CN104211138A - Method for preparing membrane electrode based on carbon nanotubes and electrolytic removal method of organic pollutants with membrane electrode - Google Patents
Method for preparing membrane electrode based on carbon nanotubes and electrolytic removal method of organic pollutants with membrane electrode Download PDFInfo
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Abstract
The invention relates to a method for preparing a membrane electrode based on carbon nanotubes and an application technology of the membrane electrode in the aspect of sewage treatment. The invention is basically characterized in that filtering is carried out while catalytic degradation of organic pollutants flowing through fenestra is carried out by the combination of filter membrane and electro-catalysis techniques. According to the invention, carbon nanotubes are firstly pretreated, the pretreated carbon nanotubes are uniformly dispersed in an organic solvent, and a carbon nanotube membrane is prepared by steps of vacuum filtration, cleaning and the like; the carbon nanotube membrane is assembled in a plate-type filtration reactor, a DC power supply is connected, and sewage drowns out the membrane electrode through a pump. The carbon nanotube membrane electrode has large specific surface area and nanoscale voids. Pollutants flow through the nanoscale voids among the carbon nanotubes to be filtered while organic pollutants can effectively be degraded by an electric field loaded on each carbon nanotube. According to the invention, mass transfer efficiency is raised effectively; large specific surface area of the carbon nanotube membrane is utilized fully; and efficient low-consumption catalytic degradation of organic pollutants is achieved at the pressure far lower than routine operating voltage of a two-dimensional parallel-plate electrode. The technology can widely be used in dye wastewater and phenolic wastewater.
Description
Technical field
The present invention relates to the method preparing membrane electrode based on carbon nanotube, and this membrane electrode is used for Electrocatalysis Degradation organic pollutant, is a kind of green technology combining membrane filtration and electrocatalysis.
Background technology
For a long time, for the miscellaneous organic wastewater with difficult degradation thereby of China, still lack the Treatment process of economical and efficient on the whole, these waste water are often unprocessed or only after simple process, directly enter environment, pollute the natural water body that we depend on for existence, compromise HUMAN HEALTH.In the face of this challenge, urgently develop novel material, new technology and novel process and in field of waste water treatment, this become that developing national economy preserves the ecological environment in the urgent need to.
Electrocatalysis Degradation organic pollutant has the development course of decades, itself is not a new technology.It does not need, and additional chemical oxidizing agent, non-secondary pollution, equipment are simple, controllability good and run under normal temperature and pressure, therefore receive much concern at sewage treatment area.But for a long time owing to being subject to the restrictions such as reactor mass-transfer efficiency, electrode materials and electrode side reaction, the energy consumption of By Electrocatalytic Oxidation degradable organic pollutant is large, running cost is high, thus this method also fails to play its due potential advantages and process effect at present, need badly at present reduce energy consumption just likely large-scale application in treatment of Organic Wastewater field.For this reason, Development of Novel reactor to improve electrode materials be one of important approach.
Carbon nanotube (CNT) is as a kind of type material with high strength, bigger serface, excellent mechanical property, good conductive capability and electrochemical activity, since last century, the nineties was found, its huge potential using value obtains to be paid close attention to widely.Only 2011, article more than 24000 section relevant to carbon nanotube is delivered in the whole world, granted patent more than 2000 example, about its application and theoretical investigation mainly concentrate on the fields such as matrix material, specific adsorption parting material, support of the catalyst, hydrogen storage, battery, ultracapacitor, electron device, sensor and microscope probe, and many impressive progresses are obtained.And by carbon nanotube through suitable regulation and control and functionalization, be applied in electrolysis organic waste water as novel electrode, to likely present different chemical properties, after finding carbon nanotube from 1991 soon, namely having with carbon nanotube is the report of electrode degrading organic waste water, subsequently for the research rapid temperature increases of this technology.But research in the past mostly be by carbon nanotube by method loads such as sol-gel, hydro-thermal, galvanic deposit on matrix, as titanium plate obtains, utilization are all outer wall performances of carbon nanotube.And correspondingly, reactor also adopts traditional electrolyzer, i.e. two-dimensional parallel plate electrode system.Obviously within the system, pollutent is only flow through electrode surface, and by the restriction of diffusibility, it is inner that it not easily reaches porous carbon nanotube electrode, and what cause porous electrode in traditional electrolyte pond actually utilizes that area is little, efficiency is low.And pollutent is delivered to the prerequisite and basis that electrode surface is electrochemical degradation, improving mass transfer condition has obvious effect to raising electrochemical treatment efficiency reduction energy consumption.If the waste water containing pollutent can be allowed directly to pass porous carbon nanotube films electrode, and be not only the electrode surface that flows through in traditional electrolyte pond, this can shorten the distance of Pollutants Diffusion to electrode surface, the thickness of liquid film of reduction electrode surface quiescent layers, finally will improve mass-transfer efficiency greatly and the actual of porous carbon nanotube films utilizes area.Therefore prepare carbon nanotube porous-film, be assemblied in plate filter, and for Electrocatalysis Degradation organic waste water, will be the striving direction of this invention.
