CN105967287A - Method for removing manganese ions in water through S element decorated graphene electrode - Google Patents

Method for removing manganese ions in water through S element decorated graphene electrode Download PDF

Info

Publication number
CN105967287A
CN105967287A CN201610517023.9A CN201610517023A CN105967287A CN 105967287 A CN105967287 A CN 105967287A CN 201610517023 A CN201610517023 A CN 201610517023A CN 105967287 A CN105967287 A CN 105967287A
Authority
CN
China
Prior art keywords
electrode
water
graphite alkene
manganese ion
adsorption
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610517023.9A
Other languages
Chinese (zh)
Inventor
魏永
徐斓
赵威
廖旭
崔文怡
王钰
李如意
吕晓港
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou University
Original Assignee
Changzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changzhou University filed Critical Changzhou University
Priority to CN201610517023.9A priority Critical patent/CN105967287A/en
Publication of CN105967287A publication Critical patent/CN105967287A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/206Manganese or manganese compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/46Apparatus for electrochemical processes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention relates to a method for removing manganese ions in water through an S element modified graphene electrode. The method comprises the following steps of preparing sulphur-doped graphene aerogel, preparing a sulphur-doped graphene aerogel paper electrode and absorbing different manganese ions through the paper electrode in a three-electrode system. The method has the advantages that a preparation method of the sulphur-doped graphene aerogel is convenient and easy; pollution in a preparation process is avoided, and environment is protected; the electrode modified by the materials is high in absorbing efficiency for the manganese ions in water, quick in speed and convenient to operate; the manganese ions in the water can be effectively removed.

