tooth form functional group, belongs to polybasic carboxylic acid
Part, 1,3,5- benzenetricarboxylic acid is rigidly good, and it advantageously forms the larger polymer in aperture, and its own heat endurance is good,
Substructural unit (SBU) structure is easily formed, and then is conducive to being obtained the poroid MOFs of crystalline state of stabilization.
MOF (Fe/Co) material of the present invention is prepared by hydro-thermal method, and the presoma that will prepare MOF (Fe/Co) is molten
Liquid and the carbon aerogels (CA) with high-specific surface area are inserted in reactor together, using the high absorption property of CA, by MOF (Fe/
Co presoma) is adsorbed onto the surface of CA, then forms MOF (Fe/Co) metal organic framework compound on CA surfaces again, obtains final product
To a kind of carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode.
Be combined for photocatalysis technology and electric Fenton by the present invention, realizes that the high-level oxidation technology of more efficient and low power consuming is degraded
Organic pollution, one is provided for electric Fenton negative electrode is used for photocatalysis with electric Fenton GC-MS treatment persistent organic pollutants
Plant new approach.
Compared with prior art, the invention has the characteristics that：
(1) compared with traditional method for treating water, the present invention is by the Fenton technology with superelevation oxidability and with light
The MOF of catalytic capability is combined, while realizing the efficient, degradable organic pollutant of low energy consumption；
(2) compared with existing electric Fenton cathode material, it is basal electrode that the present invention uses porous material carbon aerogels, it
Not only there is electro-chemical activity and specific surface area high higher, this is oxygen in negative electrode two electronic reduction reactions of generation in situ
(ORR) H is produced2O2There is provided good condition, meanwhile, the addition of bimetallic MOF (Fe/Co) can also improve the reaction work of ORR
Property；
(3) in the present invention, bimetallic MOF (Fe/Co) is grown on CA basal electrodes, moreover it is possible to realize photoelectricity Fenton one
Bodyization is degraded so that degradation effect is more safe and efficient；
(4) preparation process letter of the present invention is answered, easy control of reaction conditions, and operation is easy, and the prices of raw materials are cheap, system
Standby low cost, efficient stable, the carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode obtained by preparation has drop wider
Solution pH scopes, with prominent degrading activity, can realize the fast degradation to Recalcitrant chemicals, it is adaptable to expand chemical industry
Production, with good application prospect.
Brief description of the drawings
Fig. 1 is the SEM figures of obtained MOF (the Fe/Co)/CA negative electrodes of the present invention；
Fig. 2 helps electric Fenton degraded RhB kinetics figures for obtained MOF (the Fe/Co)/CA negative electrode light of the present invention；
Fig. 3 is obtained MOF (the Fe/Co)/CA negative electrodes of the present invention to the simulated wastewater degradation efficiency figure of different pH.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
Carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode, it is using the carbon aerogels of excellent electric conductivity as base
Hearth electrode, is electric fenton catalyst with MOF (Fe/Co), and is combined with the photocatalysis technology of low energy consumption, is capable of achieving quickly and efficiently
Removal of the ground to persistent organic pollutants.
The specific preparation process of MOF (Fe/Co)/CA electricity Fenton cathode materials is as follows in the present embodiment：
(1) by resorcinol, formaldehyde, water and sodium carbonate according to mol ratio be 1：2：17.5：0.0008 is well mixed, and pours into
In glass mold, it is then placed in closed container, stands reaction, phenolic resin aerogel obtained by taking out, then use surface tension
Organic reagent less than 30mN/m carries out solvent displacement, and the time is 5-7 days, and an acetone was changed every 1-2 days；By resulting phenol
Urea formaldehyde aeroge is placed and is dried at room temperature, and the drying at room temperature time is that control program heats up in tube furnace after 5-7 days,
It is warmed up to 800-950 DEG C and is kept at this temperature with the speed of 1.5-3.5 DEG C/min and reacts 3-5h, it is then cold at the same rate
But to room temperature, block carbon aerogels are obtained；
(2) control Fe (NO3)3·9H2O and CoCl2·6H2The amount of O total materials is 7-8mmol, takes Fe:The ratio of Co is
(1-3):1 metal salt mixture.Every part of metal salt mixture again with the 1 of 4-6mmol, 3,5- benzenetricarboxylic acids (BTC), 2-
The hydrofluoric acid (HF) of 4mmol is together added in the distilled water of 30-50mL, is mixed one hour.
