CN102680546A - Nickel ion electrochemical sensor and method for synthesizing electrode material chelating resin - Google Patents
Nickel ion electrochemical sensor and method for synthesizing electrode material chelating resin Download PDFInfo
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- CN102680546A CN102680546A CN201210167621XA CN201210167621A CN102680546A CN 102680546 A CN102680546 A CN 102680546A CN 201210167621X A CN201210167621X A CN 201210167621XA CN 201210167621 A CN201210167621 A CN 201210167621A CN 102680546 A CN102680546 A CN 102680546A
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Abstract
A nickel ion electrochemical sensor comprises a reaction tank (6), an electrode support (5), a reference electrode (3), a work electrode (2) and an auxiliary electrode (1), and is characterized in that a modified electrode with a tripolycyanamide-formaldehyde- ethylenediamine-tetra-oxaloacetic acid chelating resin/carboxylation carbon nano-tube composite modified layer (4) on the end surface of a wax-filled graphite electrode is used as the work electrode (2); and the mass ratio of the chelating resin to a carboxylation carbon nano-tube is 10:1-100:1. The chelating resin is formed by using tripolycyanamide, formaldehyde and ethylene dinitrilotetra oxaloacetic acid as monomers, and performing ultrasonic polymerization at normal temperature under the condition that aqueous solution has a dispersing agent, a colloid protecting agent, porogen and an anti-blocking agent. The sensor is stable in performance, high in anti-interference ability, long in service life and low in detection limit, and can reach 1X10<-13>mol*L<-1>.
Description
One, technical field
The present invention relates to the preparation method of a kind of electrochemical sensor and electrode material thereof; The nickel ion electrochemical sensor that specifically to adopt carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin and carboxylated CNT compound modified electrode be working electrode, and the synthetic method of carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin.
Two, background technology
Heavy metal nickel mainly is present in the water environment with ion and compound form, in case take in human body, can produce accumulation; And then cause kidney and a series of diseases such as cardiovascular system poisoning, tumour canceration, harm humans healthy (E.Denkhaus, K.Salnikow; Crit Rev Oncol Hematol.; 2002,42,35; R.Segura, M.Pradena, D.Pinto, F.Godoy, E.Nagles, V.Arancibia, Talanta, 2011,85,2316).Therefore, detect delicately accurately that heavy metal nickel has great importance in the water environment.Electrochemical process has instrument miniaturization, characteristics such as quick easy and simple to handle, sensitive, has been used to the monitoring of nickel ion in the water sample (Ni (II)).Its principle mainly is based on the sensitivity of complexing agent to the complexing inrichment raising detection of Ni (II), adopts stripping voltammetry to realize the detection to Ni (II).For example, based on the complex scheme of diacetyl oximes material, can realize Electrochemical Detection (F.O.Tartarotti, M.F.de Oliveira from different perspectives to Ni (II) to Ni (II); V.R.Balbo, N.R.Stradiotto, Microchim Acta; 2006,155,397; R.P.Baldwin, J.K.Christensen, L.Kryger, Anal.Chem., 1986,58,1790; H.Zhang, R.Wollast, J.C.Vire, G.J.Patriarche, Analyst, 1989,114,1597; M.Morfobos, A.Economou, A.Voulgaropoulos, Analytica Chimica Acta, 2004,519,57), wherein, the method for Zhang etc. is relatively low to the detectability of Ni (II), is 5 * 10
-11MolL
-1(H.Zhang, R.Wollast, J.C.Vire, G.J.Patriarche, Analyst, 1989,114,1597).In addition, based on 1-Nitroso-2-naphthol, 5-[(p-methylphenyl) azo]-8-aminoquinoline and calcium carboxylate complexing, can realize respectively that also detectability is respectively 1.7 * 10 to the detection of Ni (II) to Ni (II)
-9, 3.0 * 10
-11With 8.5 * 10
-10MolL
-1(R.Segura, M.Pradena, D.Pinto, F.Godoy, E.Nagles, V.Arancibia, Talanta, 2011,85,2316; Z.Q.Zhang, Z.P.Cheng, S.Z.Cheng, G.F.Yang, Talanta, 1991,38,1487; M.K.Amini, M.Kabiri, Journal ofthe Iranian Chemical Society, 2005,2,32).In a word; Significant achievement has been obtained in the Electrochemical Detection field of correlative study person Ni (II) in the WS both at home and abroad; But still exist such as problems such as the complex reaction equilibration time is long to cause detection time long, and equilibrium condition is wayward, and electrode stability is not high; Thereby be necessary development can efficiently concentrating Ni the compound substance of (II), prepare more sensitivity nickel ion electrochemical sensor fast.
