CN106442666A - Ionic liquid functional carbon nitride nanosheet modified electrode as well as preparation and application of electrode in chlorphenol detection - Google Patents
Ionic liquid functional carbon nitride nanosheet modified electrode as well as preparation and application of electrode in chlorphenol detection Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002135 nanosheet Substances 0.000 title claims abstract description 27
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000001514 detection method Methods 0.000 title abstract description 20
- 239000002608 ionic liquid Substances 0.000 title abstract description 10
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims description 52
- 229910052799 carbon Inorganic materials 0.000 claims description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 238000007306 functionalization reaction Methods 0.000 claims description 36
- 150000002500 ions Chemical class 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000001273 butane Substances 0.000 claims description 14
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 14
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000001548 drop coating Methods 0.000 claims description 9
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000834 fixative Substances 0.000 claims description 2
- 230000007246 mechanism Effects 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 abstract 1
- 238000002848 electrochemical method Methods 0.000 abstract 1
- 238000005956 quaternization reaction Methods 0.000 abstract 1
- 238000011896 sensitive detection Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000008055 phosphate buffer solution Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- -1 Chlorophenols compound Chemical class 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000006056 electrooxidation reaction Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses an ionic liquid functional C3N4 modified electrode as well as a preparation method and application of the electrode in chlorphenol detection. C3N4 is protonated in acid to prepare a C3N4 nanosheet, and then quaternization is realized with n-butyl bromide in an alkaline condition to prepare an ionic liquid functional C3N4 nanosheet; the catalytic active sites of the obtained ionic liquid functional C3N4 nanosheet are increased while the dispersity, electrical conductivity and electrochemical catalytic performance are obviously improved; and the ionic liquid functional C3N4 nanosheet is dropwise applied to the electrode surface to obtain an ionic liquid functional C3N4 nanosheet modified electrode and is applied to efficient and sensitive detection of 2,4-dichlorophenol in a water medium. According to the invention, the obtained modified electrode imposes low detection limit on 2,4-dichlorophenol and has relatively high selectivity, stability and anti-interference performance and relatively wide linear range; and a quick and sensitive electrochemical method is provided for quantitative detection of 2,4-dichlorophenol.
Description
Technical field：
The invention belongs to Electroanalytical Chemistry technical field is and in particular to a kind of ion liquid functionalization azotized carbon nano piece is repaiied
Decorations electrode and preparation method thereof and the application of quantitative determination chlorophenol.
Background technology：
Chlorophenols compound can also may be used as the intermediate of medicine synthesis, agricultural fungicides, the main component of herbicide
For the preservation of timber against decay agent, bactericide etc..Therefore pass through industrial production and agricultural use cause substantial amounts of residual in the environment,
Especially pollute the most serious in water environment.Chlorophenols compound content in water body is very low, but P electronics and phenyl ring in chlorine atom
Upper pi-electron can form stable π-conjugated systems, and most of chlorophenol all has very big toxicity, and can be by food chain in biosphere
Accumulation, is difficult to biodegradable, has " three cause " (carcinogenic, teratogenesis, mutagenesis) effect and genetoxic, is in environment there to be persistence
The Typical Representative of organic pollutants (Persistent Organic Pollutants, POPs).Chlorophenols compound in water environment
Content is very low, and analysis detection has great difficulty.The detection method commonly used at present mainly has AAS, fluorescence method, HPLC,
GC-MS, LC-MS, LC-MS/MS and enzyme-linked immunosorbent assay are although these methods have reliable sensitivity and relatively low detection
Limit, but expensive equipment, sample pretreatment be complicated, operation time-consuming numerous and diverse, significantly limit them the shortcomings of be unable to Site Detection should
With [Banimuslem H, Hassan A, Basova T, Gulmez A D, Tuncel S, Durmus M, Gurek A G,
Ahsen V.Copper phthalocyanine/single walled carbon nanotubes hybrid thin
films for pentachlorophenol detection.Sensor Actuat.B 2014,190,990-998.].Electrification
Learn sensing method because its analyze speed is fast, instrument is simple, easy and simple to handle, with low cost, sensitivity is high, selectivity is good and can be real-time
The advantages such as detection, the context of detection in chlorophenols compound is applied, such as based on ZnSe-CTAB/GCE, HRP/Au/
The detection of the electrochemical sensor parachlorphenol of GCE, NNH-MWCNTs/GCE, CD/GRs/CPE composite modified electrode.But current report
Such electrochemical sensor in road exists mostly as built " Ping-Pong that is complicated, needing medium or probe, need biology enzyme
" defect such as catalysis and parachlorphenol catalysis oxidation ability is highly detrimental to their practical application and extensive development.Cause
This, find the novel electrode decorative material with high electrocatalysis characteristic, develop and still have for the electrochemical sensor detecting chlorophenol
Very big challenge.