(3) the block carbon aerogels and MOF (Fe/Co) precursor solution one obtained in step (2) of step (1) preparation are taken
Rise addition reactor it is closed after, be heated to 150-170 DEG C and holding three days；Then after hydro-thermal terminates, baking oven is closed, allows reactor
Temperature fall is to room temperature；After being filtered to product, in 70-90 DEG C of aqueous wash medium 6 hours, then again in 50-70 DEG C of ethanol
Washed in solution 6 hours and remove unreacted organic matter, finally vacuum drying obtains the double gold of described carbon aerogel load for 24 hours
Category organic backbone electricity Fenton negative electrode, i.e. MOF (Fe/Co)/CA electricity Fenton negative electrodes, as shown in Figure 1.
Embodiment 2：
The experiment of the photoelectricity Fenton rhodamine B of MOF (Fe/Co)/CA electrodes is carried out in cylinder single entry circulating water chennel,
(air) is constantly aerated in experimentation and ON cycle cooling water maintains tank temperature.Sun radiant is using 500W's
Xenon lamp.Rhodamine B (20mg/L) and Na2SO4The mixed solution 100mL of (0.1M) is used as simulated wastewater.MOF (Fe/Co)/CA (works
Make area fixed bit 2cm2), used as negative electrode, the BDD of identical work area is used as anode, and the distance between two electrodes are protected for electrode
Hold in 2cm；During degradation experiment, the source of air supplemental oxygen is constantly blasted, air velocity is 300mL min-1；According to
Dynamic analysis, it is first order reaction that light helps electric Fenton degraded RhB reactions, and its reaction constant is 0.02min-1, this is electric Fenton drop
5 times of solution reaction (0.004), as shown in Figure 2.
Embodiment 3：
In order to assess MOF (the Fe/Co)/stability of the CA electrodes in actual water process of preparation, different pH are prepared respectively
Simulated wastewater (the RhB aqueous solution), the light for being then followed by MOF (Fe/Co)/CA electrodes helps electric Fenton rhodamine B, and degraded is real
Test is carried out in cylinder single entry circulating water chennel, is constantly aerated (air) in experimentation and ON cycle cooling water is tieed up
Water holding bath temperature degree.Sun radiant uses the xenon lamp of 500W.Rhodamine B (20mg/L) and Na2SO4The mixed solution of (0.1M)
100mL is used as simulated wastewater.MOF (Fe/Co)/CA (work area fixed bit 2cm2) electrode as negative electrode, identical work area
BDD as anode, and the distance between two electrodes are maintained at 2cm；During degradation experiment, air delivery of supplemental oxygen is constantly blasted
The source of gas, air velocity is 300mL min-1.Result shows that MOF (Fe/Co)/CA electrodes all show in the range of PH wide
Degrading activity high, the result of degraded is as shown in Figure 3.
Embodiment 4：
The preparation method of the present embodiment carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode, specifically includes following step
Suddenly：
(1) block carbon aerogels are prepared；
(2) it is 1 by the mol ratio that metal Fe salt and metal Co salt press Fe and Co:1 mixing, with organic ligand, hydrofluoric acid one
Rise in addition distilled water, mix 2h, then by the precursor solution of Fe/Co bimetallic organic backbones and block carbon aerogels
It is placed in reactor together, seals, carry out hydro-thermal reaction, after question response terminates, reactor naturally cools to room temperature, filtering, then
Scrubbed treatment, removes unreacted impurity, by vacuum drying, that is, the described organic bone of carbon aerogel load bimetallic is obtained
Frame electricity Fenton negative electrode.
Wherein, in step (1), block carbon aerogels are prepared from using following methods：By resorcinol, formaldehyde, water and
Sodium carbonate is 1 according to mol ratio：2：17.5：0.0008 is well mixed, and pours into glass mold, is then placed in closed container,
Reaction is stood, resulting phenolic resin aerogel is taken out, then solvent is carried out with the organic reagent that surface tension is less than 30mN/m and put
Change, the time is 5 days, an acetone is changed every 1 day, after after solvent replacement completion, by resulting phenolic resin aerogel in room
The lower drying of temperature, it is 5 days control drying time, transfers to and carry out in tube furnace high-temperature heat treatment (high-temperature heat treatment condition is：With
The speed of 3.5 DEG C/min is warming up to 950 DEG C, and constant temperature processes 3h, then is cooled to room temperature with the speed of 3.5 DEG C/min), that is, institute is obtained
The block carbon aerogels stated.