On the other hand, Ghaffar etc. are through 6～7 hours emulsion polymerization, in the time of 90 ℃; Synthesized micron-sized carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin (MFT), discovered: MFT has good adsorption effect (M.A.A.Ghaffar, Z.H.A.Wahab to Cu (II); K.Z.Elwakeel, Hydrometallurgy, 2009; 96,27).Because this resin is non-conductive, can up till now for this reason, also MFT be used to prepare the research report of Ni (II) sensor directly as the trim of electrode.In addition, CNT has unique photoelectric catalytically active, good electronic conduction and absorption property (S.Mohanapriya, V.Lakshminarayanan, Talanta, 2007,71,493).CNT is (G.P.Jin, Y.F.Ding, P.P.Zheng, 2007,166,80) after strong acid treatment, and carboxylated CNT and the surface adhesion between organic substrate obviously improved (J.Kathi, K.Y.Rhee, J Mater Sci, 2008,43,33).
Three, summary of the invention
The present invention is directed in the prior art electrochemical process and detect the existing defective of nickel ion (Ni (II)) in the water; Aim to provide a kind of nickel ion electrochemical sensor that has new working electrode; Technical matters to be solved is raising stability and sensitivity, reduces detectability, and realizes fast detecting.
The alleged nickel ion electrochemical sensor of the present invention comprises reaction tank 6, electrode suppor 5 and contrast electrode 3, working electrode 2 and to electrode (auxiliary electrode) 1, difference with the prior art be described working electrode 2 be the end face at the graphite electrode of propolizing (WGE) carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/carboxylated CNT compound (MFT/MWCNT) decorative layer 4 is arranged modified electrode as working electrode 2.As shown in Figure 1.
The mass ratio of MFT and MWCNT is 10: 1-100: 1.Preferred 10: 1-40: 1.
Alleged carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin (MFT) structural formula of the present invention is following, and wherein functional group is melamine group and ethylenediamine tetraacetic oxaloacetic acid group.
The existing synthetic method of above-mentioned chelating resin is emulsion polymerization; The present invention is improved to ultrasonic polymerization; With melamine, formaldehyde and ethylenediamine tetraacetic oxaloacetic acid is polymerization single polymerization monomer; Comprise polymerization, separation, washing and drying; Difference with the prior art is that described polymerization is to add polymerization single polymerization monomer and spreading agent, colloid protective agent, pore-foaming agent and anticaking agent at water, slowly adds hydrochloric acid adjust pH 4-5 again, under nitrogen protection and normal temperature sonic oscillation 10-40 minute then; Add end of the chain terminator and continue ultrasonic reaction and obtained polymerized emulsion in 1-10 minute, through leave standstill, Separation of Solid and Liquid, washing, drying obtain micron level spherical melamine-formaldehyde-ethylenediamine tetraacetic oxaloacetic acid chelating resin (MFT) behind the breakdown of emulsion.
The mol ratio of said melamine, formaldehyde and ethylenediamine tetraacetic oxaloacetic acid is 1: 5: 1-1: 10: 3; Said spreading agent is a lauryl sodium sulfate, and addition is the 0.15-2% of monomer gross mass; Said colloid protective agent is a polyvinyl alcohol (PVA), and addition is the 0.05-0.2% of monomer gross mass; Said pore-foaming agent is selected from one or both in acetone, phenol or the polyglycol, and addition is the 0.02-0.2% of monomer gross mass, and when pore-foaming agent was two kinds, ratio between the two was any; Said anticaking agent is a kind of in sodium sulphate or the sodium chloride, and addition is the 0.15-2% of monomer gross mass; Said end of the chain terminator is selected from o-toluic acid or triethanolamine, and addition is the 0.01-0.2% of monomer gross mass.
