CN107321327A - The preparation and application of the graphene-based adsorbent of heavy metal and organic matter in a kind of synergistic sorption water - Google Patents

The preparation and application of the graphene-based adsorbent of heavy metal and organic matter in a kind of synergistic sorption water Download PDF

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Publication number
CN107321327A
CN107321327A CN201710560300.9A CN201710560300A CN107321327A CN 107321327 A CN107321327 A CN 107321327A CN 201710560300 A CN201710560300 A CN 201710560300A CN 107321327 A CN107321327 A CN 107321327A
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graphene
polypyrrole
solution
preparation
graphene oxide
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张梅
张一梅
张丹丹
赵亚龙
王利群
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North China Electric Power University
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North China Electric Power University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen

Abstract

The invention discloses the preparation method of the graphene-based aeroge of heavy metal and organic matter and its application in water process in a kind of synergistic sorption water.Graphene is combined with pyrrole monomer using hydro-thermal method, polypyrrole/redox graphene aeroge is obtained（PGAs）.The aeroge had not only had the porous of graphene but also the reproducibility with polypyrrole, and the porous and dispersiveness of graphene can be very good to solve the shortcoming of the excessive reunion of pyrroles so that material can give full play to its advantage.Compared with existing adsorbent, adsorbent prepared by the present invention has more preferable absorption property, adapts to broader pH scopes, has good stability.Can be with synergistic sorption water middle and high concentration, high toxicity, persistent organic pollutants weight and metal mixed waste water, the characteristics of non-secondary pollution.

