CN103063719A - Preparation method of glassy carbon electrode modified by gold/cobalt hydroxide film - Google Patents
Preparation method of glassy carbon electrode modified by gold/cobalt hydroxide film Download PDFInfo
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- CN103063719A CN103063719A CN2012105880032A CN201210588003A CN103063719A CN 103063719 A CN103063719 A CN 103063719A CN 2012105880032 A CN2012105880032 A CN 2012105880032A CN 201210588003 A CN201210588003 A CN 201210588003A CN 103063719 A CN103063719 A CN 103063719A
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- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 title claims abstract description 27
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000010931 gold Substances 0.000 title claims abstract description 17
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 title claims abstract description 15
- 229910021397 glassy carbon Inorganic materials 0.000 title abstract 5
- 229910018916 CoOOH Inorganic materials 0.000 claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract description 81
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 32
- 238000001514 detection method Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 abstract description 2
- 102000003846 Carbonic anhydrases Human genes 0.000 abstract 2
- 108090000209 Carbonic anhydrases Proteins 0.000 abstract 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 abstract 2
- LJSAJMXWXGSVNA-UHFFFAOYSA-N a805044 Chemical compound OC1=CC=C(O)C=C1.OC1=CC=C(O)C=C1 LJSAJMXWXGSVNA-UHFFFAOYSA-N 0.000 abstract 1
- 230000006399 behavior Effects 0.000 abstract 1
- 238000001903 differential pulse voltammetry Methods 0.000 abstract 1
- 235000010333 potassium nitrate Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 239000008055 phosphate buffer solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- -1 hydroxy cobalt oxide Chemical compound 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of a gold/cobalt hydroxide film-modified glassy carbon electrode, which is characterized by comprising the following steps: taking the glassy carbon electrode as a base electrode, modifying the base electrode by utilizing a gold/cobalt hydroxide film, putting the gold/cobalt hydroxide film-modified glassy carbon electrode into KNO3 solution containing HAuCI4, taking an SCE (Saturated Calomel Electrode) as a reference and taking a platinum filament as a counter electrode to obtain the GNPs/CoOOH composite modified electrode. The preparation method has the benefits that the composite modified electrode has good electrical conductivity, biological compatibility and electrocatalytic activity; CA (Carbonic Anhydrase) and HQ (Hydroquinone Quinol) are simultaneously analyzed and detected by utilizing the modified electrode, and the electrochemical behaviors of two matters on bare GCE (Glassy Carbon Electrode), CoOOH/GCE and GNPs-CoOOH/GCE are investigated by using a cyclic voltammetry CV (CV) and a differential pulse voltammetry (DPV); and the GNPs-CoOOH/GCE has higher electric catalytic ability to pyrocatechol and hydroquinone, an electrical signal is greatly enhanced, the lower detection limit is obtained, and the reproducibility, the stability and the anti-interference performance are good.
Description
Technical field
The present invention relates to the composite modified electrode synthesis technical field, be specifically related to detect when the preparation method of the film modified glass-carbon electrode of a kind of gold/cobalt hydroxide and this composite modified electrode are applied to catechol and p-dihydroxy-benzene and analyze.
Background technology
Catechol (catechol claims again catechol, CA) and p-dihydroxy-benzene (Hydroquinone claims again quinhydrones, HQ) is two kinds of isomerss of benzenediol, has a wide range of applications in fields such as agricultural, dyestuff, medicine, rubber, photosensitive materials.These two kinds of materials are hard degradation under field conditions (factors), and has certain toxicity, and international cancer research organization (IARC) classifies respectively CA, HQ as 2B, 3 grades of carcinogenic substances.Therefore, to the two carry out fast, accurately, trace analysis detects tool and is of great significance.At present, both analyzing detecting method is mainly contained high phase liquid phase chromatography, take the Flow Injection Analysis of pH as the basis, synchronous fluorimetry.But liquid phase chromatography in these methods is because its instrument is expensive, consuming time and optical means needs extra its application of reagent generation light signal greatly to be restricted.Electrochemical method is cheap, easy and simple to handle, highly sensitive owing to its instrument, Site Detection receives the concern of researcher fast.Because
CA and HQOxidation-reduction potential close, the redox peak easily overlaps, and can vie each other at electrode surface, so that the concentration of its electrochemical response and material can not present linear relationship, is the greatest problem that faces in the present electrochemical research.Therefore the mutual interference problem of selecting suitable chemically modified electrode to solve both is the primary goal of present electrochemical method.