Summary of the invention
The present invention designs a kind of electro-catalysis membrane based on carbon nanotube of preparation, and film integral thickness about 6 ~ 280 μm, the hole between carbon nanotube is 50 ~ 100nm, and specific surface area is 100 ~ 800m about
2/ g (see Figure of description 1).The residence time 0.1-10 second of organic pollutant in carbon nano-tube film, be diffused into the time (2.14 μ s) of carbon nano tube surface much larger than pollutent (50 ~ 100nm) in carbon nanotube level gap.Then this carbon nano-tube film is assemblied on the device being similar to Plate Filtration as anode, and titanium ring is pressed over the carbon nanotube film as terminal stud connection power supply, in addition using porous stainless steel plate or another carbon nano-tube film as negative electrode, constitute whole electrode system; Then sewage is added by peristaltic pump with certain flow velocity, waste water containing organic pollutant is by the nanoscale gap of carbon nano-tube film, the carbon nanotube that every velamen is loaded with electric field all can regard a nanometer micro-electrode as, absorption electrolysis organic pollutant (see Figure of description 2), the carbon nano-tube film of such high dispersive, bigger serface can degradable organic pollutant effectively.
The preparation process of carbon nano-tube film is summarized as follows:
(1) selection of carbon nanotube: many walls or Single Walled Carbon Nanotube; Outer tube diameter (5-50nm); Ash oontent (1-10%);
Surface functional groups (hydroxyl, carboxyl, carbonyl etc.).
(2) pre-treatment--calcining: in order to remove decolorizing carbon in CNT and other carbon-containing impurities, first CNT is placed in tube furnace in experiment to calcine, from room temperature, 300 ~ 400 DEG C are warming up to the speed program of 1 ~ 20 DEG C/min, and calcining 30 ~ 120min is continued at 300 ~ 400 DEG C, then naturally cool to room temperature;
(3) pre-treatment--pickling: for removing metal oxide on carbon nanotube and other impurity further, further acidification is carried out to the carbon nanotube after calcining.Concrete grammar is: carbon nanotube is placed in round-bottomed flask, adds the hydrochloric acid (or 35% ~ 70% nitric acid, the sulfuric acid of 45 ~ 98%, or the mixture of these sour different ratioss) that concentration is 15% ~ 37%, and reflux at 50 ~ 90 DEG C 5 ~ 24h; After having heated, allow sample be cooled to room temperature, then through vacuum filtration by the carbon nanotube suction filtration after acidifying in the PTFE film in aperture, then use washed with de-ionized water suction filtration, until filter after water outlet pH weakly acidic pH; Finally the carbon nanotube after cleaning is collected, to be positioned in air dry oven kept dry at 60 DEG C for subsequent use.
(4) film forming: first carbon nanotube is dispersed in the mixed solvent of the single or arbitrary proportion of DMSO (or DMF, NMP, ethanol, hexane, toluene) through ultrasonic apparatus, then by vacuum filtration, carbon nanotube is coated on the filter membranes such as PTFE, then dehydrated alcohol, dehydrated alcohol/water, deionized water drip washing suction filtration is used successively, take out after cleaning completely, and suppress film 1 ~ 60min under pressure, finally obtain carbon nanotube membrane electrode; Density is about 0.2 ~ 10mg/cm
2, thickness about 6 ~ 280 μm, the hole between carbon nanotube is 50 ~ 100nm, and specific surface area is 100 ~ 800m about
2/ g.