Description

The preparation of the graphene-based adsorbent of heavy metal and organic matter in a kind of synergistic sorption water And application
Technical field
The present invention relates to the preparation method of a kind of synergistic sorption heavy metals ion and the graphene-based material of organic matter And application, the water treatment field belonged in environmental protection.
Background technology
With the continuous complication of waste component, the processing of heavy metal and organic matter composite waste is gradually closed by people Note.The toxicity of metal ion is big, distribution is wide, not degradable, and long-term existence will pass through the low forms of life and plant etc. in the environment Constantly enrichment, enters human body eventually through food chain, causes carcinogenic mutagenesis of teratogenesis etc. to have a strong impact on to human body.Organic wastewater Colourity is high, there is peculiar smell.Some waste water give out pungent stench, are had undesirable effect to surrounding environment.The physico-chemical process typically commonly used There are extraction, absorption method, concentration method, sonication etc..Research show heavy metal and organic matter be discharged into environment general Serious threaten is produced to ecological and human health.Therefore, it is necessary to take appropriate measures, these are removed from water body has serious danger Harmful composite waste.
Absorption has proved to be one of effective ways of processing Pollutants in Wastewater.Its mechanism and dynamics have been widely studied. The method of traditional adsorption treatment waste water is mostly just in the pollutant of single component.Can be while going accordingly, it would be desirable to prepare There is the stability study of pollutant and material to be in itself vital except a variety of.
Graphene as a kind of high-performance novel material of the three-dimensional pore space structure with high-specific surface area it is extensive be applied to The research in each field.Such as Huaiping Cong（ASC Nano, volume 6, the 3rd phase in 2016）It is prepared for a kind of multifunctionality Graphene hydrogel, for the heavy metal Cr in adsorption aqueous solution（VI）And Pb（II）, its adsorbance can reach 139.2 With 373.8 mg/g.The graphene composite material for the N doping that this seminar early stage is done is applied to bisphenol-A（BPA）Absorption obtain Adsorption effect be 127.2 mgg-1（Journal of Hazardous Materials, the 332nd phase, 70- in 2017 Page 78）.Polypyrrole also has as a kind of conducting polymer to the removal of the heavy metal in water to have certain effect.Sun Wanhong etc. （Material protection, volume 49, the 10th phase, the 94-99 pages in 2016）Polypyrrole be have studied to Cr in solution in water（VI）Suction It is attached, and the influence of adsorption time, pH value, initial concentration and temperature to Cr (VI) ionic adsorption performance.Experiment proves that polypyrrole can To remove the Cr of high concentration well（VI）.
M. Isidora Bautista-Toledo etc.（Carbon, the 73rd phase, the 338-350 pages in 2014）It has studied activity Carbon granule is to Cr（III）And removed while BPA, show Cr in text（VI）There is certain collaboration in waste water removal with BPA Effect.Due to Cr in water environment with Cr（VI）And Cr（III）Two kinds of forms are present, and Cr（VI）Compare Cr（III）Toxicity more By force, it is not easily removed, with farther migration, through plants enriched again through food chain, health will be made in aqueous Into very big threat.Cr（VI）It is one of five poisonous creatures: scorpion, viper, centipede, house lizard, toad heavy metal that Environmental Protection Agency is assert, with the carcinogenic mutagenic work of teratogenesis With.Present invention is generally directed to the removal of the mixed solution of two kinds of pollutants of Cr (VI) and BPA in water, prepare collaboration and remove two kinds The graphene-based material of heavy metal.
The content of the invention
The graphene-based of synergistic sorption organic matter and heavy metal mixed solution is prepared it is an object of the invention to provide a kind of The method of aeroge and its application in water process, may be implemented in has in wider pH range to difficult for biological degradation in aquatic system The efficient synergistic sorption of organic pollutants and high toxicity heavy metal contaminants.
The present invention provides a kind of preparation method of the graphene-based aeroge of synergistic sorption organic matter and heavy metal mixed solution, bag Include following steps：
（1）200 mg graphene oxides are used into ultrasonically treated 10 h of ultrasonic cell-break device in 100 ml ultra-pure waters, obtained Finely dispersed graphene oxide solution is stand-by；
（2）Pyrrole monomer solution is subjected to vacuum distillation, combination unit is vacuumized, package unit is wrapped up with tinfoil, is prevented The pyrroles's re-oxidation only distilled, distills in 100 °C of hot baths, obtains fresh pyrrole monomer stand-by under a nitrogen atmosphere；
（3）By appropriate FeCl3·6H2O is added in 10 ml deionizations ultrasonic disperse to FeCl3·6H2O, which is completely dissolved, to be treated With；
（4）25 ml polytetrafluoroethyllining linings are taken, 5 ml graphene oxide dispersions is added, adds the fresh pyrroles of 0.5 ml Monomer, by mixed solution 10 min of ultrasound in ultrasonic cell-break device, is well mixed two kinds of solution stand-by；
（5）Liner is put into ultrasonic washing instrument, then by FeCl3·6H2O solution is poured into liner in the case of ultrasound, is treated Stable reaction, liner is covered and is put into reactor, 180 °C of 12 h of heating；
（6）Question response kettle is cooled to after room temperature, by reacted product --- and redox graphene polypyrrole hydrogel is used super Pure water and alcohol clean the removal of impurity repeatedly；
（7）Hydrogel after purification is freeze-dried 24 h, polypyrrole/redox graphene aeroge is obtained（PGAs）It is standby With.