Graphite phase carbon nitride (C3N4) two-dimensional nano piece be nitridation carbon compound in a kind of most stable of allotrope, its
Graphite plane is made up of the triazine ring that flat amino is formed by connecting, and the C-N covalent bond being formed by π-πconjugation makes three
Piperazine ring element constitutes C3N4Condensate.Due to good heat endurance, high containing N than with special electronic structure, C3N4In photoelectricity
The field such as chemical catalysis sensing and energy conversion is widely applied.But common large volume C3N4Due to poorly water-soluble and
Particle diameter limits greatly its deep application in electrochemical field.Therefore, scientist is generally using directly ultrasonic in aqueous medium
Method prepares C3N4Nanometer sheet, to improve its dispersiveness in water, reduces toxicity and improves the performances such as its Optical Electro-Chemistry.Another
Aspect, due to C3N4, originally as semiconductor, its electric conductivity is too poor, also largely hinders it in electrochemical field for nanometer sheet
Application.But C3N4Planar molecular structure in contain substantial amounts of tertiary N atom, quaternized be changed into ion liquid type in fact existing
Provide possibility, and the electric charge on its surface can also be increased during being changed into ion liquid type, improve overall electric conductivity
Can, thus improving it as electrocatalysis characteristic during electrode material.Based on this, the present invention is first by C3N4Acid is protonated
Preparation C3N4Nanometer sheet, then occurs substitution reaction to realize with n-bromide butane in the basic conditions more quaternized, prepares ionic liquid
The C of functionalization3N4Nanometer sheet, gained ion liquid functionalization azotized carbon nano piece is provided with the active site of increase, raising
Dispersiveness, improve electric conductivity and raising electrochemical catalysis performance, its drop coating is prepared ionic liquid work(in electrode surface
Azotized carbon nano sheet modified electrode, and the efficient and sensible detection for 2,4- Dichlorophenol in aqueous medium can be changed, thus improving tested
Survey Direct Electrochemistry on modified electrode for the material and electrocatalysis characteristic, have to setting up novel high-sensitivity electrochemical detection method
Significance.
Content of the invention：
For the demand of the deficiencies in the prior art and this area research and application, a kind of ion liquid functionalization carbonitride
Nano-sheet modified electrode, i.e. the prepared modified electrode by ion liquid functionalization azotized carbon nano piece modified glassy carbon electrode.
A kind of ion liquid functionalization azotized carbon nano sheet modified electrode provided by the present invention is it is characterised in that described repair
The basal electrode of decorations electrode is glass-carbon electrode, and decorative material is ion liquid functionalization azotized carbon nano piece；Described ionic liquid
Functionalization azotized carbon nano piece is to be reacted with the azotized carbon nano piece peeled off by n-bromide butane to be obtained；Described glass-carbon electrode is designated as
GCE, described azotized carbon nano piece is designated as C3N4, described ion liquid functionalization azotized carbon nano piece is designated as IL-C3N4, described from
Sub- liquid functional azotized carbon nano sheet modified electrode is designated as IL-C3N4/GCE.