This ultrasonic converging operation step is following:
A, melamine, formaldehyde and ethylenediamine tetraacetic oxaloacetic acid added obtain monomer mixed solution in the entry; In monomer mixed solution, add spreading agent, colloid protective agent, pore-foaming agent and anticaking agent, and make the solid reactant dissolving obtain homogeneous reaction liquid with hydrochloric acid adjust pH 4-5;
B, under nitrogen protection with step a gained reactant liquor in normal temperature sonic oscillation 10-40 minute, add terminator, continue ultrasonic reaction finished in 1-10 minute to react polymerized emulsion;
C, the gained polymerized emulsion is left standstill 2-10 hour breakdown of emulsion in 4-15 ℃; After the Separation of Solid and Liquid; In 30-70 ℃ of following vacuum drying 3-10 hour, and dry after water, acetone and the washing with alcohol successively, obtain micron level spherical carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin.
Described carboxylated CNT (MWCNT) be exactly CNT through strong acid treatment, concrete processing procedure and method are referring to document G.P.Jin, Y.F.Ding, P.P.Zheng, 2007,166,80.10mg MWCNT was mixed the back sonic oscillation 7 hours with 10mL nitric acid and perchloric acid mixed solution (volume ratio is 7: 3), with secondary water MWCNT is washed till neutrality then, again with being placed on air drying after the acetone.Get the MWCNT that 2.5mg handles well and place 10mL acetone (containing 0.5%nafion), obtain the MWCNT suspending liquid of black behind the sonic oscillation.
The preparation of carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/carboxylated CNT compound modified electrode:
Get the MFT chelating resin and add in formic acid, toluene or the methyl alcohol and be suspending liquid, centrifuging goes out solid, with drying behind the second distillation water wash.With dried MFT chelating resin and carboxylated CNT ultrasonic mixing in the 50mL ethanol solution, obtain the suspending liquid (MFT/MWCNT) of carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/carboxylated CNT compound; 10～40 μ L MFT/MWCNT are dripped be coated in the graphite electrode surface of propolizing, obtain carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/carboxylated CNT compound modified electrode (MFT/MWCNT/WGE) after drying naturally.
MFT and MWCNT mass ratio are 10 in the described compound: 1-100: 1, preferred 10: 1-40: 1.
The detection of nickel ion:
Under the room temperature, with 0.1molL
-1Potassium rhodanide, potassium chloride and potassium phosphate in a kind of be supporting electrolyte; With the modified electrode MFT/MWCNT/WGE of above-mentioned preparation as working electrode, with platinum filament for being contrast electrode to electrode (auxiliary electrode), saturated calomel electrode; Enrichment time is 3-15min,, to the potential range of-1.7 ~ 0.6V, through anodic stripping voltammetry Ni (II) is detected at-1.25 ~ 0.5V, and the cleaning current potential that at every turn detects rear electrode is at-0.4 ~ 0.2 volt, and scavenging period is at 1-7min.
Compared with present technology, beneficial effect of the present invention is following:
1, MFT chelating resin/carboxylated CNT composite properties is good
The carboxylated CNT (MWCNT) that the present invention adopted has stronger affinity to the MFT chelating resin, can make the MFT chelating resin of micron level spherical be easy to disperse, and is adsorbed on the MWCNT equably.The MFT/MWCNT compound that constitutes not only has good chelation to Ni (II), also has good electric conductivity concurrently.The modified electrode that makes has less background current, can be used for preparing the electrochemical sensor of the Ni (II) that detects water-soluble middle trace.