Description

A kind of grapheme modified electrode of S element removes the method for manganese ion in water
Technical field
The present invention relates to a kind of grapheme modified electrode of S element and remove the method for manganese ion in water, belong to water and process and materials synthesis Field.
Technical background
Manganese is one of more rich element in nature, is also one of trace element necessary to organism.If but water containing The manganese of amount, it will make water for industrial use and Drinking Water utilizes Quality Down.The main source of Mn-bearing waste water is: iron and steel enterprise Efflux wastewater, electrolytic manganese production enterprise wastewater, manganese ore mine contaminant water, ferrous metal mine, metallurgy, chemical industry emission Waste water etc..China " drinking water sanitary standard " (GB5749-2006) specifies: in water, Fe content is less than 0.1mg/L the most not Health can be produced harm.When in former water, the content of manganese exceedes above-mentioned standard it is necessary to process.
The processing method of manganese ion in water is had a variety of: electro-adsorption, reverse osmosis, chemical precipitation method etc..Electro-adsorption is relative to it His method for treating water, has that non-secondary pollution, energy consumption be low, small investment, length in service life and an easy advantage such as regeneration, is a kind of Economical and effective method.Therefore, electro-adsorption technology is a kind of water technology with development prospect.
Graphene aerogel, as a kind of emerging superior adsorbent, has specific surface area big, and adsorption rate is fast, and adsorption capacity is big, The advantages such as acid-fast alkali-proof, main is that its regeneration is convenient, meets manganese ion and processes requirement, is widely used in water purification and processes. The present invention utilizes the bigger serface of graphene aerogel and high electron transfer rate for the manganese ion removing in water.
Summary of the invention
It is an object of the invention to grapheme modified for S element application of electrode in a new field electro-adsorption water in manganese ion. The manganese ion that can effectively adsorb in water after adsorption electrode made by sulfur graphite alkene aeroge will be mixed.
The present invention relates to a kind of grapheme modified electrode of S element and remove the method for manganese ion in water, comprise the following steps:
Sulfur graphite alkene aeroge is mixed in a, preparation: by graphene oxide ultrasonic disperse in deionized water, ultrasonic 10~30min make it It is uniformly dispersed.Adding dithiothreitol, DTT after it is uniformly dispersed, stirring makes it be uniformly dispersed.Then by mixed liquor at the bar of 95 DEG C Heating in water bath 2h is carried out under part.After reaction terminates, product is placed in distilled water and immerses 2~3 days, then lyophilization, To mixing sulfur graphite alkene aerogel material;
Sulfur graphite alkene Aerogel paper electrode is mixed in b, preparation: step a prepared mixes sulfur graphite alkene aeroge and the poly-second prepared in advance Enolate solution mixes, and forms the dispersion liquid of pasty state, pipettes the homogeneous dispersion of 0.1~0.4mL and is applied on hard paper, freezing dry Dry, obtain mixing sulfur graphite alkene Aerogel paper electrode;
C, electrochemical process remove manganese ion in water: prepare manganese ion solution, measure manganese ion solution and be placed in electro-adsorption container, will The sulfur graphite alkene Aerogel paper electrode of mixing prepared in step b carries out electro-adsorption experiment to manganese ion.The experiment of electro-adsorption manganese ion uses Three-electrode system, with paper electrode as working electrode, platinum plate electrode is to electrode, and calomel electrode is reference electrode.Make electricity consumption simultaneously Electrical conductivity instrument monitors the change of electrical conductivity of solution in real time, and when electrical conductivity keeps constant, the absorption of the most each paper electrode reaches balance.
Further, in step a, dithiothreitol, DTT is 3:1 with the mass ratio of graphene oxide, and reaction temperature is 95 DEG C, during reaction Between be 2~4h.
Further, in step c, the ion in electro-adsorption water is Mn2+
The invention has the beneficial effects as follows: the preparation method mixing sulfur graphite alkene aeroge is simple and easy to do, and preparation process is environment friendly and pollution-free, The electrode modified with these materials in water, the adsorption efficiency of manganese ion is higher, the time is short, easy and simple to handle, the electro-adsorption of material Performance there has also been compared with conventional material and significantly promotes.
Accompanying drawing explanation
The present invention is further described below in conjunction with the accompanying drawings.
Fig. 1 is the infrared spectrum (FT-IR figure) mixing sulfur graphite alkene aeroge of preparation in embodiment one;
Fig. 2 is Mn in solution in embodiment two2+Initial concentration is to Mn2+The impact of clearance;
Fig. 3 is the absorption property mixing sulfur graphite alkene Aerogel paper electrode in embodiment three change with regeneration times.
Detailed description of the invention
Presently in connection with specific embodiment, the present invention will be further described, and following example are intended to illustrate rather than this Bright further restriction.
Describe in detail in the present invention and measure as follows with the manganese ion clearance shown in examples of implementation:In formula, %R, C0、CeRepresent Mn respectively2+Clearance, initial concentration, equilibrium concentration.
Embodiment one:
Preparation is mixed sulfur graphite alkene aerogel material paper electrode and is included following step:
(1) by graphene oxide (GO) ultrasonic disperse of 0.15g in 100mL distilled water, the two sulfur Soviet Unions of 0.45g are added Sugar alcohol, mechanical agitation makes it be sufficiently mixed, and then mixed liquor carries out under conditions of 95 DEG C heating in water bath 2h.After reaction terminates, Being immersed in by the product of generation in distilled water 2~3 days, final sample, at-52 DEG C of lyophilization 24h, must mix sulfur graphite alkene aeroge.
(2) 90mg step (1) prepared mixes the poly-vinyl alcohol solution that sulfur graphite alkene aerogel material adds 2mL 4wt%, Ultrasonic composite is made to be uniformly dispersed in solution.Take the above-mentioned homogeneous dispersion of 0.16mL and be applied in the cardboard of 35mm × 8mm On sheet (thick 400 μm), in-52 DEG C of lyophilization 12h, make and mix sulfur graphite alkene Aerogel paper electrode.
Embodiment two:
The preparation process mixing sulfur graphite alkene Aerogel paper electrode is identical with embodiment one.
Nitrogen-doped graphene Aerogel paper electrode by preparation is respectively used to the Mn of 0.25,0.4,0.8,1,3 and 6mM2+Solution Electrochemical treatments, applying voltage is 0.3V, and the process time is 2min, Mn2+Clearance see Fig. 2, it is seen that nitrating graphite The alkene aerogel material Mn to low concentration2+Solution has preferable adsorption effect..
Embodiment three:
The preparation process mixing sulfur graphite alkene Aerogel paper electrode is identical with embodiment one.
It is circulated electro-adsorption test to mixing sulfur graphite alkene Aerogel paper electrode.Sulfur graphite alkene Aerogel paper electrode will be mixed and be placed in 80mL Concentration is the Mn of 0.25mmol/L2+In solution, apply current potential-0.3V, and recording solution electrical conductivity, again record molten after 2min The electrical conductivity of liquid, calculates clearance.Removing current potential subsequently to be desorbed by it, circulation is repeatedly continuously.Experimental result is as shown in Figure 3. Adsorb Mn first2+Clearance is 78.7%, at the recycling rear electrode through 30 times to Mn2+Clearance is 77.3%, only There is decline slightly, but electro-adsorption clearance has significantly decline when proceeding circulation experiment, goes after recycling for 80 times Except rate is 72.3%.