Step（1）Described in ultrasonic method be per ultrasonic 30 min, to stir a dispersion liquid, every 1 h be mixed solution more An ice bath is changed, the ultrasonication in the case of 0 °C is maintained.
Step（1）In used graphene oxide there is larger specific surface area, can arrive the sufficient dispersin polymerization of polypyrrole In graphene oxide layer, the dispersion problem of polypyrrole is improved.
Step（1）In the concentration of prepared graphene oxide dispersion be 2 mg/ml.
Step（2）N should be in the vacuum distillation process of middle pyrrole monomer all the time2Flow down.
Step（3）Middle pyrrole monomer and FeCl3·6H2O molal weight ratio is, 1：2.3.
This adsorbent prepared by the inventive method is characterised by：Graphene oxide plays support effect in system, prevents The reunion of polypyrrole so that system is fully dispersed, while itself can also adsorb pollutant, this composite construction is more beneficial for sewage Enrichment of the middle pollutant in compound system, precipitation or absorption.Polypyrrole has certain oxidisability because of it, can be by high toxicity Heavy metal ion be reduced to the metal ion of hypotoxicity, so as to improve its adsorption capacity.
The advantage of the invention is that：The big specific area of graphene oxide is to have polymerize pyrrole monomer, it is therefore prevented that the reunion of particulate, again It greatly strengthen absorption of the material to persistence organic pollutant in water body and heavy metal mixed solution.Polypyrrole can be by a part Heavy metal is reduced to the metal ion of hypotoxicity.Contained in whole absorption system：Electrostatic Absorption, ion exchange, reduction etc..This Adsorbent prepared by invention has synergistic sorption ability, adapts to broader pH scopes, stability and reusing are good.To water Middle and high concentration, high toxicity, persistent organic pollutants and heavy metal mixed solution have synergic sorption, non-secondary pollution Feature.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the graphene-based aeroge that the embodiment of the present invention 1 is provided；
Fig. 2 a are the X ray diffracting spectrum of the graphene-based aeroge that the embodiment of the present invention 2 is provided and graphene oxide；
Fig. 2 b are the X ray diffracting spectrum for the graphene-based aeroge that the embodiment of the present invention 2 is provided；
The adsorbance that Fig. 3 a are Cr (VI) in the graphene-based aeroge absorption mixed solution that the embodiment of the present invention 3 is provided is with the time Change；
The adsorbance that Fig. 3 b are Cr (VI) in the graphene-based aeroge absorption mixed solution that the embodiment of the present invention 3 is provided is with the time Change dynamics fitted figure；
The adsorbance that Fig. 3 c are BPA in the graphene-based aeroge absorption mixed solution that the embodiment of the present invention 3 is provided is with the time Change；The adsorbance that Fig. 3 d are BPA in the graphene-based aeroge absorption mixed solution that the embodiment of the present invention 3 is provided is with the time The dynamics fitted figure of change；
Fig. 4 is the adsorbance that the graphene-based aeroge that the embodiment of the present invention 4 is provided adsorbs Cr (VI) and BPA in mixed solution Situation is influenceed by pH.
Embodiment
To enable above-mentioned purpose, the feature and advantage of invention more obvious understandable, below to the specific implementation of the present invention Mode is described in detail.
Embodiment 1：
（1）200 mg graphene oxides are used into ultrasonically treated 10 h of ultrasonic cell-break device in 100 ml ultra-pure waters, Obtain finely dispersed graphene oxide solution stand-by；
（2）Pyrrole monomer solution is subjected to vacuum distillation, combination unit is vacuumized, package unit is wrapped up with tinfoil, is prevented The pyrroles's re-oxidation only distilled, distills in 100 °C of hot baths, obtains fresh pyrrole monomer stand-by under a nitrogen atmosphere；
（3）Appropriate FeCl36H2O is added to ultrasonic disperse in 10 ml deionizations be completely dissolved to FeCl36H2O and treated With；
（4）25 ml polytetrafluoroethyllining linings are taken, 5 ml graphene oxide dispersions is added, adds the fresh pyrroles of 0.5 ml Monomer, by mixed solution 10 min of ultrasound in ultrasonic cell-break device, is well mixed two kinds of solution stand-by；
（5）Liner is put into ultrasonic washing instrument, then FeCl36H2O solution is poured into liner in the case of ultrasound, is treated Stable reaction, liner is covered and is put into reactor, 180 °C of 12 h of heating；
（6）Question response kettle is cooled to after room temperature, by reacted product --- and redox graphene polypyrrole hydrogel is used super Pure water and alcohol clean the removal of impurity repeatedly；
（7）Hydrogel after purification is freeze-dried 24h, PGAs is obtained standby.
The polypyrrole redox graphene material of preparation is placed in SEM（SEM）The morphology of lower observation material And particle diameter, find to be attached with bar-shaped polypyrrole chain on redox graphene lamella, show that pyrrole monomer is very good scattered Property is aggregated on redox graphene lamella, as shown in Figure 1.
Embodiment 2：
（1）200 mg graphene oxides are used into ultrasonically treated 10 h of ultrasonic cell-break device in 100 ml ultra-pure waters, Obtain finely dispersed graphene oxide solution stand-by；
（2）Pyrrole monomer solution is subjected to vacuum distillation, combination unit is vacuumized, package unit is wrapped up with tinfoil, is prevented The pyrroles's re-oxidation only distilled, distills in 100 °C of hot baths, obtains fresh pyrrole monomer stand-by under a nitrogen atmosphere；
（3）Appropriate FeCl36H2O is added to ultrasonic disperse in 10 ml deionizations be completely dissolved to FeCl36H2O and treated With；