The research of transition metal oxide and hydroxide film such as nickel, cobalt, iron, copper etc. has attracted the interest of a large amount of researchers.Wherein, the cobalt hydroxide film is because its unique performance has been applied to the every field such as the preparation, electroanalysis detection of battery, sensor widely.The cobalt hydroxide film is in the application of electroanalysis context of detection, mainly be to have utilized the oxide that under alkali condition, contains high valence state cobalt ions that a large amount of electric active molecules is had stronger electrochemical catalysis activity, and the existence of CoOOH play very important effect.In addition, golden nanometer particle (GNPs) is widely used the preparation of galvanochemistry and biology sensor owing to its good electric conductivity, biocompatibility and electro catalytic activity.Therefore, nm of gold/hydroxy cobalt oxide (GNPs/CoOOH) is a kind of material of ideal modified electrode, and expects that this modified electrode can be used in the analyzing and testing of some electroactive materials.
Summary of the invention
The preparation method of the film modified glass-carbon electrode of a kind of gold/cobalt hydroxide that purpose of the present invention is developed for the existing defective of above-mentioned prior art just detects when utilizing this composite modified electrode to can be applicable to catechol and p-dihydroxy-benzene and analyzes.
The objective of the invention is to be achieved through the following technical solutions:
The preparation method of the film modified glass-carbon electrode of a kind of gold/cobalt hydroxide take glass-carbon electrode as basic electrode, utilizes the cobalt hydroxide film to modify basic electrode, and the film modified electrode of cobalt hydroxide is placed HAuCl
4KNO
3In the solution, take SCE as reference, platinum filament is to electrode, obtains the GNPs/CoOOH composite modified electrode.Concrete steps are as follows:
A, glass-carbon electrode Al
2O
3Powder is polished to minute surface, and ultrasonic cleaning in absolute ethyl alcohol and redistilled water is placed on H successively
2SO
4Middle scanning;
B, the above-mentioned glass-carbon electrode of handling well is dried up under nitrogen, then adopt plated film/cyclic voltammetry to prepare the film modified electrode of cobalt hydroxide;
C, above-mentioned electrode is placed HAuCl
4KNO
3In the solution, take SCE as reference, platinum filament is to electrode, keeps 4 min under-0.2 V, and water washes repeatedly after taking out, and obtains the GNPs/CoOOH composite modified electrode, and the PBS solution top that is suspended in pH 10.0 saves backup.
In the present invention, described HAuCl
4KNO
3Solution is 5 mM HAuCl
40.5 M KNO
3Solution.
In step a, glass-carbon electrode is used respectively 1.0 μ m, 0.3 μ m, 0.05 μ m Al
2O
3Powder is polished to minute surface, after the water flushing, and in absolute ethyl alcohol and redistilled water ultrasonic cleaning 1-2 minute successively.For obtaining thoroughly clean glass-carbon electrode surface, the glass-carbon electrode after cleaning is placed 1.0 M H
2SO
4In under-0.3-1.5 V potential window scanning 12 circles (sweeping fast 50mV/S).
The film modified glass-carbon electrode of gold/cobalt hydroxide that the present invention is prepared is applied to the detection analysis of catechol and p-dihydroxy-benzene, compare with other traditional electrode, can be so that electrocatalysis provides, electric signal strengthens, antijamming capability is strong, also obtain lower detection limit.
Electrochemistry experiment of the present invention adopts three-electrode system, glass-carbon electrode (GCE), cobalt hydroxide membrane electrode (CoOOH/GCE), gold/cobalt hydroxide film (GNPs/CoOOH) are working electrode, SCE is contrast electrode, and the CHI115 platinum filament is to electrode; At ambient temperature, choosing 0.1 M PBS is supporting electrolyte, in the certain potentials window, tests with CV and DPV method, records its volt-ampere curve.