Claims (3)

1. the grapheme modified electrode of S element removes the method for manganese ion in water, it is characterised in that: step is as follows:
Sulfur graphite alkene aeroge is mixed in a, preparation: by graphene oxide ultrasonic disperse in deionized water, ultrasonic 10~30min make it It is uniformly dispersed.Adding dithiothreitol, DTT after it is uniformly dispersed, stirring makes it be uniformly dispersed, then by mixed liquor at the bar of 95 DEG C Heating in water bath 2h is carried out under part.After reaction terminates, product is placed in distilled water and immerses 2~3 days, then lyophilization, To mixing sulfur graphite alkene aerogel material;
Sulfur graphite alkene Aerogel paper electrode is mixed in b, preparation: step a prepared mixes sulfur graphite alkene aeroge and the poly-second prepared in advance Enolate solution mixes, and forms the dispersion liquid of pasty state, pipettes the homogeneous dispersion of 0.1~0.4mL and is applied on hard paper, freezing dry Dry, obtain mixing sulfur graphite alkene Aerogel paper electrode;
C, electrochemical process remove manganese ion in water: prepare manganese ion solution, measure manganese ion solution and be placed in electro-adsorption container, will The sulfur graphite alkene Aerogel paper electrode of mixing prepared in step b carries out electro-adsorption experiment to manganese ion.The experiment of electro-adsorption manganese ion uses Three-electrode system, with paper electrode as working electrode, platinum plate electrode is to electrode, and calomel electrode is reference electrode.Make electricity consumption simultaneously Electrical conductivity instrument monitors the change of electrical conductivity of solution in real time, when electrical conductivity keeps constant, i.e. mixes sulfur graphite alkene Aerogel paper electrode adsorption Reach balance;
D, desorption and regeneration use after electrode: saturated mix sulfur graphite alkene Aerogel paper electrode for reaching to adsorb, remove on electrode Voltage after, the electrical conductivity of solution is recovered to close to initial value, it is achieved the desorption and regeneration of electrode.
A kind of grapheme modified electrode of S element removes the method for manganese ion in water, it is characterized in that: In described step a, dithiothreitol, DTT is 3:1 with the mass ratio of graphene oxide, and reaction temperature is 95 DEG C, and the response time is 2~4h.
A kind of grapheme modified electrode of S element removes the method for manganese ion in water, it is characterized in that: In described step c, the ion in electro-adsorption water is Mn2+
CN201610517023.9A 2016-07-04 2016-07-04 Method for removing manganese ions in water through S element decorated graphene electrode Pending CN105967287A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610517023.9A CN105967287A (en) 2016-07-04 2016-07-04 Method for removing manganese ions in water through S element decorated graphene electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610517023.9A CN105967287A (en) 2016-07-04 2016-07-04 Method for removing manganese ions in water through S element decorated graphene electrode

Publications (1)

Publication Number Publication Date
CN105967287A true CN105967287A (en) 2016-09-28

Family

ID=56954792

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610517023.9A Pending CN105967287A (en) 2016-07-04 2016-07-04 Method for removing manganese ions in water through S element decorated graphene electrode

Country Status (1)