In step (2), metal Fe salt is Fe2(SO4)3, metal Co salt is CoSO4, organic ligand is 1,3,5- benzene front threes
Acid.Wherein, Fe2(SO4)3With CoSO4The ratio between amount and 1,3,5- benzenetricarboxylic acids, the amount of material of hydrofluoric acid of total material be 8:
6:4。
In step (3), the condition of hydro-thermal reaction is：In 170 DEG C, isothermal reaction 48h；The condition of carrying out washing treatment is：Prior to
6h is cleaned in 90 DEG C of aqueous solution, then 6h is cleaned in 70 DEG C of ethanol solutions.
The carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode that the present embodiment is prepared drops for catalysis oxidation
The reaction temperature for solving pollutant is 25-30 DEG C, and pH scopes are 3-9.
Embodiment 5：
The preparation method of the present embodiment carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode, specifically includes following step
Suddenly：
(1) block carbon aerogels are prepared；
(2) it is 3 by the mol ratio that metal Fe salt and metal Co salt press Fe and Co:1 mixing, with organic ligand, hydrofluoric acid one
Rise in addition distilled water, mix 1h, then by the precursor solution of Fe/Co bimetallic organic backbones and block carbon aerogels
It is placed in reactor together, seals, carry out hydro-thermal reaction, after question response terminates, reactor naturally cools to room temperature, filtering, then
Scrubbed treatment, removes unreacted impurity, by vacuum drying, that is, the described organic bone of carbon aerogel load bimetallic is obtained
Frame electricity Fenton negative electrode.
Wherein, in step (1), block carbon aerogels are prepared from using following methods：By resorcinol, formaldehyde, water and
Sodium carbonate is 1 according to mol ratio：2：17.5：0.0008 is well mixed, and pours into glass mold, is then placed in closed container,
Reaction is stood, resulting phenolic resin aerogel is taken out, then solvent is carried out with the organic reagent that surface tension is less than 30mN/m and put
Change, the time is 7 days, an acetone is changed every 1 day, after after solvent replacement completion, by resulting phenolic resin aerogel in room
The lower drying of temperature, it is 7 days control drying time, transfers to and carry out in tube furnace high-temperature heat treatment (high-temperature heat treatment condition is：With
The speed of 1.5 DEG C/min is warming up to 800 DEG C, and constant temperature processes 5h, then is cooled to room temperature with the speed of 1.5 DEG C/min), that is, institute is obtained
The block carbon aerogels stated.
In step (2), metal Fe salt is FeCl3, metal Co salt is Co (NO3)2, organic ligand is 1,3,5- benzenetricarboxylic acids.
Wherein, FeCl3With Co (NO3)2The ratio between amount and 1,3,5- benzenetricarboxylic acids, the amount of material of hydrofluoric acid of total material be 7:4:2.
In step (3), the condition of hydro-thermal reaction is：In 150 DEG C, isothermal reaction 72h；The condition of carrying out washing treatment is：Prior to
6h is cleaned in 70 DEG C of aqueous solution, then 6h is cleaned in 50 DEG C of ethanol solutions.
The carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode that the present embodiment is prepared drops for catalysis oxidation
The reaction temperature for solving pollutant is 25-30 DEG C, and pH scopes are 3-9.
Embodiment 6：
The preparation method of the present embodiment carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode, specifically includes following step
Suddenly：
(1) block carbon aerogels are prepared；
(2) it is 2 by the mol ratio that metal Fe salt and metal Co salt press Fe and Co:1 mixing, with organic ligand, hydrofluoric acid one
Rise in addition distilled water, mix 2h, then by the precursor solution of Fe/Co bimetallic organic backbones and block carbon aerogels
It is placed in reactor together, seals, carry out hydro-thermal reaction, after question response terminates, reactor naturally cools to room temperature, filtering, then
Scrubbed treatment, removes unreacted impurity, by vacuum drying, that is, the described organic bone of carbon aerogel load bimetallic is obtained
Frame electricity Fenton negative electrode.