2, stable, the long service life of sensor performance, be easy to upgrade
Dimethylglyoxime and 1-nitroso--2 hydroxy naphthalene sequestrant used in the Ni of bibliographical information (II) sensor are water miscible, are modified to be easy on the electrode run off, and serviceable life is short, and the hanging mercury electrode that adopts is poisonous.The used MFT/MWCNT trim of the present invention is water insoluble, can be coated on equably on the graphite electrode after processing suspending liquid, and preparation technology is simple, is difficult for running off, and is easy to change through mechanical friction.See table 1.The applicant selects four kinds of Ni (II) electrochemical sensors and this sensor of bibliographical information to compare, and each item performance sees the following form 1.Comparative result shows that the sensor performance that the present invention prepares is best relatively.Document 1 (M.K.Amini, M.Kabiri, J.the Iranian Chemical Society, 2005,2,32), document 2 (R.Segura; M.Pradena, D.Pinto, F.Godoy, E.Nagles, V.Arancibia, Talanta, 2011; 85,2316), document 3 (F.O.Tartarotti, M.F.de Oliveira, V.R.Balbo, N.R.Stradiotto; Microchim Acta, 2006,155,397), document 4 (H.Zhang, R.Wollast; J.C.Vire, G.J.Patriarche, Analyst, 1989,114,1597).
The performance of four kinds of Ni (II) electrochemical sensors of table 1 and this sensor relatively
3, low, the interference free performance raising of the detectability of working electrode
The electrochemical sensor of the present invention's preparation can sensitive be monitored the Ni (II) in the water sample apace, and detectability is low, can reach 1 * 10
-13MolL
-1The Zn (II) of 100 times of Ni (II) concentration, Cu (II), Hg (II), the Cd (II) of 30 times of Ni (II) concentration, Pb (II) all do not disturb the mensuration of Ni (II).See table 2.
The influence that the different coexistent metallic ions of table 2 are measured Ni (II)
4, one of electrode modification thing MFT chelating resin synthesis technique is simple
The used trim of Ni among the present invention (II) electrochemical sensor; The synthetic deficiency at normal temperatures of carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin (MFT) one hour; Compare with existing emulsion phase synthesi, need not add initiating agent, need not heat and stir; Reaction time shortens more than 70%, simple and reliable process.
Four, description of drawings
Fig. 1 is the structural representation of Ni (II) electrochemical sensor for preparing of the present invention.Among the figure, 1, auxiliary electrode (Pt, Φ 1mm), 2, working electrode (graphite; Φ 3mm), 3, contrast electrode (saturated calomel electrode, SCE; Φ 2mm), porous Teflon shell electrode suppor 4, carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/CNT complexes membrane (MFT/MWCNT), 5; 6, electrochemical reaction cell, 7, air admission hole, 8, venthole.
Fig. 2 is the carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin for preparing of the present invention and the infrared spectrogram (FT-IR) of related raw material thereof.The functional group of said chelating resin is identified that by FT-IR (KBr) spectrum the ownership of having carried out each spectrum peak reaches the comparative analysis with raw material.Wherein curve a, b, c, d distinguish the FT-IR spectrum of corresponding carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin, melamine, formaldehyde, ethylenediamine tetraacetic oxaloacetic acid.The analysis result of infared spectrum shows: characteristic peaks all among curve b, c, the d also can observe in curve a, thereby show that above-mentioned chelating resin is synthesized.For example: among the curve a, at 1630 ~ 1437cm
-1, 813cm
-1The stretching vibration peak of visible melamine self framed structure in place and ring outerplanar distortion peak (AI.Balabanovich, Polymer Degradation and Stability, 2004,84,451.); At 1549.3cm
-1The stretching vibration peak of C=O in the visible acid amides in place; At 1344.8cm
-1The place is the plain bending vibration peak of O-H in the carboxyl; At 3341cm
-1, 1549.4cm
-1And 739.2cm
-1The visible ethylenediamine tetraacetic oxaloacetic acid jackshaft in place is connected on the stretching vibration peak of imines N-H on the methylene, the flexural vibrations peak of imines N-H and the ring outerplanar distortion peak (M.A.A.Ghaffar et.al.Hydrometallurgy, 2009,96,27) of imines N-H.
Fig. 3 is the thermogravimetric analysis figure of carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin of preparing of the present invention.Visible by figure: chelating resin quality before being warming up to 100 ℃ is kept constant basically; Between 125～373 ℃; Loss 12.5%; Deviate from residual moisture and the intact monomer of unreacted for this chelating resin, show this chelating resin good thermal stability in this temperature range, do not have signs of degradation to take place; This chelating resin weightlessness is obvious between 373～499 ℃, is decomposable process.