（4）25 ml polytetrafluoroethyllining linings are taken, 5 ml graphene oxide dispersions is added, adds the fresh pyrroles of 0.5 ml Monomer, by mixed solution 10 min of ultrasound in ultrasonic cell-break device, is well mixed two kinds of solution stand-by；
（5）Liner is put into ultrasonic washing instrument, then FeCl36H2O solution is poured into liner in the case of ultrasound, is treated Stable reaction, liner is covered and is put into reactor, 180 °C of 12 h of heating；
（6）Question response kettle is cooled to after room temperature, by reacted product --- and redox graphene polypyrrole hydrogel is used super Pure water and alcohol clean the removal of impurity repeatedly；
（7）Hydrogel after purification is freeze-dried 24 h, redox graphene polypyrrole aeroge is obtained standby.
, will in order to further determine that on the whether poly- polymer and graphite alkene of pyrroles and pay close attention to whether graphene oxide is reduced to graphene Prepared sample carries out X-ray diffractogram analysis of spectrum.Such as Fig. 2（a）Shown, compared with GO, PGAs has lacked 9.06 ° of peak, This shows that GO is reduced to graphene.Such as Fig. 2（b）It is shown, there are three obvious 17.56 ° of polypyrrole peaks in PGAs figure, 26.66 ° and 40.23 °, show that polypyrrole is aggregated to graphene oxide in hydrothermal reaction process（GO）On.
Embodiment 3：
（1）200 mg graphene oxides are used into ultrasonically treated 10 h of ultrasonic cell-break device in 100 ml ultra-pure waters, Obtain finely dispersed graphene oxide solution stand-by；
（2）Pyrrole monomer solution is subjected to vacuum distillation, combination unit is vacuumized, package unit is wrapped up with tinfoil, is prevented The pyrroles's re-oxidation only distilled, distills in 100 °C of hot baths, obtains fresh pyrrole monomer stand-by under a nitrogen atmosphere；
（3）Appropriate FeCl36H2O is added to ultrasonic disperse in 10 ml deionizations be completely dissolved to FeCl36H2O and treated With；
（4）25 ml polytetrafluoroethyllining linings are taken, 5 ml graphene oxide dispersions is added, adds the fresh pyrroles of 0.5 ml Monomer, by mixed solution 10 min of ultrasound in ultrasonic cell-break device, is well mixed two kinds of solution stand-by；
（5）Liner is put into ultrasonic washing instrument, then FeCl36H2O solution is poured into liner in the case of ultrasound, is treated Stable reaction, liner is covered and is put into reactor, 180 °C of 12 h of heating；
（6）Question response kettle is cooled to after room temperature, by reacted product --- and redox graphene polypyrrole hydrogel is used super Pure water and alcohol clean the removal of impurity repeatedly；
（7）Hydrogel after purification is freeze-dried 24h, redox graphene polypyrrole aeroge is obtained standby.
By the material of preparation with Cr（VI）It is that target contaminant carries out adsorption experiment, the prepared material of checking with BPA mixed solutions Absorption property.By the Cr that 50 mL concentration are 80 mg/L（VI）50 ml tapers are put into 20 mg/L BPA reaction solution Graphene-based adsorbent prepared by 5 mg is added in bottle.1.0mL samples are collected at predetermined intervals, and then, sample is stood Filter to remove solid particle by 0.22 micron of PES injection filter.Pass through high performance liquid chromatography（HPLC）Determine residual BPA concentration, the Cr remained in mixed solution concentration is determined using diphenyl carbazide spectrophotometry.As a result show, When pH is 3,2 hours are can be achieved to Cr（VI）（Fig. 3（a））And BPA（Fig. 3（c））Adsorbance reach 173.56 mg/g and 47.91 mg/g.And kinetic reaction equation has been fitted, the removal of two kinds of pollutants meets pseudo-second order kinetic, such as Fig. 3（b） And Fig. 3（d）It is shown.
Embodiment 4：
（1）200 mg graphene oxides are used into ultrasonically treated 10 h of ultrasonic cell-break device in 100 ml ultra-pure waters, Obtain finely dispersed graphene oxide solution stand-by；
（2）Pyrrole monomer solution is subjected to vacuum distillation, combination unit is vacuumized, package unit is wrapped up with tinfoil, is prevented The pyrroles's re-oxidation only distilled, distills in 100 °C of hot baths, obtains fresh pyrrole monomer stand-by under a nitrogen atmosphere；
（3）Appropriate FeCl36H2O is added to ultrasonic disperse in 10 ml deionizations be completely dissolved to FeCl36H2O and treated With；
（4）25 ml polytetrafluoroethyllining linings are taken, 5 ml graphene oxide dispersions is added, adds the fresh pyrroles of 0.5 ml Monomer, by mixed solution 10 min of ultrasound in ultrasonic cell-break device, is well mixed two kinds of solution stand-by；
（5）Liner is put into ultrasonic washing instrument, then FeCl36H2O solution is poured into liner in the case of ultrasound, is treated Stable reaction, liner is covered and is put into reactor, 180 °C of 12 h of heating；
（6）Question response kettle is cooled to after room temperature, by reacted product --- and redox graphene polypyrrole hydrogel is used super Pure water and alcohol clean the removal of impurity repeatedly；
（7）Hydrogel after purification is freeze-dried 24 h, redox graphene polypyrrole aeroge is obtained standby.
The absorption situation of Cadmium Pollutants On The Chinese in mixed solution and single component solution is compared for respectively under condition of different pH, wherein scheming Solid line is the removal situation of each pollutant in mixed solution in 4, and for the solution of single component, its adsorbance has substantially Change.Cr（VI）It is essentially identical with the pH trend for changing its absorption in both cases, and the adsorbance in mixed solution More than Cr in the solution of single component（VI）Adsorbance.In mixed solution BPA adsorbance in acid condition when than single The adsorbance of BPA in title point solution is small, but in pH>When 5, BPA adsorbance claims to divide apparently higher than single in mixed solution The adsorbance of BPA in solution.Above experimental result can substantially prove Cr in mixed solution（VI）Collaboration is there is with BPA to inhale Attached effect.

