CN104897765A - Method for detecting hydrogen peroxide and nitrite by electrochemical sensor based on dual-metal porphyrin coordination polymer - Google Patents
Method for detecting hydrogen peroxide and nitrite by electrochemical sensor based on dual-metal porphyrin coordination polymer Download PDFInfo
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Abstract
The invention discloses a method for detecting hydrogen peroxide and nitrite by an electrochemical sensor based on a dual-metal porphyrin coordination polymer. A dual-metal porphyrin coordination polymer (CoTCPP-Cu or CoTCPP-Cu/CNTs) composite material modification electrode is used as a working electrode; hydrogen peroxide or nitrite is detected by a timing current method; CoTCPP-Cu is a coordination polymer assembled by dual metals Co and Cu and tetra-(p-carboxyphenyl) porphyrin. The electrochemical sensor adopted in the method is a current type sensor, has unique dual-metal activity and is high in sensitivity; the method has the advantages of convenience in detection and wide application range; the detection limit for hydrogen peroxide can reach 5.0*10<-7>M and the detection limit for nitrite can reach 2.5*10<-6>. The detection method disclosed by the invention has the characteristics of quick on-site detection, high sensitivity, low cost and the like.
Description
Technical field
The present invention relates to a kind of electrochemical detection method, particularly relate to a kind of method that electrochemical sensor based on bimetallic porphyrin coordination polymer is detected hydrogen oxide or nitrite.
Background technology
Coordination polymer is a class by coordination bond by metallic ion or bunch hybrid inorganic-organic materials be formed by connecting with organic ligand, a lot of aspect such as catalysis, atmosphere storage and separation, optical material, magnetic material etc. is widely used in (see (a) SR Batten because of its stability, multifunctionality, Modulatory character etc., SM Neville, DR Turner, Coordination Polymers:Design, Analysis and Application, 2008. (b) Chemical Society Reviews, 38 (2009) .).But, research that coordination polymer is used for fax sense as eelctro-catalyst is also seldom (see (a) Zhang, W., Wang, L.L., Zhang, N., Wang, G.F., Fang, B., 2009.Functionalization of Single-Walled Carbon Nanotubes with Cubic Prussian Blue and Its Application for Amperometric Sensing.Electroanalysis 21 (21), 2325-2330. (b) Zhou, B., 2012.Co
iI/ Zn
iI-(L-Tyrosine) Magnetic Metal-Organic Frameworks.European Journal of Inorganic Chemistry.).
Metal-porphyrin coordination polymer is using metalloporphyrin as part (construction unit, skeleton part) be because it has biocompatibility, be applied in bionic catalysis (see: (a) Liu, J.Y., et al., Comparative study on heme-containing enzyme-like catalytic activities of water-soluble metalloporphyrins.Journal of Molecular Catalysis a-Chemical, 2002.179 (1-2), 27-33. (b) Vago, M., et al., Metalloporphyrin electropolymerization:electrochemical quartz crystal microgravimetric studies.Journal of Electroanalytical Chemistry, 2004.566 (1), 177-185.).Metalloporphyrin is the conjugate ring compound that a class has stable π key, therefore there is light, electricity, catalysis, the character of the aspect such as bionical (see: (a) Kosal, M.E., et al., A functional zeolite analogue assembledfrom metalloporphyrins.Nature Materials, 2002.1 (2), 118-121. (b) Shultz, A.M., et al., A Catalytically Active, Permanently Microporous MOF with Metalloporphyrin Struts.Journal of the American Chemical Society, 2009.131 (12), 4204-4205. (c) Sheldon, R.A., Metalloporphyrins in Catalytic Oxidations.Marcel Dekker, 1994.).Therefore, metal-porphyrin coordination polymer is the functional material with splendid application prospect, all has potential advantages in galvanochemistry and biological association area.