Fig. 4 is the ethylenediamine tetraacetic oxaloacetic acid chelating resin (A) for preparing of the present invention and the field emission scanning electron microscope figure (FE-SEM) of ethylenediamine tetraacetic oxaloacetic acid chelating resin/carboxylated CNT compound (B).Visible by Fig. 4 A: the ethylenediamine tetraacetic oxaloacetic acid chelating resin of the present invention's preparation is a micron level spherical; Visible by Fig. 4 B: carboxylated CNT has stronger bounding force to the MFT chelating resin, this chelating resin is disperseed effectively, and be adsorbed on the CNT equably.
Fig. 5 is in 0.1Mol/L potassium rhodanate (KSCN) supporting electrolyte solution, 1 * 10
-12MolL
-1Ni (II) (NiSO
4) at graphite electrode (WGE; Curve b), chelating resin/graphite electrode (MFT/WGE; Curve c), the stripping volt-ampere curve on carboxylated CNT/graphite electrode (MWCNT/WGE, curve d) and the chelating resin/carboxylated CNT/graphite electrode (MFT/MWCNT/WGE, curve e); Curve a is the stripping volt-ampere curve of MFT/MWCNT/WGE in blank KSCN solution.Visible by figure: with respect to other electrode, the peak current of Ni (II) on MFT/MWCNT/WGE (curve e) is the highest, and detection has good effect to Ni (II) to show this modified electrode.
Fig. 6 is in 0.1Mol/L potassium rhodanate (KSCN) supporting electrolyte solution, 1 * 10
-12~ 1 * 10
-11MolL
-1(interval 2 * 10
-12MolL
-1) the stripping voltammogram of Ni (II) (nickelous sulfate) on MFT/MWCNT/WGE.Dotted line is blank.Visible by figure: the oxidation peak current of Ni (II) demonstrates good linear relationship (illustration) in above-mentioned concentration range, linear equation is: i (μ A)=2.39 * 10
-2+ 17.15C (1 * 10
-12Mol/L, pM), R=0.9816 detects and is limited to 1 * 10
-13MolL
-1(3 σ).
Five, embodiment
Embodiment 1:
Take by weighing 0.8g lauryl sodium sulfate solid; Add in the 100mL water; In sodium dodecyl sulfate solution, add 34.8g ethylenediamine tetraacetic oxaloacetic acid, 37wt% (mass percentage concentration; Down together) formaldehyde 50mL, 12.6g melamine, 0.06g polyvinyl alcohol (PVA), 0.02g phenol and 0.4g sodium sulphate transfer to pH 5.0 with 0.1mol/L HCl solution; Logical nitrogen deoxygenation 10 minutes, (power was 12.5Wcm in ultrasonic at normal temperatures 30 minutes
-1); Add 0.025g o-toluic acid terminator, continue ultrasonic 5min and finish reaction; The gained polymerized emulsion under 4 ℃, is placed breakdown of emulsion after 2 hours, after the Separation of Solid and Liquid,, obtain the dried glue of thick chelating resin 60 ℃ of following vacuum drying 3 hours; With dry behind the dried glue of thick chelating resin water, acetone, washing with alcohol successively, obtain carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin.
Get the MFT chelating resin of a certain amount of step 1 preparation, transfer to suspending liquid with formic acid solution, centrifuging goes out solid, with drying behind the second distillation water wash.Take by weighing 20.0mg MFT chelating resin and the carboxylated CNT of 2.0mg ultrasonic mixing in the 50mL ethanol solution, obtain carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/CNT compound suspending liquid (MFT/MWCNT); 20 μ L MFT/MWCNT are dripped be coated in the graphite electrode surface of propolizing, obtain carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/CNT compound modified electrode (MFT/MWCNT/WGE) after drying naturally.