Claims (6)

1. a kind of method for preparing the graphene-based aeroge of heavy metal and organic matter in synergistic sorption water, it is characterised in that the party Method comprises the following steps：
（1）200 mg graphene oxides are used into ultrasonically treated 10 h of ultrasonic cell-break device in 100 ml ultra-pure waters, obtained Finely dispersed graphene oxide solution is stand-by；
（2）Pyrrole monomer solution is subjected to vacuum distillation, combination unit is vacuumized, package unit is wrapped up with tinfoil, is prevented The pyrroles's re-oxidation only distilled, distills in 100 °C of hot baths, obtains fresh pyrrole monomer stand-by under a nitrogen atmosphere；
（3）By appropriate FeCl3·6H2O is added in 10 ml deionizations ultrasonic disperse to FeCl3·6H2O is completely dissolved stand-by；
（4）25 ml polytetrafluoroethyllining linings are taken, 5 ml graphene oxide dispersions is added, adds the fresh pyrroles of 0.5 ml Monomer, by mixed solution 10 min of ultrasound in ultrasonic cell-break device, is well mixed two kinds of solution stand-by；
（5）Liner is put into ultrasonic washing instrument, then by FeCl3·6H2O solution is poured into liner in the case of ultrasound, treats anti- It should stablize, liner is covered and is put into reactor, 180 °C of 12 h of heating；
（6）Question response kettle is cooled to after room temperature, by reacted product --- and redox graphene polypyrrole hydrogel is used super Pure water and alcohol clean the removal of impurity repeatedly；
（7）Hydrogel after purification is freeze-dried 24 h, polypyrrole/redox graphene aeroge is obtained（PGAs）It is standby With.
2. preparation method according to claim 1, it is characterised in that step（1）Described in ultrasonic method be per ultrasound 30 min, stir a dispersion liquid, are that mixed solution changes an ice bath every 1 h, maintain the ultrasonication in the case of 0 °C.
3. step（1）In used graphene oxide there is larger specific surface area, the sufficient dispersin polymerization of polypyrrole can be made Onto graphene oxide layer, the dispersion problem of polypyrrole is improved.
4. preparation method according to claim 1, it is characterised in that step（1）In prepared graphene oxide disperse The concentration of liquid is 2 mg/ml.
5. preparation method according to claim 1, it is characterised in that step（2）The vacuum distillation process of middle pyrrole monomer In should be in N all the time2Flow down.
6. preparation method according to claim 1, it is characterised in that step（3）Middle pyrrole monomer and FeCl3·6H2O's Molal weight ratio is, 1：2.3.
CN201710560300.9A 2017-07-11 2017-07-11 The preparation and application of the graphene-based adsorbent of heavy metal and organic matter in a kind of synergistic sorption water Withdrawn CN107321327A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108242341A (en) * 2017-12-21 2018-07-03 华北电力大学 A kind of preparation of multifunctional graphite vinyl sill and its application in terms of ultracapacitor and water process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108242341A (en) * 2017-12-21 2018-07-03 华北电力大学 A kind of preparation of multifunctional graphite vinyl sill and its application in terms of ultracapacitor and water process

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Application publication date: 20171107