A kind of Ti/ charcoal-aero gel/MnO2Electrode and its preparation method and application
Technical field
The present invention relates to electro-catalytic oxidation technology fields, and in particular, to a kind of Ti/ charcoal-aero gel/MnO2Electrode and its
Preparation method and application.
Background technique
Electrochemical oxidation is widely applied in treatment of Organic Wastewater, mild, good degrading effect, use with reaction condition
The advantages that facilitating, it has also become one of the method for environmental area efficient process hardly degraded organic substance.
The performance of electro-catalysis anode is to influence one of the key factor of electroxidation efficiency, and in recent years, researcher uses various
Anode material, such as platinum electrode, titanium supported oxide electrode(Ti/Sn-SbO2、Ti/PbO2、Ti/MnO2), rear-earth-doped oxide electricity
Pole, carbon fiber electrode, boron-doped diamond electrode(BDD)Deng.Wherein, Ti/MnO2It is before the most having energy large-scale application at present
One of electrode of scape, this is mainly due to MnO2Rich reserves, cheap, environmental pollution is small;Moreover, manganese is with special
Electronic configuration(3d54s2), oxide has a more nonequilibrium condition in high-energy, and electro-chemical activity is high.Currently, Ti/
MnO2Electrode preparation method is usually to contain manganese compound with coating or electro-deposition(Mn(NO3)2、MnCl2Deng), directly MnO2It is negative
It is loaded on Titanium base, but the Ti/MnO of this method preparation2It is also easy to produce oxygen atom in electrolytic process and diffuses to titanium substrate, causes
MnO2Non-conductive film is generated between Ti substrate, makes MnO2It cracks and falls off, cause Ti/MnO2Service life is shorter.For asking above
Topic has research using tin-sb oxide(SbOx+SnO2)As middle layer(Yan-Hua Shi, et al. Effect of
SbOx+SnO2 Intermediate Layer on the Properties of Ti-based MnO2 Anode[J]. Acta
Physico-ChimicaSinca, 2007, 23(10): 1553-1559.), but SbOx+SnO2The preparation of middle layer needs anti-
Multiple coating-drying-calcining, preparation process is complicated, while SbOx+SnO2The loss of middle layer will also result in secondary pollution.Cause
This, the existing technology needs to be improved and developed.
Charcoal-aero gel is a kind of carbon nano-material of three-dimensional net structure, has high-specific surface area(Up to 600 ~ 1100
m2/g), high porosity(Up to 80~98%)With high conductivity(100 S/m).Therefore, charcoal-aero gel can be used as carrier, electrode material
Material and adsorbent are used in supercapacitor, lithium ion battery and environment protection field.About charcoal-aero gel/MnO2The preparation of electrode is reported
It is less, it can be retrieved at present about charcoal-aero gel/MnO2Patent mostly be to prepare nano particle, Chinese patent
CN200810028173 discloses a kind of nano thread-shaped manganese dioxide load carbon silica aerogel and the preparation method and application thereof, directly
Manganese dioxide load on carbon aerogel particle, Filamentous charcoal-aero gel/MnO has been prepared2Nano particle, and by above-mentioned nanometer
Particle is applied to serve as electrode filler sum aggregate fluid active substance in three-diemsnional electrode and supercapacitor.In the above method, because
The preparation of charcoal-aero gel ex situ, and without shuttering supporting, the charcoal-aero gel microcellular structure prepared is easy to collapse.Obviously, this method
It is only used for preparing nano particle, cannot be directly used to preparation large scale anode sheet material.
Therefore, it is necessary to research and develop the simple and environmentally-friendly Ti/ charcoal-aero gel/MnO of a kind of long service life, preparation method2Electricity
Pole and preparation method thereof.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of Ti/ charcoal-aero gel/MnO2The preparation of electrode
Method, preparation method provided by the invention is simple, the long service life of electrode that is prepared and environment friendly and pollution-free.
Another object of the present invention is to Ti/ charcoal-aero gel/MnO that the above method is prepared2Electrode.