Wherein, in step (1), block carbon aerogels are prepared from using following methods：By resorcinol, formaldehyde, water and
Sodium carbonate is 1 according to mol ratio：2：17.5：0.0008 is well mixed, and pours into glass mold, is then placed in closed container,
Reaction is stood, resulting phenolic resin aerogel is taken out, then solvent is carried out with the organic reagent that surface tension is less than 30mN/m and put
Change, the time is 6 days, an acetone is changed every 2 days, after after solvent replacement completion, by resulting phenolic resin aerogel in room
The lower drying of temperature, it is 6 days control drying time, transfers to and carry out in tube furnace high-temperature heat treatment (high-temperature heat treatment condition is：With
The speed of 2 DEG C/min is warming up to 860 DEG C, constant temperature treatment 4h, then is cooled to room temperature with the speed of 2 DEG C/min), that is, it is obtained described
Block carbon aerogels.
In step (2), metal Fe salt is Fe (NO3)3, metal Co salt is Co (NO3)2, organic ligand is 1,3,5- benzene front threes
Acid.Wherein, Fe (NO3)3With Co (NO3)2The amount of total material be with the ratio between 1,3,5- benzenetricarboxylic acids, the amount of material of hydrofluoric acid
7:5:3。
In step (3), the condition of hydro-thermal reaction is：In 165 DEG C, isothermal reaction 60h；The condition of carrying out washing treatment is：Prior to
6h is cleaned in 85 DEG C of aqueous solution, then 6h is cleaned in 60 DEG C of ethanol solutions.
The carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode that the present embodiment is prepared drops for catalysis oxidation
The reaction temperature for solving pollutant is 25-30 DEG C, and pH scopes are 3-9.
Embodiment 7：
The preparation method of the present embodiment carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode, specifically includes following step
Suddenly：
(1) block carbon aerogels are prepared；
(2) it is 1.5 by the mol ratio that metal Fe salt and metal Co salt press Fe and Co:1 mixing, with organic ligand, hydrofluoric acid
Add together in distilled water, mix 1.5h, then by the precursor solution of Fe/Co bimetallic organic backbones and block carbon gas
Gel is placed in reactor together, sealing, carries out hydro-thermal reaction, and after question response terminates, reactor naturally cools to room temperature, mistake
Filter, then scrubbed treatment, remove unreacted impurity, by vacuum drying, that is, described carbon aerogel load bimetallic are obtained
Organic backbone electricity Fenton negative electrode.
Wherein, in step (1), block carbon aerogels are prepared from using following methods：By resorcinol, formaldehyde, water and
Sodium carbonate is 1 according to mol ratio：2：17.5：0.0008 is well mixed, and pours into glass mold, is then placed in closed container,
Reaction is stood, resulting phenolic resin aerogel is taken out, then solvent is carried out with the organic reagent that surface tension is less than 30mN/m and put
Change, the time is 6 days, an acetone is changed every 2 days, after after solvent replacement completion, by resulting phenolic resin aerogel in room
The lower drying of temperature, it is 6 days control drying time, transfers to and carry out in tube furnace high-temperature heat treatment (high-temperature heat treatment condition is：With
The speed of 3 DEG C/min is warming up to 900 DEG C, constant temperature treatment 3h, then is cooled to room temperature with the speed of 3 DEG C/min), that is, it is obtained described
Block carbon aerogels.
In step (2), metal Fe salt is FeCl3, metal Co salt is CoSO4, organic ligand is 1,3,5- benzenetricarboxylic acids.Its
In, FeCl3With CoSO4The ratio between amount and 1,3,5- benzenetricarboxylic acids, the amount of material of hydrofluoric acid of total material be 7:6:2.
In step (3), the condition of hydro-thermal reaction is：In 168 DEG C, isothermal reaction 72h；The condition of carrying out washing treatment is：Prior to
6h is cleaned in 80 DEG C of aqueous solution, then 6h is cleaned in 68 DEG C of ethanol solutions.
The carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode that the present embodiment is prepared drops for catalysis oxidation
The reaction temperature for solving pollutant is 25-30 DEG C, and pH scopes are 3-9.
The above-mentioned description to embodiment is to be understood that and apply this hair for ease of those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation here
Example, those skilled in the art's announcement of the invention, the improvement made for the present invention and modification all should be of the invention
Within protection domain.