The present invention adopts a kind of simple method to prepare the GNPs/CoOOH composite modified electrode, utilizes oxyhydroxide (CoOOH) the joining gold nano particle (GNPs) of transition metal cobalt, has good electric conductivity, biocompatibility and electro catalytic activity.Utilize this modified electrode to CA and HQ while analyzing and testing, investigated the electrochemical behavior of two kinds of materials on naked GCE, CoOOH/GCE and GNPs-CoOOH/GCE with cyclic voltammetric (CV) method and differential differentiated pulse volt-ampere (DPV) method.GNPs-CoOOH/GCE has higher electro-catalysis ability to catechol and p-dihydroxy-benzene, and electric signal strengthens greatly, and has obtained lower detection limit.In addition, this modified electrode also has good reappearance, stability, stronger advantages such as antijamming capability.
Description of drawings
The cyclic voltammogram of Fig. 1 80 μ M CA in 0.1 M PBS (pH 10.0) solution; Wherein: a:GCE; B:CoOOH/GCE; C:GNPs-CoOOH/GCE; Sweep speed: 50 mV/S.
The HQ of Fig. 2 variable concentrations and CA coexisting body tie up to the differential pulse volt figure of GNPs-CoOOH/GCE; Interior illustration is: the linear relationship chart of HQ and CA peak current and concentration.P-dihydroxy-benzene (HQ) is (a-j): 7,9,11,14,20,35,50,65, and 80,100 μ M; Catechol (CA) is (a-j): 6,8,10,13,20,35,50,65, and 80,100 μ M.
Fig. 3 phenol, adjacent,, the DPV figure of paracresol on GNPs-CoOOH/GCE.
Fig. 4 (A) EDTA (a), benzopyrene (b), NH
4 +(c), Br
-(d), NO
3 -(e), SO
4 2-(f) to CA and HQ interference experiment;
(B) Mg
2+(a), Al
3+(b), Fe
3+(c) add before the EDTA and Mg after adding
2+(d), Al
3+(e), Fe
3+(f) CA and HQ are disturbed.
Embodiment
The present invention is described further below in conjunction with embodiment (accompanying drawing), but is not restriction the present invention.
Preparation is implemented
The preparation of GNPs/CoOOH composite modified electrode
The polishing of 1 glass-carbon electrode
Glass-carbon electrode is used respectively 1.0 μ m, 0.3 μ m, 0.05 μ m Al
2O
3Powder is polished to minute surface, after the water flushing, and in absolute ethyl alcohol and redistilled water ultrasonic cleaning 1-2 minute successively.For obtaining thoroughly clean glass-carbon electrode surface, be placed on 1.0 M H
2SO
4In under-0.3 ~ 1.5 V potential windows scanning 12 the circle (sweeping fast 50mV/S);
The preparation of the film modified electrode of 2 cobalt hydroxides
Under nitrogen, dry up for subsequent use.Adopt plated film/cyclic voltammetry to prepare the film modified electrode of cobalt hydroxide the above-mentioned glass-carbon electrode of handling well;
The assembling of 3 electrodes
Above-mentioned electrode is placed 5 mM HAuCl
40.5 M KNO
3In the solution, take SCE as reference, platinum filament is to electrode, keeps 4 min under-0.2 V, and water washes repeatedly after taking out, and gets the GNPs/CoOOH composite modified electrode, and the PBS solution top that is suspended in pH 10.0 saves backup.
?
Instrument and reagent
CHl660D type electrochemical analyser (Shanghai occasion China instrument company); Three-electrode system: glass-carbon electrode (GCE), CoOOH/GCE, GNPs-CoOOH/GCE are working electrode, and saturated calomel electrode (SCE) is contrast electrode, and the CHI115 platinum filament is to electrode; KQ-3200 ultrasonic cleaner (city of Kunshan's ultrasonic instrument manufacturing plant); PHS-25 type acidometer (Shanghai thunder magnetic instrument plant); The experiment parameter of DPV is: amplitude 50 mV, pulse width 60 ms, recurrence intervals 200 ms.