Another object of the present invention is to provide above-mentioned Ti/ charcoal-aero gel/MnO2Electrode is useless in degradation as efficient anode
Application in Organic substance in water.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of Ti/ charcoal-aero gel/MnO2The preparation method of electrode, the method are as follows:
S1:POROUS TITANIUM substrate is pre-processed to remove surface and oil contaminant and oxidation film;
S2:By resorcinol, formaldehyde and water with 1~1.1:2~2.4:18~30 molar ratio is mixed and stirred for uniformly, then plus
Enter NaMnO4, to NaMnO4Mixed solution is persistently stirred to obtain after dissolution;
S3:Mixed solution obtained by S1 treated POROUS TITANIUM substrate and S2 is poured into mold, adjust solution make its pH 7.0~
7.5;
S4:Mold described in S3 is placed in 30~60 DEG C of thermostat water bath and stands 24~48h to carry out gelation, then in 80
48~96h carries out aging in~95 DEG C of thermostat water bath, removes mold up to Ti/ phenolic resin/MnO2Wet gel;
S5:By Ti/ phenolic resin/MnO obtained by S42Wet gel impregnates in the small organic solvent of surface tension, must do after dry
Then aeroge carbonizes the xerogel in inert atmosphere, cool down up to the Ti/ charcoal-aero gel/MnO2Electrode;
Wherein, in S1, the aperture of the POROUS TITANIUM substrate is 0.5~20 μm, and porosity is 40~85%.
In the present invention, the porosity of POROUS TITANIUM substrate and the size in aperture and the Ti/ charcoal-aero gel/MnO prepared2Electricity
Pole quality is closely related.Excessive aperture(>20μm)And porosity(>85%)Titanium base will be made big to the supporting role of aeroge
Big to reduce, the pore structure of aeroge is easy to collapse;Too small aperture(<0.5μm)And porosity(<40%)It can make the electricity prepared
The permeability of pole substantially reduces, and reduces the place to go effect of pollutant and the service life of electrode.After numerous tests, invention
People's discovery is only when the aperture of the POROUS TITANIUM substrate is when porosity is 40%~85%, to be prepared between 0.5~20 μm
Ti/ charcoal-aero gel/MnO2The permeability of electrode is best.The charcoal-aero gel and Ti base of three-dimensional network-like structure prepared by the present invention
Bottom is firmly combined, and hinders MnO2The generation of non-conductive hydrate film between Ti substrate, long service life and charcoal-aero gel is led
It is electrically good.
The present invention using POROUS TITANIUM substrate is support shuttering, charcoal-aero gel is carrier and NaMnO4It easily decomposes when heated
Property, dexterously solve MnO2It is easy to cause the microcellular structure of charcoal-aero gel to be easy collapsing when depositing on charcoal-aero gel
Problem prepares MnO on electrode2It is evenly distributed, charcoal-aero gel microcellular structure keeps good.Preparation method letter provided by the invention
Ti/ charcoal-aero gel/MnO that is single, environment friendly and pollution-free, being prepared2Electrode life is long.
Preferably, in S1, the aperture of the POROUS TITANIUM substrate is 1~10 μm, and porosity is 60~75%.
Preferably, in S1, the POROUS TITANIUM substrate with a thickness of 4~12mm.In the present invention, the mold thickness and big
It is small consistent with titanium-based material.
Preferably, in S2, the molar ratio of the resorcinol, formaldehyde and water is 1:2:25.
Preferably, in S2, the NaMnO4Additive amount be mixed solution gross mass 5~40%.
Preferably, in S4, the temperature of gelation is 45 DEG C, and time of repose is for 24 hours;The time of aging is 96h.
Preferably, in S5, the temperature program of charing is:Heating rate is 3 DEG C/min, is warming up to 790~820 DEG C, is kept
Time is 2~3h.
Preferably, in S1, the pretreatment is:POROUS TITANIUM substrate is placed in alkali cleaning 20 in 80 DEG C of 10% NaOH solution
Min removes surface and oil contaminant, then is placed in pickling in 88 DEG C of 5% oxalic acid solution, place to go oxidation film, then with deionized water ultrasound 10
min。
Preferably, in S5, the organic solvent of replacement in every 12 hours is repeated four days, then dries 3 days in air, wet solidifying
Moisture in glue is obtained after removing completely using POROUS TITANIUM as skeleton, load MnO2, dry gas gel with network structure.