Country Link
CN (1) CN105967287A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130134964A (en) * 2012-05-31 2013-12-10 에스케이이노베이션 주식회사 Flowable electrode for energy storage
CN103996830A (en) * 2014-05-12 2014-08-20 上海大学 A preparation method of a sulfur-supported graphene aerogel composite material
CN105478074A (en) * 2015-12-23 2016-04-13 中国科学院烟台海岸带研究所 Preparation method and application of heavy metal ion remover
CN105692818A (en) * 2016-03-18 2016-06-22 常州大学 Sulfur-doped graphene aerogel synthesized by one-step method and electric adsorption removal of sulfur-doped graphene aerogel on various heavy metal ions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130134964A (en) * 2012-05-31 2013-12-10 에스케이이노베이션 주식회사 Flowable electrode for energy storage
CN103996830A (en) * 2014-05-12 2014-08-20 上海大学 A preparation method of a sulfur-supported graphene aerogel composite material
CN105478074A (en) * 2015-12-23 2016-04-13 中国科学院烟台海岸带研究所 Preparation method and application of heavy metal ion remover
CN105692818A (en) * 2016-03-18 2016-06-22 常州大学 Sulfur-doped graphene aerogel synthesized by one-step method and electric adsorption removal of sulfur-doped graphene aerogel on various heavy metal ions

Similar Documents

Publication Publication Date Title
CN104984728A (en) Method for synthesizing nitrogen-doped graphene hydrogel in one step and using nitrogen-doped graphene hydrogel for electrically adsorbing heavy metal ions in water
CN105692818B (en) One-step synthesis method mixes sulfur graphite alkene aeroge and its Electro Sorb of contents of many kinds of heavy metal ion is removed
Zaini et al. Adsorption of aqueous metal ions on cattle-manure-compost based activated carbons
Su et al. The characterization and application of prussian blue at graphene coated carbon fibers in a separated adsorption and electrically switched ion exchange desorption processes of cesium
CN105668724A (en) One-step synthesized nitrogen and sulfur co-doped graphene aerosol and electro-adsorption removal of various heavy metal ions thereby
CN104941661B (en) A kind of metal nanoparticle is uniformly embedded into the controllable method for preparing of the ordered mesopore carbon elctro-catalyst of hole wall structure
Lu et al. A novel quinone/reduced graphene oxide composite as a solid-phase redox mediator for chemical and biological Acid Yellow 36 reduction
CN104558598A (en) One-step method for synthesizing poly(m-phenylenediamine) and graphene composite material and application of composite material to electric adsorption of heavy metal ions in water
CN106512935A (en) Amination graphene oxide modified diatomite adsorbing material
Zhou et al. Electrosorption for organic pollutants removal and desalination by graphite and activated carbon fiber composite electrodes
CN106115869A (en) The nitrogen-doped graphene aeroge of one-step synthesis method is applied to electro-adsorption mercury ions in waste water
Bhagawan et al. Fluoride removal from groundwater using hybrid cylindrical electrocoagulation reactor
Zhang et al. A novel electrochemiluminescence sensor based on nitrogen-doped graphene/CdTe quantum dots composite
Zhang et al. Accelerating effect of bio-reduced graphene oxide on decolorization of acid red 18 by Shewanella algae
CN105967287A (en) Method for removing manganese ions in water through S element decorated graphene electrode
CN106396031A (en) One-step synthesis method of nitrogen-sulfur codoped graphene aerogel and zinc ion electro-adsorption removing by utilizing the aerogel
CN106145284A (en) The nitrogen-doped graphene aeroge of one-step synthesis method is applied to heavy metal ion zinc in electro-adsorption water
CN105948191A (en) Method for removing manganese ions in water by using N-S element synergetic modified graphene electrode
CN114014414B (en) Copper ion treatment method
CN101805044A (en) Clay/carbon material-based composite electrode and production method and application thereof
CN106185909B (en) A kind of nonmetal doping graphene and preparation method thereof and its application in electrocatalytic oxidation reduction reaction
CN111426734A (en) Nano Cu/graphene composite material modified electrode, preparation method thereof and application of nano Cu/graphene composite material modified electrode in detection of hydroquinone
CN106115871A (en) The grapheme modified electrode of a kind of N element removes the method for manganese ion in water
CN105967288A (en) Method for removing hard calcium ions in water through S element modified graphene electrode
CN106115854A (en) A kind of grapheme modified electrode of S element removes the method for arsenic ion in water

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160928

WD01 Invention patent application deemed withdrawn after publication