CN102728330A - Preparation method for carbon nanometer material with adsorption performance - Google Patents
Preparation method for carbon nanometer material with adsorption performance Download PDFInfo
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Abstract
The invention discloses a preparation method for a carbon nanometer material with an adsorption performance, and belongs to the technical field of organic adsorption material preparation. The preparation method disclosed by the invention is characterized in that graphite material is gradually peeled into small carbon nanometer particles under the action of electrolyte and current with an electrochemistry anodic oxidation method under a certain voltage and electrolyte condition, and the small carbon nanometer particles are separated and dried with methods of filtering, drying in vacuum and the like, so the carbon nanometer material with adsorption can be prepared. The adsorption performance of the carbon nanometer material prepared with the preparation method is obviously improved. The method has the advantages that the raw material has low cost and is abundant in nature, the device is simple and easy to operate, and the environmental friendliness is realized.
Description
Technical field
The present invention relates to a kind of preparation method, belong to inorganic adsorbing material fabricating technology field with carbon nanomaterial of absorption property.Be specifically related to a kind ofly have preparation method than the nano-carbon material of high absorption property for dyestuff.
Background technology
Got into since the twentieth century, human industrial civilization is able to fast development, and the energy crisis and the environmental pollution that cause thus become problem demanding prompt solution.Therefore developing cleaning, low energy consumption, high efficiency and can realizing the energy conversion of suitability for industrialized production and pollute treatment technology is the target that scientist and national governments pursue and pay close attention to.Pollution treatment method commonly used at present mainly contains physics method, method of chemical treatment, physical-chemical process and biological treatment etc.; Wherein absorption method is a pollution treatment method comparatively commonly used in the physical-chemical process; Applied range is arranged, the advantage that method of operating is simple and result of use is good.Having adsorbing material has a lot, and material with carbon element occupies very important low level in adsorbing domain.Common material with carbon element adsorbent comprises active carbon, ketjenblack EC, porous carbon materials, carbon molecular sieve, carbon back porous polymer.In recent years; Existing a lot of to the research of carbon nanomaterials such as Nano carbon balls, CNT, carbon nanosheet; The research of different field all more or less confirmation the value of carbon nanomaterial; Yet be adsorbed with carbon nanomaterial in the processing of organic pollutants as adsorbent and application, a lot of problems such as the selection of carbon nanomaterial, adsorption conditions also are worth doing further exploration.
The traditional preparation process method of carbon current nano material has arc discharge method, catalystic pyrolysis and template or the like.These methods not only require high temperature, high vacuum, and complex apparatus and strict experimental arrangement, and also reappearance is relatively poor, is difficult to control the pattern of material, has greatly hindered their widespread usage.
Summary of the invention
The objective of the invention is to shortcoming and defect, a kind of preparation method with carbon nanomaterial of absorption property is provided to existing material with carbon element adsorption technology.
The step of the inventive method is:
The step 1) electrolysis: the DC stable power supply anode is connect graphite rod, and negative electrode connects graphite cake, with test tube clamp graphite rod and graphite cake is fixed in the beaker that is placed with 250-1000mL electrolyte.
After in beaker, putting into magnetic agitation, place it on the magnetic stirring apparatus, energized is regulated DC stable power supply, and starting voltage is 4.0-8.0V.When graphite rod is consumed to total length 1/5, turn off power supply and magnetic stirring apparatus.
Step 2) filters:, go to use the distilled water rinsing after the supernatant, after leaving standstill once more step 1) gained solution left standstill deposition; Rinsing once more, through rinsing repeatedly, with the pH test paper measure solution acid-basicity up to it when neutral; Neutral solution is filtered, filter residue is moved in the evaporating dish.
Step 3) drying: with step 2) the gained filter residue is put into vacuum drying chamber, regulates temperature 60-90 degree, under vacuum condition, takes out after dry 5-8 hour, promptly obtains having the carbon nanomaterial of absorption property.
Furtherly, described water solution system preferably sulfuric acid solution.
Beneficial effect of the present invention:
The present invention has that equipment is simple, reaction rate is fast, can carry out at normal temperatures and pressures, cost is low, eco-friendly advantage, is expected to carry out suitability for industrialized production.The absorption property of the carbon nanomaterial tool of gained has had and has significantly improved, and in the organic pollution adsorbing domain good prospects for application is arranged.