Preferably, in S5, the small organic solvent of the surface tension is ethyl alcohol, acetone or n-hexane.
Ti/ charcoal-aero gel/MnO that the present invention protects above-mentioned preparation method to be prepared simultaneously2Electrode.
Above-mentioned Ti/ charcoal-aero gel/MnO2Electrode as efficient anode in degrading waste water in organic matter application also this
Within the protection scope of invention.By the Ti/ charcoal-aero gel/MnO2Applied to bisphenol-A, the acetparaminosalol in oxidative degradation water
The persistent organic pollutants such as phenol.It specifically includes:
With the Ti/ charcoal-aero gel/MnO2Electrode is anode, using copper or stainless steel substrate as cathode, adds 0.1 M Na2SO4Make
Supporting electrolyte, using constant current mode, current density is 2~30 mA/cm2, pole plate spacing is 5~25 mm, electroxidation drop
Organic pollutant in Xie Shui.
Compared with prior art, the present invention has the advantages that:
Preparation method preparation process provided by the invention is simple, prepares the painting of tin antimony middle layer in the process repeatedly without existing report
Cover-dry-calcination procedure.The charcoal-aero gel of Ti/ prepared by the present invention/MnO2Electrode performance is stablized, and Ti/MnO is compared2Electrode is shown
Longer service life out, for the bisphenol-A of 10~1000 mg/L, Electrooxidation degradation rate in 60min up to 98% or more, can
Realize the high-efficient purification of organic wastewater.
Detailed description of the invention
Fig. 1 is that the test life span comparison for the electrode that Examples 1 to 3 and comparative example 1 are prepared schemes.
Fig. 2 is Ti/ charcoal-aero gel/MnO prepared by the embodiment of the present invention 12To the Electrooxidation degradation effect picture of bisphenol-A.
Fig. 3 is Ti/ charcoal-aero gel/MnO prepared in the embodiment of the present invention 12The Ti/ being prepared with comparative example 1
SnO2–Sb/MnO2The contrast effect figure of electrode degrading perfluoro caprylic acid.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method
And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1
A kind of Ti/ charcoal-aero gel/MnO2The preparation method of electrode, includes the following steps:
(1)It is 1 μm by aperture, porosity 60%, is 3cm with a thickness of 5 mm, side length and the POROUS TITANIUM substrate of 5cm is placed in 80 DEG C
10% NaOH solution in 20 min of alkali cleaning, remove surface and oil contaminant, then be placed in pickling in 88 DEG C of 5% oxalic acid solution, place to go oxygen
Change film, then with 10 min of deionized water ultrasound;
(2)By Resorcino, formaldehyde, water with 1:2:The mixing of 25 molar ratios, is stirred with magnetic stirring apparatus with the speed of 350 rpm/min
15 min are mixed, solution is mixed, NaMnO4Dosage is 6%, NaMnO of mixed liquor gross mass4After being completely dissolved, continue stirring 20
min;
(3)By step(1)Pretreated POROUS TITANIUM substrate and step(2)It is 3cm × 5 that the mixed solution of preparation, which pours into volume,
In the organic mold of the mm of cm × 5, the Na that mass fraction is 10% is added dropwise2CO3Aqueous solution makes the pH 7.0 of solution;
(4)Then, by step(3)In organic mold be put into stand in 45 DEG C of thermostat water bath and carry out gelation for 24 hours, 85 DEG C
Thermostat water bath in 96h carry out aging, while NaMnO4It is heated that selfdecomposition reaction generation MnO occurs2, organic mold is removed,
Obtain Ti/ phenolic resin/MnO2Wet gel;
(5)By step(4)Obtained Ti/ phenolic resin/MnO2Wet gel impregnates in 35 DEG C of acetone solns, replaces within every 12 hours
Acetone repeats 4 days, then dries 3 days in air, obtains blocky dry gas gel;Then the xerogel prepared is put into tubular type
It is carbonized in furnace, in N2Under the protection that atmosphere is enclosed, temperature programming is carried out, heating rate is 3 DEG C/min, 800 DEG C is warming up to, when holding
Between be 2 hours, Ti/ charcoal-aero gel/MnO is obtained after cooling2。
Ti/ charcoal-aero gel/MnO that the present embodiment obtains2Preparation process is simple, and electrode performance is stablized, and the test service life is super
Cross 650h, hence it is evident that the Ti/SnO being prepared greater than comparative example 12–Sb/MnO2(Fig. 1), this may be due to MnO2Particle dispersion
Property it is good, the associativity of charcoal-aero gel and substrate is secured so that electrode life increase.