CoCl
26H
2O, NaH
2PO
4, Na
2HPO
4, Na
3PO
4, KCl (Tianjin Ke Miou chemicals company limited); Catechol and p-dihydroxy-benzene (Aldrich); HAuCl
44H
2O (Shanghai reagent three factories); Phosphate buffer solution (PBS): with 0.1 M NaH
2PO
4, Na
2HPO
4, Na
3PO
4Preparation (pH 10.0).It is pure that agents useful for same is analysis, and all solution are the redistilled water preparation.
Application example
The cyclic voltammetric behavior of catechol on the different modifying electrode
In-0.6-0.3 V scope, 80 μ M CA+0.1 M PBS (pH 10.0) have been studied at GCE, CoOOH/GCE and GNPs-CoOOH/GCE electrochemical behavior, as shown in Figure 1 with cyclic voltammetry.Catechol (refers to that a) upper generation will definitely be against redox reaction among Fig. 1 at naked glass-carbon electrode, wherein the redox peak-peak potential difference (PD) (Δ Epa) of catechol is 159 mV, and electric current a little less than, illustrate that the electron transfer rate on naked GCE is slower.On CoOOH/GCE (referring to b among Fig. 1), although the electrochemical reversibility of the two does not obviously improve, its peak current slightly increases, and this shows that the cobalt hydroxide membrane electrode has definitely catalytic action to catechol.And see c among Fig. 1 at GNPs-CoOOH/GCE() on, catechol is compared redox peak-peak potential difference (PD) (Δ Epa) with CoOOH/GCE be 75 mV, and peak current obviously increases.Therefore, GNPs-CoOOH/GCE takes full advantage of the catalytic effect of two kinds of nano particles, can accelerate the electron transfer rate of electrochemical reaction, and catechol has been shown stronger catalytic activity.
The selective determination of catechol and p-dihydroxy-benzene
Referring to Fig. 2: the HQ of Fig. 2 variable concentrations and CA coexisting body tie up to the differential pulse volt figure of GNPs-CoOOH/GCE; Interior illustration is: the linear relationship chart of HQ and CA peak current and concentration.P-dihydroxy-benzene (HQ) is (a-j): 7,9,11,14,20,35,50,65, and 80,100 μ M; Catechol (CA) is (a-j): 6,8,10,13,20,35,50,65, and 80,100 μ M;
Under the experiment condition of optimizing, adopt the DPV method to investigate the relation of catechol and p-dihydroxy-benzene concentration and peak current.Fig. 2 is catechol and the resulting DPV figure of p-dihydroxy-benzene that adds variable concentrations in 0.1 M PBS (pH 10.0) solution.The oxidation peak current of p-dihydroxy-benzene and its concentration are good linear relationship in 7 μ M ~ 100 μ M scopes, equation of linear regression Ipa (μ A)=﹣ 0.0357C (μ M)-0.6993, r=0.9949 detects and is limited to 0.9 μ M (S/N=3); The oxidation peak current of catechol and its concentration are good linear relationship in 6 μ M ~ 100 μ M scopes, equation of linear regression Ipa (μ A)=﹣ 0.0223C (μ M)-0.4942, r=0.9984 detects and is limited to 0.8 μ M (S/N=3).
Stability, reappearance and interference test
To the continuous replicate determination of mixed solution of 80 μ M HQ and 80 μ M CA 7 times, the RSD of its oxidation peak current is respectively 2.60% and 4.02%; To electrode modification 5 times, measure in 80 μ M HQ and 80 μ M CA mixed solutions under the same conditions, its RSD is respectively 1.15% and 4.01%.Place 0.1 M PBS (pH 10.0) to preserve 7 days at 4 ℃ of refrigerators this modified electrode, peak current still can keep 94.2% of initial value.The above results shows that GNPs-CoOOH/GCE has good stability and reappearance.