(5) study on its developing of electrochemical reactor: then this carbon nano-tube film is assemblied on the device being similar to Plate Filtration as anode, and titanium ring is pressed over the carbon nanotube film as terminal stud connection power supply, in addition using porous stainless steel plate or another carbon nano-tube film as negative electrode, constitute whole electrode system, also comprise rubber ring pad in addition, seal; Titanium ring mainly plays electric action, connects negative electrode and anode and external circuit, and forms loop.Then add sewage by peristaltic pump with certain flow velocity, the carbon nanotube that every velamen is loaded with electric field all can regard a nanometer micro-electrode as, and absorption is electrolysis organic pollutant also.
Accompanying drawing explanation
Fig. 1. the material object of carbon nanotube membrane electrode and SEM figure
Be that carbon nanotube is dispersed in DMSO equal solvent through high-energy ultrasonic instrument in example, then by vacuum filtration, carbon nanotube be coated on the filter membranes such as PTFE, be i.e. obtained carbon nano-tube film, namely usually said " Buckie paper ".Film integral thickness about 50 μm, the hole between carbon nanotube is 50 ~ 100nm, and specific surface area is 100 ~ 800m about
2/ g.
Fig. 2. carbon nanotube membrane electrode uses schematic diagram
Then this carbon nano-tube film is assemblied on the device being similar to Plate Filtration as anode, and titanium ring is pressed over the carbon nanotube film as terminal stud connection power supply, in addition using porous stainless steel plate or another carbon nano-tube film as negative electrode, constitute whole electrode system; Then add sewage by peristaltic pump with certain flow velocity, force the waste water containing pollutent by the nanoscale gap of carbon nano-tube film, the carbon nanotube that every velamen is loaded with electric field all can regard a nanometer micro-electrode as.
The schematic diagram directly perceived of Fig. 3 carbon nano-tube film electrode degrading tropeolin-D and removal efficiency
For observing the performance of carbon nano-tube film electrode catalyst degradation of contaminant intuitively, first we select tropeolin-D as simulating pollution thing, carries out related experiment.Under not making alive, run methyl orange solution after 20 minutes and namely penetrate membrane electrode because adsorbing saturated, from figure below, visible water outlet is in yellow; And when improving voltage to 3V, tropeolin-D can almost have been removed completely, water outlet is in colourless.
Embodiment
Exemplifying embodiment 1.
Select 5g external diameter to be that the multi-walled carbon nano-tubes of 17nm puts into tube furnace, from room temperature, be warming up to 400 DEG C with the speed program of 5 DEG C/min, and at 400 DEG C, continue calcining 60min, then naturally cool to room temperature; Then get 1g and put into hydrochloric acid flask containing 500mL37%, the 24h that refluxes at 70 DEG C refluxes 24h, sample is cooled to room temperature, then in the PTFE film that the carbon nanotube suction filtration after acidifying to aperture is 5 μm by vacuum filtration, then washed with de-ionized water suction filtration is used, until water outlet pH weakly acidic pH after filter; Get the carbon nanotube after 15mg acidifying through ultrasonic disperse in DMSO, then by vacuum filtration, carbon nanotube is coated on the filter membranes such as PTFE, then dehydrated alcohol, dehydrated alcohol-water (V/V=1:1), deionized water drip washing suction filtration is used successively, after taking-up, suppress 15min under pressure, finally obtain the carbon nanotube membrane electrode prepared.
Be assemblied in this carbon nano-tube film as anode on the device being similar to Plate Filtration, stainless steel is as negative electrode; And with the tropeolin-D of 1mM (MO) for simulating pollution thing, the sodium sulfate of 10mM is ionogen, squeezes in reactor by peristaltic pump (flow velocity 1.5mL/min) by above-mentioned solution; Switch on power, when voltage 2V and 3V, the clearance of MO is respectively 74% and 95% simultaneously.