The second object of the present invention is to provide a kind of preparation side of ion liquid functionalization azotized carbon nano sheet modified electrode
Method is it is characterised in that include step in detail below：
(a)C3N4The preparation of nanometer sheet
Under nitrogen atmosphere, a certain amount of melamine is calcined 4h, prepared carbonitride in 550 DEG C, weigh 1g carbonitride and be dissolved in
In the 20mL concentrated sulfuric acid, be stirred at room temperature after 2h and add the dilution of 200mL deionized water, by dilution ultrasonic disperse 8h, ultrasonic after upper
In 3800rpm centrifugation, gained bottom precipitation is C to layer solution3N4Nanometer sheet；
(b)IL-C3N4Preparation
Weigh the C taking gained in 0.5～0.8g (a)3N4Add mixed to 50mL absolute ethyl alcohol and 5～10mL n-bromide butane
Close liquid in, ultrasonic after 40～80 DEG C of water bath with thermostatic control heating stirring 24～48h, resulting solution is in 12000rpm centrifugation
15min, takes bottom precipitation respectively deionized water and absolute ethanol washing three times, has obtained liquid functional after drying and grinding
Azotized carbon nano piece：IL-C3N4；
(c)IL-C3N4The preparation of modified electrode
Glass-carbon electrode polishing grinding is become minute surface, uses dust technology, absolute ethyl alcohol and high purity water to be cleaned by ultrasonic 1min, room respectively
The lower nature of temperature dries standby；Weigh the IL-C obtaining in step (b)3N4Deionized water is dispersed so as to mass concentration is
3mg/mL, pipettes the uniform drop coating of 5～10 μ L in the glassy carbon electrode surface of pretreatment with liquid-transfering gun, obtains final product after drying under infrared lamp
Arrive ion liquid functionalization azotized carbon nano sheet modified electrode：IL-C3N4/GCE.
It is characterized in that IL-C in step (b)3N4Preparating mechanism be that the generation of n-bromide butane and upper tertiary N atom is quaternized
Reaction；Described IL-C3N4With respect to C3N4Its dispersiveness of nanometer sheet and electric conductivity have obtained significant raising；System in step (c)
Standby IL-C3N4During/GCE, only need to be by decorative material IL-C3N4Slurry drops be applied to electrode surface, without other film forming agents and fixation
Agent.
The three of the object of the invention are to provide a kind of ion liquid functionalization azotized carbon nano sheet modified electrode fixed in electrochemistry
Application in amount detection chlorophenol.Specifically it is simply that described modified electrode detects answering in 2,4- Dichlorophenol in electrochemical quantitative
With.
The present invention passes through n-bromide butane and the C peeling off3N4There is substitution reaction in the tertiary N atom in nanometer sheet, make C3N4Receive
Rice piece ion liquid functionalization, has obtained the C of ion liquid functionalization3N4Nanometer sheet, is prepared for IL-C using drop-coating3N4/
GCE, and constructed based on IL-C3N4The third generation chlorophenol electrochemical sensor of/GCE.
The present invention compared with prior art, has following remarkable advantage：The ion liquid functionalization nitridation of gained of the present invention
Without other film forming agents and fixative during the preparation of carbon nanosheet modified electrode；Described modified electrode is in electro-catalysis 2,4- Dichlorophenol side
Face has given full play to ion liquid functionalization and has peeled off C3N4The synergy of nanometer sheet；By n-bromide butane to C3N4Nanometer
The substitution reaction of piece, increased the specific surface area of nanometer sheet, avtive spot, electric conductivity, with entering to inhibit C3N4Nanometer sheet poly-
Collection, IL-C3N4As electrode modified material for providing bridge between chlorophenol and basal electrode, substantially increase to 2,4- Dichlorophenol
Capture and electro-catalysis ability, specifically, IL-C3N4Composite membrane creates expectation not to the electrochemical catalysis of 2,4- Dichlorophenol
The technique effect arriving；The complex film modified electrode pair 2 of gained of the present invention, the electrocatalytic effect of 4- Dichlorophenol, with single C3N4
Nano-sheet modified electrode is compared, and tool is significantly improved；Sensor of the present invention has that quick response, Monitoring lower-cut be low, inspection
The features such as survey wide ranges and be applied to Site Detection, method is simple to operate, mild condition, preparation cost are low.
Brief description：
Fig. 1 is embodiment 1 gained IL-eC3N4Transmission electron microscope photo.
Fig. 2 is embodiment 2 (c), comparative example 1 (a), comparative example 2 (b) gained modified electrode containing 5.0mmol/L [Fe
(CN)6]3-/4-With the electrochemical impedance figure in the 0.1mol/L KCl aqueous solution.
Fig. 3 is embodiment 2 (c), comparative example 1 (a), comparative example 2 (b) gained modified electrode containing 0.1mmol/L2,4- bis-
In the phosphate buffer solution of the pH=7 of chlorophenol, sweep speed for cyclic voltammogram during 0.1V/s.
Fig. 4 A is embodiment 2 gained modified electrode Dichlorophenol of 2,4- containing 0.1mmol/L under the conditions of different scanning speed
Cyclic voltammogram in the phosphate buffer solution of pH=7；Fig. 4 B is the line of embodiment 2 gained modified electrode electric current and sweep speed
Sexual intercourse figure.