In 0.1 M PBS (pH 10.0), the materials such as some common ions and little molecule have been studied to HQ and the common interference test of measuring of CA, as shown in Figure 3, Figure 4 with the DPV method.Test findings shows: be lower than 10
-2The NH of M
4 +, Br
-, NO
3 -, SO
4 2-, EDTA, benzopyrene, phenol, neighbour,, paracresol (1 * 10
-4M) do not disturb the mensuration of HQ and CA.Owing to have a large amount of OH in the solution
-, Mg
2+, Al
3+, Fe
3+With the OH in the solution
-Exist to interact, to measuring the interference that produces in various degree, still add the interference that a small amount of EDTA can remove these ions before the test, the result is shown in Fig. 4 B.
Sample determination
Choosing of extraction solution: the glass fiber filter that will not capture total particulate matter in mainstream smoke folds puts into 200 mL conical flasks, accurately adds 50 mL, 0.1 M PBS (pH 10.0) extraction solution, and ultrasonic extraction 20 min leave standstill 5 min under the room temperature.Get about 8 mL extracts, with 0.45 μ m filtering with microporous membrane, for eliminating Mg
2+, Al
3+, Fe
3+Deng interference, add an amount of EDTA before the test, carry out the mark-on recovery test, the result is as shown in table 1.
Catechol and p-dihydroxy-benzene recovery result (n=5) in the table 1 flue gas blank solution
Claims (5)
1. the preparation method of the film modified glass-carbon electrode of gold/cobalt hydroxide is characterized in that: take glass-carbon electrode as basic electrode, utilize the cobalt hydroxide film to modify basic electrode, the film modified electrode of cobalt hydroxide is placed HAuCl
4KNO
3In the solution, take SCE as reference, platinum filament is to electrode, obtains the GNPs/CoOOH composite modified electrode.
2. the preparation method of the film modified glass-carbon electrode of gold/cobalt hydroxide according to claim 1, it is characterized in that: the concrete steps in the preparation method are as follows:
A, glass-carbon electrode Al
2O
3Powder is polished to minute surface, and successively ultrasonic cleaning in absolute ethyl alcohol and redistilled water places H with the glass-carbon electrode after cleaning
2SO
4Middle scanning;
B, the above-mentioned glass-carbon electrode of handling well is dried up under nitrogen, then adopt plated film/cyclic voltammetry to prepare the film modified electrode of cobalt hydroxide;
C, above-mentioned electrode is placed HAuCl
4KNO
3In the solution, take SCE as reference, platinum filament is to electrode, keeps 4 min under-0.2 V, and water washes repeatedly after taking out, and obtains the GNPs/CoOOH composite modified electrode, and the PBS solution top that is suspended in pH 10.0 saves backup.
3. the preparation method of the film modified glass-carbon electrode of gold/cobalt hydroxide according to claim 2 is characterized in that: described HAuCl
4KNO
3Solution is 5 mM HAuCl
40.5 M KNO
3Solution.
4. the preparation method of the film modified glass-carbon electrode of gold/cobalt hydroxide according to claim 2, it is characterized in that: in step a, glass-carbon electrode is used respectively 1.0 μ m, 0.3 μ m, 0.05 μ m Al
2O
3Powder is polished to minute surface, after the water flushing, and in absolute ethyl alcohol and redistilled water ultrasonic cleaning 1-2 minute successively.
5. the preparation method of the film modified glass-carbon electrode of gold/cobalt hydroxide according to claim 2 is characterized in that: for obtaining thoroughly clean glass-carbon electrode surface, the glass-carbon electrode after cleaning is placed 1.0 M H
2SO
4In under-0.3-1.5 V potential window scanning 12 circles, sweep fast 50mV/S.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN115165989A (en) * | 2022-03-29 | 2022-10-11 | 苏州科技大学 | An electrochemical flexible sensor chip and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114563452A (en) * | 2022-03-03 | 2022-05-31 | 桂林理工大学 | Preparation method of layered rare earth hydroxide composite membrane modified electrode and application of electrode in detection of benzenediols |
| CN115165989A (en) * | 2022-03-29 | 2022-10-11 | 苏州科技大学 | An electrochemical flexible sensor chip and its application |
| CN115165989B (en) * | 2022-03-29 | 2023-10-24 | 苏州科技大学 | Electrochemical flexible sensing chip and application thereof |
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