Embodiment 2
A kind of Ti/ charcoal-aero gel/MnO2The preparation method of electrode, includes the following steps:
(1)It is 15 μm by aperture, porosity 80%, is 3cm with a thickness of 5 mm, side length and the POROUS TITANIUM substrate of 5cm is placed in 80 DEG C
10% NaOH solution in 20 min of alkali cleaning, remove surface and oil contaminant, then be placed in pickling in 88 DEG C of 5% oxalic acid solution, place to go oxygen
Change film, then with 10 min of deionized water ultrasound;
(2)By Resorcino, formaldehyde, water with 1.1:2.4:18 molar ratios mixing, with magnetic stirring apparatus with the speed of 350 rpm/min
Degree 15 min of stirring, mix solution, NaMnO4Dosage is 20%, NaMnO of mixed liquor gross mass4After being completely dissolved, continue
Stir 20 min;
(3)By step(1)Pretreated POROUS TITANIUM substrate and step(2)It is 3cm × 5 that the mixed solution of preparation, which pours into volume,
In the organic mold of the mm of cm × 5, the NaOH aqueous solution that mass fraction is 10% is added dropwise, makes the pH 7.5 of solution;
(4)Then, by step(3)In organic mold be put into 30 DEG C of thermostat water bath stand 48h carry out gelation, 95 DEG C
Thermostat water bath in 48h carry out aging, while NaMnO4It is heated that selfdecomposition reaction generation MnO occurs2, organic mold is removed,
Obtain Ti/ phenolic resin/MnO2Wet gel;
(5)By step(4)Obtained Ti/ phenolic resin/MnO2Wet gel impregnates in 35 DEG C of ethanol solutions, replaces within every 12 hours
Ethyl alcohol repeats 4 days, then dries 3 days in air, obtains blocky dry gas gel;Then the xerogel prepared is put into tubular type
It is carbonized in furnace, in N2Under the protection that atmosphere is enclosed, temperature programming is carried out, heating rate is 3 DEG C/min, 800 DEG C is warming up to, when holding
Between be 2 hours, Ti/ charcoal-aero gel/MnO is obtained after cooling2。
Ti/ charcoal-aero gel/MnO that the present embodiment obtains2Preparation process is simple, electrode performance stablize, test the service life be
450h, slightly below embodiment 1, the POROUS TITANIUM matrix aperture ratio embodiment 1 used this is mainly due to the embodiment is much larger, leads
POROUS TITANIUM is caused to weaken the supporting role of charcoal-aero gel, but its service life is significantly greater than the Ti/SnO that comparative example 1 is prepared2–Sb/
MnO2(Fig. 1).