Fig. 5 A, constantly increases with chlorophenol concentration for embodiment 2 gained modified electrode in the PBS cushioning liquid of pH=7
Current versus time curve, illustration is the enlarged drawing of current versus time curve in 200-600 time period second；Fig. 5 B is embodiment 2 gained
Electric current in the PBS cushioning liquid of pH=7 for the modified electrode and the linear relationship chart of concentration.
Specific embodiment：
For further understanding the present invention, the invention will be further described with reference to the accompanying drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1：
(a)C3N4The preparation of nanometer sheet
Under nitrogen atmosphere, a certain amount of melamine is calcined 4h, prepared carbonitride in 550 DEG C, weigh 1g carbonitride and be dissolved in
In the 20mL concentrated sulfuric acid, be stirred at room temperature after 2h and add the dilution of 200mL deionized water, by dilution ultrasonic disperse 8h, ultrasonic after upper
In 3800rpm centrifugation, gained bottom precipitation is C to layer solution3N4Nanometer sheet；
(b)IL-C3N4Preparation
Weigh the C taking gained in 0.6g (a)3N4Add to the mixed liquor of 50mL absolute ethyl alcohol and 8mL n-bromide butane, surpass
After 50 DEG C of water bath with thermostatic control heating stirrings 48h, resulting solution, in 12000rpm centrifugation 15min, takes bottom precipitation respectively to sound
Deionized water and absolute ethanol washing three times, have obtained liquid functional azotized carbon nano piece after drying and grinding：IL-C3N4；
(c)IL-C3N4The preparation of modified electrode
Glass-carbon electrode polishing grinding is become minute surface, uses dust technology, absolute ethyl alcohol and high purity water to be cleaned by ultrasonic 1min, room respectively
The lower nature of temperature dries standby；Weigh the IL-C obtaining in step (b)3N4Deionized water is dispersed so as to mass concentration is
3mg/mL, pipettes the uniform drop coating of 8 μ L in the glassy carbon electrode surface of pretreatment with liquid-transfering gun, obtains after drying under infrared lamp
Ion liquid functionalization azotized carbon nano sheet modified electrode：IL-C3N4/GCE.
Embodiment 2：
(a)C3N4The preparation of nanometer sheet
According to the method in step (a) in embodiment 1 and condition preparation；
(b)IL-C3N4Preparation
Weigh the C taking gained in 0.8g (a)3N4Add to the mixed liquor of 50mL absolute ethyl alcohol and 8mL n-bromide butane, surpass
After 60 DEG C of water bath with thermostatic control heating stirrings 36h, resulting solution, in 12000rpm centrifugation 15min, takes bottom precipitation respectively to sound
Deionized water and absolute ethanol washing three times, have obtained liquid functional azotized carbon nano piece after drying and grinding：IL-C3N4；
(c)IL-C3N4The preparation of modified electrode
Glass-carbon electrode polishing grinding is become minute surface, uses dust technology, absolute ethyl alcohol and high purity water to be cleaned by ultrasonic 1min, room respectively
The lower nature of temperature dries standby；Weigh the IL-C obtaining in step (b)3N4Deionized water is dispersed so as to mass concentration is
3mg/mL, pipettes the uniform drop coating of 6 μ L in the glassy carbon electrode surface of pretreatment with liquid-transfering gun, obtains after drying under infrared lamp
Ion liquid functionalization azotized carbon nano sheet modified electrode：IL-C3N4/GCE.
Embodiment 3：
(a)C3N4The preparation of nanometer sheet
According to the method in step (a) in embodiment 1 and condition preparation；
(b)IL-C3N4Preparation
Weigh the C taking gained in 0.5g (a)3N4Add to the mixed liquor of 50mL absolute ethyl alcohol and 8mL n-bromide butane, surpass
After 70 DEG C of water bath with thermostatic control heating stirrings 48h, resulting solution, in 12000rpm centrifugation 15min, takes bottom precipitation respectively to sound
Deionized water and absolute ethanol washing three times, have obtained liquid functional azotized carbon nano piece after drying and grinding：IL-C3N4；
(c)IL-C3N4The preparation of modified electrode
Glass-carbon electrode polishing grinding is become minute surface, uses dust technology, absolute ethyl alcohol and high purity water to be cleaned by ultrasonic 1min, room respectively
The lower nature of temperature dries standby；Weigh the IL-C obtaining in step (b)3N4Deionized water is dispersed so as to mass concentration is
3mg/mL, pipettes the uniform drop coating of 7 μ L in the glassy carbon electrode surface of pretreatment with liquid-transfering gun, obtains after drying under infrared lamp
Ion liquid functionalization azotized carbon nano sheet modified electrode：IL-C3N4/GCE.