Under the room temperature, with 0.1molL
-1Potassium rhodanide, potassium chloride and potassium phosphate in a kind of be supporting electrolyte; With the MFT/MWCNT/WGE of gained in the step 2 as working electrode, with platinum filament for being contrast electrode to electrode, saturated calomel electrode; Enrichment time is 3min, in the potential range of-1.7～0.4V, through anodic stripping voltammetry Ni (II) is detected, and the cleaning current potential that at every turn detects rear electrode is at-0.4 volt, and scavenging period is at 3min.
Embodiment 2:
Take by weighing 1g lauryl sodium sulfate solid; Add in the 100mL water; In sodium dodecyl sulfate solution, add 52.2g ethylenediamine tetraacetic oxaloacetic acid, 37wt% formaldehyde 70mL, 12.6g melamine, 0.08g polyvinyl alcohol (PVA), 0.09g acetone and 1g sodium chloride, transfer to pH 4.2 with 0.1mol/L HCl solution; Logical nitrogen deoxygenation 10 minutes, (power was 5.5Wcm in ultrasonic at normal temperatures 20 minutes
-1); Add 0.06g triethanolamine terminator, continue ultrasonic 5min and finish reaction; The gained polymerized emulsion under 4 ℃, is placed breakdown of emulsion after 2 hours, after the Separation of Solid and Liquid,, obtain the dried glue of thick chelating resin 50 ℃ of following vacuum drying 5 hours; With dry behind the dried glue of thick chelating resin water, acetone, washing with alcohol successively, obtain carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin.
Get the MFT chelating resin of a certain amount of step 1 preparation, transfer to suspending liquid with formic acid solution, centrifuging goes out solid, with drying behind the second distillation water wash.Take by weighing 50.0mg MFT chelating resin and the carboxylated CNT of 2.0mg ultrasonic mixing in the 50mL ethanol solution, obtain carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/CNT compound suspending liquid (MFT/MWCNT); 10 μ L MFT/MWCNT are dripped be coated in the graphite electrode surface of propolizing, obtain carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/CNT compound modified electrode (MFT/MWCNT/WGE) after drying naturally.
Under the room temperature, with 0.1molL
-1Potassium rhodanide, potassium chloride and potassium phosphate in a kind of be supporting electrolyte; With the MFT/MWCNT/WGE of gained in the step 2 as working electrode, with platinum filament for being contrast electrode to electrode, saturated calomel electrode; Enrichment time is 5min, in the potential range of-1.25～0.5V, through anodic stripping voltammetry Ni (II) is detected, and the cleaning current potential that at every turn detects rear electrode is at 0.2 volt, and scavenging period is at 4min.
Embodiment 3:
Take by weighing 0.5g lauryl sodium sulfate solid; Add in the 100mL water; In sodium dodecyl sulfate solution, add 43.5g ethylenediamine tetraacetic oxaloacetic acid, 37wt% formaldehyde 30mL, 6.3g melamine, 0.08g polyvinyl alcohol (PVA), 0.1g polyglycol and 0.8g sodium chloride, transfer to pH 4.0 with 0.1mol/L HCl solution; Logical nitrogen deoxygenation 15 minutes, (power was 8.0Wcm in ultrasonic at normal temperatures 20 minutes
-1); Add 0.05g triethanolamine terminator, continue ultrasonic 5min and finish reaction; The gained polymerized emulsion under 10 ℃, is placed breakdown of emulsion after 2 hours, after the Separation of Solid and Liquid,, obtain the dried glue of thick chelating resin 70 ℃ of following vacuum drying 3 hours; With dry behind the dried glue of thick chelating resin water, acetone, washing with alcohol successively, obtain carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin.
Get the MFT chelating resin of a certain amount of step 1 preparation, transfer to suspending liquid with formic acid solution, centrifuging goes out solid, with drying behind the second distillation water wash.Take by weighing 80.0mg MFT chelating resin and the carboxylated CNT of 2.0mg ultrasonic mixing in the 50mL ethanol solution, obtain carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/CNT compound suspending liquid (MFT/MWCNT); 30 μ L MFT/MWCNT are dripped be coated in the graphite electrode surface of propolizing, obtain carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/CNT compound modified electrode (MFT/MWCNT/WGE) after drying naturally.