Exemplifying embodiment 2.
The preparation method of carbon nanotube membrane electrode is the same.
And with the phenol of 1mM for simulating pollution thing, the sodium sulfate of 10mM is ionogen, squeezes in reactor by peristaltic pump (flow velocity 1.5mL/min) by above-mentioned solution; Under 3V voltage, clearance 81%, the TOC clearance 69% of phenol.
Claims (7)
1. prepare the method for membrane electrode and the technology for organic pollutant Electrocatalysis Degradation thereof based on carbon nanotube for one kind, its feature is as follows: first the present invention optimizes, activated carbon nano-tube, and it is in organic solvent dispersed, carbon nano-tube film is obtained again by the step such as vacuum filtration, cleaning, then this carbon nano-tube film is assemblied in the reactor of plate-type filtering, and connect direct supply, and by pump, sewage is pressed through membrane electrode.While the pollutent nano level hole flow through between carbon nanotube is filtered, the electric field that every root carbon nanotube is loaded can degradable organic pollutant effectively.
2. according to claim 1, its pre-treatment and preferred feature as follows: with many walls or Single Walled Carbon Nanotube for starting material, outer tube diameter is between 5 ~ 50nm, and ash oontent is between 1 ~ 10%; Surface functional groups hydroxyl, carboxyl, carbonyl wherein one or more.
3. according to claim 1, its pre-treatment comprises calcining, feature is as follows: in order to remove decolorizing carbon in CNT and other carbon-containing impurities, CNT is placed in tube furnace calcine, from room temperature, be warming up to 300 ~ 400 DEG C with the speed program of 1 ~ 20 DEG C/min, and continue calcining 30 ~ 120min at 300 ~ 400 DEG C, then naturally cool to room temperature.
4. according to claim 1, its pre-treatment comprises pickling, and feature is as follows: for removing metal oxide on carbon nanotube and other impurity further, carry out acidification further to the carbon nanotube after calcining.Specific features is: carbon nanotube is placed in round-bottomed flask, adds the hydrochloric acid (or 35% ~ 70% nitric acid, the sulfuric acid of 45 ~ 98%, or the mixture of these sour different ratioss) that concentration is 15% ~ 37%, and reflux at 50 ~ 90 DEG C 5 ~ 24h; After having heated, allow sample be cooled to room temperature, then through vacuum filtration by the carbon nanotube suction filtration after acidifying in the PTFE film in aperture, then use washed with de-ionized water suction filtration, until filter after water outlet pH weakly acidic pH.
5. according to claim 1, its film-forming process feature comprises: be first dispersed in by carbon nanotube in the mixed solvent of the single or arbitrary proportion of DMSO (or DMF, NMP, ethanol, hexane, toluene) through ultrasonic apparatus, then by vacuum filtration, carbon nanotube is coated on the filter membranes such as PTFE, then dehydrated alcohol, dehydrated alcohol/water, deionized water drip washing suction filtration is used successively, take out after cleaning completely, and suppress film 1 ~ 60min under pressure, finally obtain carbon nanotube membrane electrode.
6. the feature of the carbon nano-tube film according to claim 1, obtained comprises: density is about 0.2 ~ 10mg/cm
2, thickness about 6 ~ 280 μm, the hole between carbon nanotube is 50 ~ 100nm, and specific surface area is 100 ~ 800m about
2/ g.
7. according to claim 1, the study on its developing feature of electrochemical reactor comprises: as anode on the device this carbon nano-tube film being assemblied in Plate Filtration, and is pressed by titanium ring and connect power supply as terminal stud over the carbon nanotube film; Using porous stainless steel plate or another carbon nano-tube film as negative electrode, form whole electrode system; Also comprise rubber ring pad in addition, seal; Titanium ring mainly plays electric action, connects negative electrode and anode and external circuit, and forms loop; Peristaltic pump is with 0.01 ~ 1.0mL/cm
2the flow velocity of-min adds sewage; Operating voltage is between 1.5V ~ 4.0V.
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| CN104211138B (en) | 2019-04-23 |
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