Embodiment 4：
(a)C3N4The preparation of nanometer sheet
According to the method in step (a) in embodiment 1 and condition preparation；
(b)IL-C3N4Preparation
Weigh the C taking gained in 0.6g (a)3N4Add to the mixed liquor of 50mL absolute ethyl alcohol and 10mL n-bromide butane, surpass
After 80 DEG C of water bath with thermostatic control heating stirrings 48h, resulting solution, in 12000rpm centrifugation 15min, takes bottom precipitation respectively to sound
Deionized water and absolute ethanol washing three times, have obtained liquid functional azotized carbon nano piece after drying and grinding：IL-C3N4；
(c)IL-C3N4The preparation of modified electrode
Glass-carbon electrode polishing grinding is become minute surface, uses dust technology, absolute ethyl alcohol and high purity water to be cleaned by ultrasonic 1min, room respectively
The lower nature of temperature dries standby；Weigh the IL-C obtaining in step (b)3N4Deionized water is dispersed so as to mass concentration is
3mg/mL, pipettes the uniform drop coating of 10 μ L in the glassy carbon electrode surface of pretreatment with liquid-transfering gun, obtains after drying under infrared lamp
Ion liquid functionalization azotized carbon nano sheet modified electrode：IL-C3N4/GCE.
Comparative example 1：
Directly use naked glass-carbon electrode (GCE).
Comparative example 2：
According to the above-mentioned method preparing modified electrode, with the C of step (a) gained in embodiment 13N4Nanometer sheet is prepared into dense
Spend the dispersion liquid for 3mg/mL, take 10 μ L drop coatings in the glassy carbon electrode surface of milled, after naturally drying, obtain C3N4/ GCE modifies electricity
Pole.
Fig. 1 is embodiment 1 gained IL-C3N4Transmission electron microscope photo.It can be seen that embodiment 1 gained
IL-C3N4Sample presents thin slice superposition shape, the C of sur-face peeling3N4Nanometer sheet has certain stacking situation, but permissible
Be clearly seen that lamellar structure as tulle, existed with the shape of fold, curling, piece interlayer is interlaced, this be probably from
Sub- liquid functional makes these nanometer sheet link together.It may also be seen that sample does not have serious gathering now
As, but presenting good dispersiveness, nanometer sheet rough surface is rough, and surface presents many dolly dimples, and this may
It is ionic liquid in C3N4Caused by the connection of nanometer sheet marginal portion, see that very thin lamella is best proof from picture,
Show that n-bromide butane achieves to C to the substitution reaction of tertiary N atom3N4The ion liquid functionalization of nanometer sheet.
Fig. 2 is embodiment 2 (c), comparative example 1 (a), comparative example 2 (b) gained modified electrode containing 5.0mmol/L [Fe
(CN)6]-3/-4With the electrochemical impedance figure in the 0.1mol/L KCl aqueous solution.It can be seen that the spectrogram of a, b is divided into two
Semicircle under part, wherein high frequency condition corresponding effective electron transfer control process, its half circular diameter represents electro transfer resistance
(Ret)；And the linear segment of low-frequency range corresponding be solutes accumulation control process.Electrochemical impedance result shows, C3N4/GCE
(curve b) presents that (the big arc diameter of curve a) shows C than naked glass-carbon electrode3N4The poor electric conductivity of nanometer sheet, this is
Determined by the semiconductor property of carbonitride itself.When to C3N4After nanometer sheet ion liquid functionalization, IL-C3N4/ GCE is (bent
The impedance diagram of line c) almost becomes straight line, illustrates that impedance substantially reduces, and shows that the electron transport rate of electrode surface adds
By force.This is mainly due to the C after ion liquid functionalization3N4Surface carries electric charge, increased the electric conductivity of decorative material, and
Increased the effective area of electrode so that more [Fe (CN)6]3-/4-Participate in electrochemical reaction, thus improve electronics
Transfer rate.