Under the room temperature, with 0.1molL
-1Potassium rhodanide, potassium chloride and potassium phosphate in a kind of be supporting electrolyte; With the MFT/MWCNT/WGE of gained in the step 2 as working electrode, with platinum filament for being contrast electrode to electrode, saturated calomel electrode; Enrichment time is 15min, in the potential range of-1.0～0.6V, through anodic stripping voltammetry Ni (II) is detected, and the cleaning current potential that at every turn detects rear electrode is at 0.1 volt, and scavenging period is at 7min.
The ultimate analysis of synthetic chelating resin among each embodiment of table 3
Can by table 3See, adopt the carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin of the inventive method preparation, contain functional group melamine proportion at 23.47-20.29%, the proportion of functional group ethylenediamine tetraacetic oxaloacetic acid is at 44.63-51.33%.
Claims (8)
1. nickel ion electrochemical sensor; Comprise reaction tank (6), electrode suppor (5) and contrast electrode (3), working electrode (2) and auxiliary electrode (1), it is characterized in that: described working electrode (2) be the end face at the graphite electrode of propolizing carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin/carboxylated CNT compound decorative layer (4) is arranged modified electrode as working electrode (2); The mass ratio of chelating resin and carboxylated CNT is 10: 1-100: 1.
2. nickel ion electrochemical sensor according to claim 1 is characterized in that: the mass ratio of chelating resin and carboxylated CNT is 10: 1-40: 1.
3. the synthetic method of carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin; With melamine, formaldehyde and ethylenediamine tetraacetic oxaloacetic acid is polymerization single polymerization monomer; Comprise polymerization, separation, washing and drying; It is characterized in that: described polymerization is in water, to add melamine, formaldehyde and ethylenediamine tetraacetic oxaloacetic acid and spreading agent, colloid protective agent, pore-foaming agent and anticaking agent; Slowly add hydrochloric acid adjust pH 4-5 again; Under nitrogen protection and normal temperature sonic oscillation 10-40 minute then, add end of the chain terminator and continue ultrasonic reaction and obtained polymerized emulsion in 1-10 minute, through leave standstill, separation behind the breakdown of emulsion, washing, drying obtain micron order carbamide-ethylenediamine tetraacetic oxaloacetic acid chelating resin; The mol ratio of melamine, formaldehyde and ethylenediamine tetraacetic oxaloacetic acid is 1: 5: 1-1: 10: 3; Addition is in the monomer gross mass, and spreading agent is 0.15-2%, and colloid protective agent is 0.05-0.2%, and pore-foaming agent is 0.02-0.2%, and anticaking agent is 0.15-2%; End of the chain terminator is 0.01-0.2%.
4. synthetic method according to claim 3 is characterized in that: described spreading agent is a lauryl sodium sulfate.
5. synthetic method according to claim 3 is characterized in that: described colloid protective agent is a polyvinyl alcohol (PVA).
6. synthetic method according to claim 3 is characterized in that: described pore-foaming agent is selected from one or both in acetone, phenol or the polyglycol.
7. synthetic method according to claim 3 is characterized in that: described anticaking agent is a kind of in sodium sulphate or the sodium chloride.
8. synthetic method according to claim 3 is characterized in that: described end of the chain terminator is selected from o-toluic acid or triethanolamine.
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| CN104502414A (en) * | 2014-12-30 | 2015-04-08 | 衡阳师范学院 | Method for manufacturing novel transformer oil water-containing sensor |
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| US20030104278A1 (en) * | 2001-11-30 | 2003-06-05 | Katsuya Ito | Nickel electrode for alkaline storage battery, process for the production thereof, alkaline storage battery comprising same and process for the production thereof |
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| CN101713759A (en) * | 2008-09-25 | 2010-05-26 | 米利波尔公司 | Electrochemical method for detecting boron in water |
| CN102327781A (en) * | 2011-07-20 | 2012-01-25 | 合肥工业大学 | Method for preparing nano-nickel/carbon fiber (Ni/CF) catalyst from chemical nickel-plating waste liquid |
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| CN104502414A (en) * | 2014-12-30 | 2015-04-08 | 衡阳师范学院 | Method for manufacturing novel transformer oil water-containing sensor |
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