Description of drawings
Fig. 1 is Electronic Speculum (SEM) figure of embodiment 4 gained carbon nanomaterials;
Fig. 2 is Electronic Speculum (SEM) figure of embodiment 7 gained carbon nanomaterials;
Fig. 3 is Electronic Speculum (SEM) figure of 10 carbon nanomaterials of embodiment;
Fig. 4 is embodiment 4,7, the N of 10 gained carbon nanomaterials
2Adsorption isothermal curve figure;
Fig. 5 is embodiment 4,7, and 10 gained carbon nanomaterials and absorbent charcoal material are to the absorption property comparison diagram of methyl orange absorption.
The specific embodiment
Specify the present invention according to specific embodiment below, it is more obvious that the object of the invention and effect will become.
Embodiment 1
1) anodic oxidation of carbon nanomaterial: the 6.94mL concentrated sulfuric acid is dissolved in the distilled water of 50mL, and adds a certain amount of distilled water and be settled in the volumetric flask of 250mL the electrolyte that obtains clarifying; (dimension D 5 * 100mm) is an anode with graphite rod; (size 10 * 2 * 100mm) is a negative electrode to graphite flake; Be fixed in the beaker that is placed with the 250mL sulfuric acid electrolyte with test tube clamp, be placed on the magnetic stirring apparatus energized after putting into magnetic agitation; Regulate DC stable power supply, starting voltage is 4.0V.
2) filtration: graphite rod is consumed to residue 1/5 o'clock, with the solution left standstill deposition of dissolving graphite powder, goes to use the distilled water rinsing after the supernatant, and after leaving standstill once more, rinsing once more, through rinsing repeatedly, it is approaching neutral up to it to measure solution acid-basicity with the pH test paper.
3) vacuum drying: with step 2) gained neutral solution is filtered, and puts into vacuum drying chamber after filter residue is moved into evaporating dish, regulates temperature 60 degree, and taking-up after dry 8 hours under vacuum condition promptly obtains having the carbon nanomaterial of absorption property.It is subsequent use that prepared carbon nanomaterial is put into the drier that fills silica gel.
Embodiment 2
1) anodic oxidation of carbon nanomaterial: the 6.94mL concentrated sulfuric acid is dissolved in the distilled water of 50mL, and adds a certain amount of distilled water and be settled in the volumetric flask of 500mL the electrolyte that obtains clarifying; (dimension D 5 * 100mm) is an anode with graphite rod; (size 10 * 2 * 100mm) is a negative electrode to graphite flake; Be fixed in the beaker that is placed with the 250mL sulfuric acid electrolyte with test tube clamp, be placed on the magnetic stirring apparatus energized after putting into magnetic agitation; Regulate DC stable power supply, starting voltage is 4.0V.
2) filtration: graphite rod is consumed to residue 1/5 o'clock, with the solution left standstill deposition of dissolving graphite powder, goes to use the distilled water rinsing after the supernatant, and after leaving standstill once more, rinsing once more, through rinsing repeatedly, it is approaching neutral up to it to measure solution acid-basicity with the pH test paper.
3) vacuum drying: with step 2) gained neutral solution is filtered, and puts into vacuum drying chamber after filter residue is moved into evaporating dish, regulates temperature 70 degree, and taking-up after dry 8 hours under vacuum condition promptly obtains having the carbon nanomaterial of absorption property.It is subsequent use that prepared carbon nanomaterial is put into the drier that fills silica gel.
Embodiment 3
1) anodic oxidation of carbon nanomaterial: the 6.94mL concentrated sulfuric acid is dissolved in the distilled water of 50mL, and adds a certain amount of distilled water and be settled in the volumetric flask of 1000mL the electrolyte that obtains clarifying; (dimension D 5 * 100mm) is an anode with graphite rod; (size 10 * 2 * 100mm) is for being negative electrode for graphite flake; Be fixed in the beaker that is placed with the 250mL sulfuric acid electrolyte with test tube clamp, be placed on the magnetic stirring apparatus energized after putting into magnetic agitation; Regulate DC stable power supply, starting voltage is 4.0V.
2) filtration: graphite rod is consumed to residue 1/5 o'clock, with the solution left standstill deposition of dissolving graphite powder, goes to use the distilled water rinsing after the supernatant, and after leaving standstill once more, rinsing once more, through rinsing repeatedly, it is approaching neutral up to it to measure solution acid-basicity with the pH test paper.