Embodiment 3
A kind of Ti/ charcoal-aero gel/MnO2The preparation method of electrode, includes the following steps:
(1)It is 0.5 μm by aperture, porosity 40%, is 3cm with a thickness of 5 mm, side length and the POROUS TITANIUM substrate of 5cm is placed in 80
DEG C 10% NaOH solution in 20 min of alkali cleaning, remove surface and oil contaminant, then be placed in pickling in 88 DEG C of 5% oxalic acid solution, place to go
Oxidation film, then with 10 min of deionized water ultrasound;
(2)By Resorcino, formaldehyde, water with 1:2.4:30 molar ratios mixing, with magnetic stirring apparatus with the speed of 350 rpm/min
15 min are stirred, solution is mixed, NaMnO4Dosage is 40%, NaMnO of mixed liquor gross mass4After being completely dissolved, continue to stir
Mix 20 min;
(3)By step(1)Pretreated POROUS TITANIUM substrate and step(2)It is 3cm × 5 that the mixed solution of preparation, which pours into volume,
In the organic mold of the mm of cm × 5, the Na that mass fraction is 10% is added dropwise2CO3Aqueous solution makes the pH 7.3 of solution;
(4)Then, by step(3)In organic mold be put into stand in 60 DEG C of thermostat water bath and carry out gelation for 24 hours, 80 DEG C
Thermostat water bath in 96h carry out aging, while NaMnO4It is heated that selfdecomposition reaction generation MnO occurs2, organic mold is removed, is obtained
To Ti/ phenolic resin/MnO2Wet gel;
(5)By step(4)Obtained Ti/ phenolic resin/MnO2Wet gel impregnates in 35 DEG C of hexane solutions, and every 12 hours more
A n-hexane is changed, is repeated 4 days, then is dried 3 days in air, blocky dry gas gel is obtained;Then the xerogel prepared is put into
It is carbonized in tube furnace, in N2Under the protection that atmosphere is enclosed, temperature programming is carried out, heating rate is 3 DEG C/min, is warming up to 820 DEG C, protects
Holding the time is 2 hours, and Ti/ charcoal-aero gel/MnO is obtained after cooling2。
Ti/ charcoal-aero gel/MnO that the present embodiment obtains2Preparation process is simple, electrode performance stablize, test the service life be
550h, service life are significantly greater than the Ti/SnO that comparative example 1 is prepared2–Sb/MnO2(Fig. 1).
1 Ti/ charcoal-aero gel of application examples/MnO2Electrode is for bisphenol-A autogamy waste water of degrading
Ti/ charcoal-aero gel/MnO that embodiment 1 is prepared2Electrode is for bisphenol-A autogamy waste water of degrading, and biodegrading process is such as
Under:
Prepare the bisphenol-A and 0.1 M Na for containing 200 g/L2SO4Solution, with Ti/ charcoal-aero gel/MnO2Electrode is anode, with stainless
Steel substrate is cathode, using constant current mode, current density 15mA/cm2, pole plate spacing is 20 mm, chromatography result table
Bright, after 60 min, the removal rate of bisphenol-A is up to 99% or more.
In order to guarantee that the experimental result of embodiment has comparability, the present embodiment also be compared with comma coating method preparation
Ti /MnO2The degradation effect to bisphenol-A, manganese source used be Mn (NO3)2, other experiment conditions are all the same, as a result such as Fig. 2 institute
Show.Ti/ charcoal-aero gel/MnO provided by the present invention2The significant effect of electrode degrading bisphenol-A is higher than general T i/MnO2, the former
Rate constant be 11.6 times of the latter.
2 Ti/ charcoal-aero gel of application examples/MnO2Electrode is for the dyeing waste water containing rhodamine B of degrading
Ti/ charcoal-aero gel/MnO that embodiment 1 is prepared2Electrode is for the dyeing waste water containing rhodamine B of degrading, degradation
Method is the same as application examples 1.After 35 min, the dyeing waste water containing rhodamine B is degradable, total organic Carbon removal 60%.
Comparative example 1
The comparative example is originated from reported in literature(Lin H, Niu J, Ding S, et al. Electrochemical
degradation of perfluorooctanoic acid (PFOA) by Ti/SnO2–Sb, Ti/SnO2–Sb/PbO2
and Ti/SnO2–Sb/MnO2anodes[J]. Water research, 2012, 46(7): 2281-2289.).
This report coats SnCl by 18 times using sol-gel method repeatedly4、SbCl3It is prepared for the Ti/ with middle layer
SnO2–Sb/MnO2Anode, to increase its service life, the removal rate that 90 min are electrolysed PFOA is only 31.7%.And the present invention is implemented
Ti/ charcoal-aero gel/MnO that example 1 is prepared2For anode to 90 min of removal rate of PFOA up to 99.5%, place to go efficiency is obviously high
In the comparative example, and electrode life ratio Ti/SnO2–Sb/MnO2It greatly improves(As shown in Figure 3).
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.