Fig. 3 is embodiment 2 (c), comparative example 1 (a), comparative example 2 (b) gained modified electrode containing 0.1mmol/L2,4- bis-
In the phosphate buffer solution of the pH=7 of chlorophenol, sweep speed for cyclic voltammogram during 0.1V/s.As seen from the figure, three kinds of electrodes
All an obvious oxidation peak in (curve a, b, c), illustrates in two kinds of electrode surfaces, 2,4- Dichlorophenol all there occurs that oxidation is anti-
Should.Due to corresponding reduction peak not occurring, illustrate that 2,4- Dichlorophenol belongs to complete in the electrochemical oxidation behavior of electrode surface
Irreversible behavior.From oxidizing potential as can be seen that 2,4- Dichlorophenols are in IL-C3N4/ GCE (the response pctential of curve c) electrode surface
Than GCE (curve a) and C3N4(curve b) has born shifting to/GCE, simultaneously IL-C3N4(oxidation peak current on curve c) is also bright for/GCE
Show and be more than GCE (curve a) and C3N4/ GCE (electric current on curve b), after ion liquid functionalization is described, IL-C3N4To 2,4- bis-
The electrochemical oxidation tool of chlorophenol is significantly improved, and this is because the carbonitride peeled off fully exposes electro catalytic activity site,
Ion liquid functionalization azotized carbon nano piece preferably can be dispersed in electrode surface simultaneously, and its surface has carried electric charge, greatly
Accelerate greatly the electro transfer in electrode process, improve electrode pair 2, the capture of 4- Dichlorophenol and electro-catalysis efficiency.
Embodiment 5：
By the IL-eC obtained by embodiment 23N4As working electrode, platinum electrode is to electrode, saturation to/GCE modified electrode
Calomel electrode is reference electrode, investigates difference using three-electrode system and sweeps the impact to 2,4- Dichlorophenol electro-oxidation process for the speed.Survey
Strip part：Electrochemical window is -1.0V-1.0V, accumulating potential：- 0.2V, enrichment time：120s, supporting electrolyte is 0.1mol/L
The phosphate buffer solution of pH=7.0.
Fig. 4 A is embodiment 2 gained modified electrode Dichlorophenol of 2,4- containing 0.1mmol/L under the conditions of different scanning speed
Cyclic voltammogram in the phosphate buffer solution of pH=7, it can be seen that increase with sweeping speed, the oxygen of 2,4- Dichlorophenols
Change peak current to be regularly gradually increased.Fig. 4 B is the linear relationship chart of embodiment 2 gained modified electrode electric current and sweep speed.
As illustrated, sweep speed is in the range of 30～350mV/s, the oxidation peak current of 2,4- Dichlorophenols becomes preferable with sweep speed
Linear relationship (R2=0.9968), the electrochemical oxidation process on embodiment 2 gained modified electrode surface for 2, the 4- Dichlorophenol is described
Belong to absorption and control process.
Embodiment 6：
By the IL-C obtained by embodiment 23N4As working electrode, platinum electrode is to electrode to/GCE modified electrode, and saturation is sweet
Mercury electrode is reference electrode, under optimized experiment condition, to probe into the linear of modified glassy carbon electrode using current-vs-time method
Detection range and test limit.Test condition：Initial potential is 0.85V, and the sampling interval is 0.1s, and time of repose is 2s, during experiment
Scale parameter is 3D.
Fig. 5 A, constantly increases with chlorophenol concentration for embodiment 2 gained modified electrode in the PBS cushioning liquid of pH=7
Current versus time curve, illustration is the enlarged drawing of current versus time curve in 200-600 time period second.It can be seen that working as
After certain density 2,4- Dichlorophenol is added into phosphoric acid buffer bottom liquid, modified electrode can sensitively detect 2,4- in solution
The change of Dichlorophenol concentration.Fig. 5 B is electric current in the PBS cushioning liquid of pH=7 for the embodiment 2 gained modified electrode and concentration
Linear relationship chart.As seen from the figure, in the range of 0.02 160 μm of ol/L, the concentration of 2,4- Dichlorophenols and oxidation peak current have
Preferably linear relationship (R2=0.9996), detection is limited to 7.96nmol/L (n=10), it can be seen that embodiment 2 gained
2, the 4- Dichlorophenol electrochemical sensor that modified electrode builds has range of linearity width, the low feature of test limit, and its performance is better than
The modified electrode of many existing detection 2,4- Dichlorophenols, the results are shown in Table 1.