3) vacuum drying: with step 2) gained neutral solution is filtered, and puts into vacuum drying chamber after filter residue is moved into evaporating dish, regulates temperature 90 degree, and taking-up after dry 8 hours under vacuum condition promptly obtains having the carbon nanomaterial of absorption property.It is subsequent use that prepared carbon nanomaterial is put into the drier that fills silica gel.
Embodiment 4
1) anodic oxidation of carbon nanomaterial: the 6.94mL concentrated sulfuric acid is dissolved in the distilled water of 50mL, and adds a certain amount of distilled water and be settled in the volumetric flask of 250mL the electrolyte that obtains clarifying; (dimension D 5 * 100mm) is an anode with graphite rod; (size 10 * 2 * 100mm) is a negative electrode to graphite flake; Be fixed in the beaker that is placed with the 250mL sulfuric acid electrolyte with test tube clamp, be placed on the magnetic stirring apparatus energized after putting into magnetic agitation; Regulate DC stable power supply, starting voltage is 7.2V.
2) filtration: graphite rod is consumed to residue 1/5 o'clock, with the solution left standstill deposition of dissolving graphite powder, goes to use the distilled water rinsing after the supernatant, and after leaving standstill once more, rinsing once more, through rinsing repeatedly, it is approaching neutral up to it to measure solution acid-basicity with the pH test paper.
3) vacuum drying: with step 2) gained neutral solution is filtered, and puts into vacuum drying chamber after filter residue is moved into evaporating dish, regulates temperature 70 degree, and taking-up after dry 8 hours under vacuum condition promptly obtains having the carbon nanomaterial of absorption property.It is subsequent use that prepared carbon nanomaterial is put into the drier that fills silica gel.
4) sample topography is measured: the prepared carbon nanomaterial of step 3) is carried out sample topography measure on Zeiss SUPRA 40/40VP type ZEISS SEM ESEM, the result sees Fig. 1.
5) specific area measuring: use N
2Adsorption isotherm is used for characterizing the specific area of carbon nanomaterial.Test is carried out on Micromeritics ASAP2020 specific surface analyzer, through test N
2The adsorption-desorption capacity of gas when normal pressure and 77K obtains the specific area of carbon nanomaterial, and the result sees Fig. 4.
1) anodic oxidation of carbon nanomaterial: the 6.94mL concentrated sulfuric acid is dissolved in the distilled water of 50mL, and adds a certain amount of distilled water and be settled in the volumetric flask of 500mL the electrolyte that obtains clarifying; (dimension D 5 * 100mm) is an anode with graphite rod; (size 10 * 2 * 100mm) is a negative electrode to graphite flake; Be fixed in the beaker that is placed with the 250mL sulfuric acid electrolyte with test tube clamp, be placed on the magnetic stirring apparatus energized after putting into magnetic agitation; Regulate DC stable power supply, starting voltage is 8.0V.
2) filtration: graphite rod is consumed to residue 1/5 o'clock, with the solution left standstill deposition of dissolving graphite powder, goes to use the distilled water rinsing after the supernatant, and after leaving standstill once more, rinsing once more, through rinsing repeatedly, it is approaching neutral up to it to measure solution acid-basicity with the pH test paper.
3) vacuum drying: with step 2) gained neutral solution is filtered, and puts into vacuum drying chamber after filter residue is moved into evaporating dish, regulates temperature 90 degree, and taking-up after dry 8 hours under vacuum condition promptly obtains having the carbon nanomaterial of absorption property.It is subsequent use that prepared carbon nanomaterial is put into the drier that fills silica gel.
Embodiment 6
1) anodic oxidation of carbon nanomaterial: 75.75g potassium nitrate is dissolved in the distilled water of 50mL, and adds a certain amount of distilled water and be settled in the volumetric flask of 250mL the electrolyte that obtains clarifying; (dimension D 5 * 100mm) is an anode with graphite rod; (size 10 * 2 * 100mm) is a negative electrode to graphite flake; Be fixed in the beaker that is placed with the 250mL sulfuric acid electrolyte with test tube clamp, be placed on the magnetic stirring apparatus energized after putting into magnetic agitation; Regulate DC stable power supply, starting voltage is 7.2V.
2) filtration: graphite rod is consumed to residue 1/5 o'clock, with the solution left standstill deposition of dissolving graphite powder, goes to use the distilled water rinsing after the supernatant, and after leaving standstill once more, rinsing once more, through rinsing repeatedly, it is approaching neutral up to it to measure solution acid-basicity with the pH test paper.