Claims (8)
1. the preparation method of carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode, it is characterised in that described electric Fenton
Negative electrode includes basal electrode and the bimetallic organic backbone being supported on basal electrode, wherein, described basal electrode is block
Shape carbon aerogels, described bimetallic organic backbone is Fe/Co bimetallic organic backbones；
The preparation method of described electric Fenton negative electrode is using block carbon aerogels as basal electrode, by hydro-thermal reaction by double gold
Category organic backbone is supported on basal electrode, and by filtering, washing, vacuum drying is obtained described carbon aerogel load double
Metal organic framework electricity Fenton negative electrode, specifically includes following steps：
(1) block carbon aerogels are prepared；
(2) it is 1-3 by the mol ratio that metal Fe salt and metal Co salt press Fe and Co:1 mixing, together with organic ligand, hydrofluoric acid
Add in distilled water, mix 1-2h, be configured to the precursor solution of bimetallic organic framework material, then bimetallic is organic
The precursor solution of framework material is placed in reactor together with block carbon aerogels, sealing, carries out hydro-thermal reaction, question response knot
Shu Hou, reactor naturally cools to room temperature, filtering, then scrubbed treatment removes unreacted impurity, by vacuum drying, i.e.,
Described carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode is obtained.
2. the preparation method of carbon aerogel load bimetallic organic backbone according to claim 1 electricity Fenton negative electrode, it is special
Levy and be, the block carbon aerogels described in step (1) are prepared from using following methods：
By resorcinol, formaldehyde, water and sodium carbonate according to mol ratio be 1：2：17.5：0.0008 is well mixed, and pours into glass molds
In tool, it is then placed in closed container, stands reaction, phenolic resin aerogel obtained by taking out, then be less than with surface tension
The organic solvents-acetone of 30mN/m carries out solvent displacement, and the time is 5-7 days, and an acetone was changed every 1-2 days, treats that solvent is replaced
After end, resulting phenolic resin aerogel is dried at room temperature, control drying time for 5-7 days, transfer to tube furnace
In carry out high-temperature heat treatment, that is, described block carbon aerogels are obtained.
3. the preparation method of carbon aerogel load bimetallic organic backbone according to claim 2 electricity Fenton negative electrode, it is special
Levy and be, the condition of described high-temperature heat treatment is：800-950 DEG C, constant temperature treatment are warming up to the speed of 1.5-3.5 DEG C/min
3-5h, then room temperature is cooled to the speed of 1.5-3.5 DEG C/min.
4. the preparation method of carbon aerogel load bimetallic organic backbone according to claim 1 electricity Fenton negative electrode, it is special
Levy and be, the metal Fe salt described in step (2) is Fe (NO3)3、Fe2(SO4)3Or FeCl3In one kind, described metal Co salt
It is CoSO4、CoCl2Or Co (NO3)2In one kind, described organic ligand is 2,2'- bipyridyls, 4,4'- bipyridyls, 1,3,5-
One kind in benzenetricarboxylic acid or 1,4- phthalic acids.
5. the preparation method of carbon aerogel load bimetallic organic backbone according to claim 4 electricity Fenton negative electrode, it is special
Levy and be, described metal Fe salt is Fe (NO3)3, described metal Co salt is CoCl2, described organic ligand is 1,3,5- benzene
Tricarboxylic acid.
6. the preparation method of carbon aerogel load bimetallic organic backbone according to claim 1 electricity Fenton negative electrode, it is special
Levy and be, amount and organic ligand, the amount of the material of hydrofluoric acid of the total material of the metal Fe salt described in step (2) and metal Co salt
The ratio between be 7-8:4-6:2-4.
7. the preparation method of carbon aerogel load bimetallic organic backbone according to claim 1 electricity Fenton negative electrode, it is special
Levy and be, the condition of the hydro-thermal reaction described in step (2) is：In 150-170 DEG C, isothermal reaction 48-72h；Described washup
The condition of reason is：Prior to cleaning 6h in the 70-90 DEG C of aqueous solution, 6h is then cleaned in 50-70 DEG C of ethanol solution.
8. the preparation of the carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode according to any one of claim 2 to 7
Method, it is characterised in that the carbon aerogel load bimetallic organic backbone electricity Fenton negative electrode that the method is prepared is used to be catalyzed
The reaction temperature of oxidative degradation pollutant is 25-30 DEG C, and pH scopes are 3-9.
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