The IL-C of table 1 present invention preparation3N4The comparison to the detection performance of 2,4- Dichlorophenol and existing electrode for/the GCE
Claims (4)
1. a kind of ion liquid functionalization azotized carbon nano sheet modified electrode is it is characterised in that the basal electrode of described modified electrode
For glass-carbon electrode, decorative material is ion liquid functionalization azotized carbon nano piece；Described ion liquid functionalization azotized carbon nano
Piece is to be reacted with the azotized carbon nano piece peeled off by n-bromide butane to be obtained；Described glass-carbon electrode is designated as GCE, described azotized carbon nano
Piece is designated as C3N4, described ion liquid functionalization azotized carbon nano piece is designated as IL-C3N4, described ion liquid functionalization carbonitride
Nano-sheet modified electrode is designated as IL-C3N4/GCE；
The preparation method of described ion liquid functionalization azotized carbon nano sheet modified electrode is it is characterised in that include walking in detail below
Suddenly：
(a)C3N4The preparation of nanometer sheet
Under nitrogen atmosphere, a certain amount of melamine is calcined 4h, prepared carbonitride in 550 DEG C, weigh 1g carbonitride and be dissolved in 20mL
In the concentrated sulfuric acid, be stirred at room temperature after 2h and add the dilution of 200mL deionized water, by dilution ultrasonic disperse 8h, ultrasonic after upper strata molten
Liquid is C in 3800rpm centrifugation, gained bottom precipitation3N4Nanometer sheet；
(b)IL-C3N4Preparation
Weigh the C taking gained in 0.5～0.8g (a)3N4Add to the mixed liquor of 50mL absolute ethyl alcohol and 5～10mL n-bromide butane
In, ultrasonic after 40～80 DEG C of water bath with thermostatic control heating stirring 24～48h, resulting solution, in 12000rpm centrifugation 15min, takes
Bottom precipitation respectively deionized water and absolute ethanol washing three times, has obtained liquid functional carbonitride and has received after drying and grinding
Rice piece：IL-C3N4；
(c)IL-C3N4The preparation of modified electrode
Glass-carbon electrode polishing grinding is become minute surface, uses dust technology, absolute ethyl alcohol and high purity water to be cleaned by ultrasonic 1min, under room temperature respectively
Naturally dry standby；Weigh the IL-C obtaining in step (b)3N4Deionized water is dispersed so as to mass concentration is 3mg/
ML, pipettes the uniform drop coating of 5～10 μ L in the glassy carbon electrode surface of pretreatment with liquid-transfering gun, obtains after drying under infrared lamp
Ion liquid functionalization azotized carbon nano sheet modified electrode：IL-C3N4/GCE.
2. the preparation method of a kind of ion liquid functionalization azotized carbon nano sheet modified electrode according to claim 1, its
It is characterised by IL-C in step (b)3N4Preparating mechanism be that n-bromide butane and upper tertiary N atom occur quaterisation；Described
IL-C3N4With respect to C3N4Its dispersiveness of nanometer sheet and electric conductivity have obtained significant raising；Preparation IL-C in step (c)3N4/
During GCE, only need to be by decorative material IL-C3N4Slurry drops be applied to electrode surface, without other film forming agents and fixative.
3. a kind of ion liquid functionalization azotized carbon nano sheet modified electrode described in claim 1 detects chlorine in electrochemical quantitative
Application in phenol.
4. a kind of ion liquid functionalization azotized carbon nano sheet modified electrode according to claim 3 is examined in electrochemical quantitative
Survey the application in chlorophenol it is characterised in that described chlorophenol is 2,4- Dichlorophenol.
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| CN110133074A (en) * | 2019-05-23 | 2019-08-16 | 上海烟草集团有限责任公司 | A kind of preparation method and applications of electrode, electrochemical sensor |
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| CN114669317A (en) * | 2022-04-08 | 2022-06-28 | 国科温州研究院(温州生物材料与工程研究所) | Nano enzyme with multistage enzyme-linked reaction performance and preparation method and application thereof |
| CN114669317B (en) * | 2022-04-08 | 2023-09-26 | 国科温州研究院(温州生物材料与工程研究所) | Nano-enzyme with multistage enzyme-linked reaction performance, and preparation method and application thereof |
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