3) vacuum drying: with step 2) gained neutral solution is filtered, and puts into vacuum drying chamber after filter residue is moved into evaporating dish, regulates temperature 60 degree, and taking-up after dry 8 hours under vacuum condition promptly obtains having the carbon nanomaterial of absorption property.It is subsequent use that prepared carbon nanomaterial is put into the drier that fills silica gel.
Embodiment 7
1) anodic oxidation of carbon nanomaterial: 75.75g potassium nitrate is dissolved in the distilled water of 50mL, and adds a certain amount of distilled water and be settled in the volumetric flask of 250mL the electrolyte that obtains clarifying; (dimension D 5 * 100mm) is an anode with graphite rod; (size 10 * 2 * 100mm) is a negative electrode to graphite flake; Be fixed in the beaker that is placed with the 250mL sulfuric acid electrolyte with test tube clamp, be placed on the magnetic stirring apparatus energized after putting into magnetic agitation; Regulate DC stable power supply, starting voltage is 7.2V.
2) filtration: graphite rod is consumed to residue 1/5 o'clock, with the solution left standstill deposition of dissolving graphite powder, goes to use the distilled water rinsing after the supernatant, and after leaving standstill once more, rinsing once more, through rinsing repeatedly, it is approaching neutral up to it to measure solution acid-basicity with the pH test paper.
3) vacuum drying: with step 2) gained neutral solution is filtered, and puts into vacuum drying chamber after filter residue is moved into evaporating dish, regulates temperature 70 degree, and taking-up after dry 8 hours under vacuum condition promptly obtains having the carbon nanomaterial of absorption property.It is subsequent use that prepared carbon nanomaterial is put into the drier that fills silica gel.
4) the prepared carbon nanomaterial of step 3) is carried out sample topography on Zeiss SUPRA 40/40VP type ZEISS SEM ESEM and measure, the result sees Fig. 2.
5) specific area measuring: use N
2Adsorption isotherm is used for characterizing the specific area of carbon nanomaterial.Test is carried out on Micromeritics ASAP2020 specific surface analyzer, through test N
2The adsorption-desorption capacity of gas when normal pressure and 77K obtains the specific area of carbon nanomaterial, and the result sees Fig. 4.
Embodiment 8
1) anodic oxidation of carbon nanomaterial: 75.75g potassium nitrate is dissolved in the distilled water of 50mL, and adds a certain amount of distilled water and be settled in the volumetric flask of 1000mL the electrolyte that obtains clarifying; (dimension D 5 * 100mm) is an anode with graphite rod; (size 10 * 2 * 100mm) is a negative electrode to graphite flake; Be fixed in the beaker that is placed with the 250mL sulfuric acid electrolyte with test tube clamp, be placed on the magnetic stirring apparatus energized after putting into magnetic agitation; Regulate DC stable power supply, starting voltage is 8.0V.
2) filtration: graphite rod is consumed to residue 1/5 o'clock, with the solution left standstill deposition of dissolving graphite powder, goes to use the distilled water rinsing after the supernatant, and after leaving standstill once more, rinsing once more, through rinsing repeatedly, it is approaching neutral up to it to measure solution acid-basicity with the pH test paper.
3) vacuum drying: with step 2) gained neutral solution is filtered, and puts into vacuum drying chamber after filter residue is moved into evaporating dish, regulates temperature 90 degree, and taking-up after dry 8 hours under vacuum condition promptly obtains having the carbon nanomaterial of absorption property.It is subsequent use that prepared carbon nanomaterial is put into the drier that fills silica gel.
Embodiment 9
1) anodic oxidation of carbon nanomaterial: 40g NaOH is dissolved in the distilled water of 50mL, and adds a certain amount of distilled water and be settled in the volumetric flask of 250mL the electrolyte that obtains clarifying; (dimension D 5 * 100mm) is an anode with graphite rod; (size 10 * 2 * 100mm) is for being negative electrode for graphite flake; Be fixed in the beaker that is placed with the 250mL sulfuric acid electrolyte with test tube clamp, be placed on the magnetic stirring apparatus energized after putting into magnetic agitation; Regulate DC stable power supply, starting voltage is 4.0V.
2) filtration: graphite rod is consumed to residue 1/5 o'clock, with the solution left standstill deposition of dissolving graphite powder, goes to use the distilled water rinsing after the supernatant, and after leaving standstill once more, rinsing once more, through rinsing repeatedly, it is approaching neutral up to it to measure solution acid-basicity with the pH test paper.
3) vacuum drying: with step 2) gained neutral solution is filtered, and puts into vacuum drying chamber after filter residue is moved into evaporating dish, regulates temperature 70 degree, and taking-up after dry 8 hours under vacuum condition promptly obtains having the carbon nanomaterial of absorption property.It is subsequent use that prepared carbon nanomaterial is put into the drier that fills silica gel.
1) anodic oxidation of carbon nanomaterial: 40g NaOH is dissolved in the distilled water of 50mL, and adds a certain amount of distilled water and be settled in the volumetric flask of 250mL the electrolyte that obtains clarifying; (dimension D 5 * 100mm) is an anode with graphite rod; (size 10 * 2 * 100mm) is a negative electrode to graphite flake; Be fixed in the beaker that is placed with the 250mL sulfuric acid electrolyte with test tube clamp, be placed on the magnetic stirring apparatus energized after putting into magnetic agitation; Regulate DC stable power supply, starting voltage is 7.2V.
2) filtration: graphite rod is consumed to residue 1/5 o'clock, with the solution left standstill deposition of dissolving graphite powder, goes to use the distilled water rinsing after the supernatant, and after leaving standstill once more, rinsing once more, through rinsing repeatedly, it is approaching neutral up to it to measure solution acid-basicity with the pH test paper.
3) vacuum drying: with step 2) gained neutral solution is filtered, and puts into vacuum drying chamber after filter residue is moved into evaporating dish, regulates temperature 70 degree, and taking-up after dry 8 hours under vacuum condition promptly obtains having the carbon nanomaterial of absorption property.It is subsequent use that prepared carbon nanomaterial is put into the drier that fills silica gel.
4) the prepared carbon nanomaterial of step 3) is carried out sample topography on Zeiss SUPRA 40/40VP type ZEISS SEM ESEM and measure, the result sees Fig. 3.
5) specific area measuring: use N
2Adsorption isotherm is used for characterizing the specific area of carbon nanomaterial.Test is carried out on Micromeritics ASAP2020 specific surface analyzer, through test N
2The adsorption-desorption capacity of gas when normal pressure and 77K obtains the specific area of carbon nanomaterial, and the result sees Fig. 4.
1) anodic oxidation of carbon nanomaterial: 40g NaOH is dissolved in the distilled water of 50mL, and adds a certain amount of distilled water and be settled in the volumetric flask of 500mL the electrolyte that obtains clarifying; (dimension D 5 * 100mm) is an anode with graphite rod; (size 10 * 2 * 100mm) is a negative electrode to graphite flake; Be fixed in the beaker that is placed with the 250mL sulfuric acid electrolyte with test tube clamp, be placed on the magnetic stirring apparatus energized after putting into magnetic agitation; Regulate DC stable power supply, starting voltage is 7.2V.
2) filtration: graphite rod is consumed to residue 1/5 o'clock, with the solution left standstill deposition of dissolving graphite powder, goes to use the distilled water rinsing after the supernatant, and after leaving standstill once more, rinsing once more, through rinsing repeatedly, it is approaching neutral up to it to measure solution acid-basicity with the pH test paper.
3) vacuum drying: with step 2) gained neutral solution is filtered, and puts into vacuum drying chamber after filter residue is moved into evaporating dish, regulates temperature 90 degree, and taking-up after dry 8 hours under vacuum condition promptly obtains having the carbon nanomaterial of absorption property.It is subsequent use that prepared carbon nanomaterial is put into the drier that fills silica gel.
Adsorption experiment of the present invention: in order to prove the absorption property of carbon nanomaterial; The present invention has carried out the adsorption experiment to the methyl orange (MO) of simulation organic pollutant wastewater 250mg/L, and (the BET specific area is 750m to take by weighing three kinds of carbon nanomaterials and the activated carbon of preparation respectively
2/ g, 70 ℃ of vacuum drying 8 hours) each 0.1g, be loaded in the 250mL ground conical flask.In four bottles, respectively add the methyl orange solution that 100mL configures, put into the constant temperature shaking table, the shaking table design temperature is 25 degree, and rotating speed is 150rpm.
Entire reaction is lasted three hours, therefrom intercepting 11 time points.The variation of the uv-vis spectra absorption value through methyl orange comes and changes into concentration through calibration curve to characterize its absorption property, and experimental result is seen Fig. 5.As can be seen from Figure 5: H
2SO
4The carbon nanomaterial absorption property that processing obtains is best, and in 30 minutes, its adsorbance can reach 56% of original MO concentration, secondly is KNO
3The carbon nanomaterial that processing obtains, in 30 minutes, its adsorbance is 16% of an original MO concentration; Secondly be that NaOH handles the carbon nanomaterial that obtains again; In 30 minutes, its adsorbance is 12% of an original MO concentration, and activated carbon is the poorest to the MO absorption property; In 30 minutes, its adsorbance has only about 2.5% of original MO concentration.This shows that graphite is that the carbon nanomaterial that raw material makes through electrochemistry anodic oxidation has the good adsorption performance, has certain application value.
Claims (2)
1. preparation method with carbon nanomaterial of absorption property is characterized in that this method may further comprise the steps:
The step 1) electrolysis: the DC stable power supply anode is connect graphite rod, and negative electrode connects graphite cake, with test tube clamp graphite rod and graphite cake is fixed in the beaker that is placed with 250-1000mL electrolyte;
After in beaker, putting into magnetic agitation, place it on the magnetic stirring apparatus, energized is regulated DC stable power supply, and starting voltage is 4.0-8.0V; When graphite rod is consumed to total length 1/5, turn off power supply and magnetic stirring apparatus;
Step 2) filters:, go to use the distilled water rinsing after the supernatant, after leaving standstill once more step 1) gained solution left standstill deposition; Rinsing once more, through rinsing repeatedly, with the pH test paper measure solution acid-basicity up to it when neutral; Neutral solution is filtered, filter residue is moved in the evaporating dish;
Step 3) drying: with step 2) the gained filter residue is put into vacuum drying chamber, regulates temperature 60-90 degree, under vacuum condition, takes out after dry 5-8 hour, promptly obtains having the carbon nanomaterial of absorption property.
2. a kind of preparation method with carbon nanomaterial of absorption property according to claim 1 is characterized in that: described water solution system is a sulfuric acid solution.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104148012A (en) * | 2014-07-01 | 2014-11-19 | 杭州电子科技大学 | Preparation method of carbon nano sheet material with adsorbing performance for parachlorophenol |
| CN108236921A (en) * | 2018-01-19 | 2018-07-03 | 杭州电子科技大学 | Ion liquid functionalization carbon nanomaterial with absorption property and preparation method thereof |
| CN108854949A (en) * | 2018-06-01 | 2018-11-23 | 杭州电子科技大学 | The preparation method and applications of nitrogen-doped carbon nano material with absorption property |
| CN108940206A (en) * | 2018-08-28 | 2018-12-07 | 武汉霖泉环保科技有限公司 | A kind of carbon-based adsorbent material and preparation method thereof |
| CN109574355A (en) * | 2018-12-25 | 2019-04-05 | 浙江大学 | A kind of method of resource of the high containing sulfate Acid Dye Wastewater of high concentration |
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| JP2005219950A (en) * | 2004-02-04 | 2005-08-18 | Nikon Corp | Carbon material, method of manufacturing carbon material, gas adsorption apparatus and composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104148012A (en) * | 2014-07-01 | 2014-11-19 | 杭州电子科技大学 | Preparation method of carbon nano sheet material with adsorbing performance for parachlorophenol |
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| CN108236921B (en) * | 2018-01-19 | 2021-06-01 | 杭州电子科技大学 | Ionic liquid functionalized carbon nano material with adsorption performance and preparation method thereof |
| CN108854949A (en) * | 2018-06-01 | 2018-11-23 | 杭州电子科技大学 | The preparation method and applications of nitrogen-doped carbon nano material with absorption property |
| CN108940206A (en) * | 2018-08-28 | 2018-12-07 | 武汉霖泉环保科技有限公司 | A kind of carbon-based adsorbent material and preparation method thereof |
| CN109574355A (en) * | 2018-12-25 | 2019-04-05 | 浙江大学 | A kind of method of resource of the high containing sulfate Acid Dye Wastewater of high concentration |
| CN109574355B (en) * | 2018-12-25 | 2022-12-09 | 浙江大学 | Recycling method of high-concentration high-sulfur-content hydrochloric acid dye wastewater |
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