Based on the electrochemical sensor of metal-porphyrin coordination polymer, there is not been reported.The material (as hydrogen peroxide) relevant to important biomolecule process and the detection of nitrite in food are the important topics of analytical chemistry (comprising Electroanalytical Chemistry) always.Electrical catalyze reduction and oxidation are then related separately to the Electrochemical Detection of hydrogen peroxide and nitrite, and the difunctional electrochemical sensor utilizing different activities position to detect different material is reported less.(see: (a) Ammam, M., Easton, E.B., 2012.Novel organic-inorganic hybrid material based on tris (2, 2 '-bipyridyl) dichlororuthenium (II) hexahydrate and Dawson-type tungstophosphate K-7H4PW 18O62center dot 18H (2) O as a bifuctional hydrogen peroxide electrocatalyst for biosensors.Sensors and Actuators B-Chemical 161 (1), 520-527. (b) Bai, Y.H., Zhang, H., Xu, J.J., Chen, H.Y., 2008.Relationship between Nanostructure and Electrochemical/Biosensing Properties of MnO (2) Nanomaterials for H (2) O (2)/Choline.Journal of Physical Chemistry C 112 (48), 18984-18990.).
Summary of the invention
The object of this invention is to provide a kind of method that electrochemical sensor based on bimetallic porphyrin coordination polymer is detected hydrogen oxide or nitrite.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of electrochemical sensor based on bimetallic porphyrin coordination polymer is detected the method for hydrogen oxide or nitrite, it is characterized in that, described method adopts electrochemical sensor based on bimetallic porphyrin coordination polymer as working electrode, adopts chronoamperometry to be detected hydrogen oxide or nitrite;
The described electrochemical sensor based on bimetallic porphyrin coordination polymer, comprises basal electrode, described basal electrode finishing bimetallic porphyrin coordination polymer or the compound of bimetallic porphyrin coordination polymer/carbon nano-tube; Described bimetallic porphyrin coordination polymer is meso-5,10,15,20-tetra--(to carboxyl phenyl) porphyrin thermometal coordination polymer (CoTCPP-Cu), be the coordination polymer that thermometal Co, Cu and four-(to carboxyl phenyl) porphyrin (TCPP) self assembly is formed, there is following structure
In formula, CoTCPP is four-(to carboxyl phenyl) Cob altporphyrin;
There is coordination in four N at wherein metal Co and four-(to carboxyl phenyl) porphyrin center, each Ni metal respectively with the oxygen coordination in the carboxyl from four four-(to carboxyl phenyl) porphyrin, each carboxyl and two Ni metal generation double coordinations.
In described electrochemical sensor, described basal electrode is preferably glass-carbon electrode.
In described electrochemical sensor, described carbon nano-tube comprises Single Walled Carbon Nanotube (SWNTs) and multi-walled carbon nano-tubes (MWNTs).
Described electrochemical sensor adopts following methods preparation:
CoTCPP-Cu ultrasonic disperse is formed suspending liquid in deionized water, this hanging drop is applied to basal electrode surface, dries; Drip at electrode surface again and be coated with nafion solution, dry, obtain described electrochemical sensor (CoTCPP-Cu modified electrode is denoted as electrochemical sensor-I).
Or, first drip on basal electrode and be coated with carbon nano tube suspension and dry, then described CoTCPP-Cu hanging drop is coated in described electrode surface and airing; Drip at electrode surface again and be coated with nafion solution, dry, obtained described electrochemical sensor (CoTCPP-Cu/CNTs modified electrode is denoted as electrochemical sensor-II).
Described electrochemical sensor, based on bimetallic porphyrin coordination polymer CoTCPP-Cu, is amperometric sensor.Mixing of carbon nano-tube can significantly improve its electric sensing capabilities.Sensor described in the inventive method adopts has bimetallic active, has the difunctional electrochemical catalysis of unique redox thermometal active, has good electrochemical sensing performance to the reduction of hydrogen peroxide and the oxidation of nitrite.
Particularly, according to the inventive method, be detected the method for hydrogen oxide based on described electrochemical sensor, comprise the following steps:
(1) electrochemical sensor based on bimetallic porphyrin coordination polymer described in preparation;
(2) chronoamperometry (i-t) measures the typical curve of hydrogen peroxide
Preparation Hydrogen peroxide standard solution, with the described electrochemical sensor based on bimetallic porphyrin coordination polymer for working electrode, platinum electrode is auxiliary electrode, saturated calomel electrode is contrast electrode composition three-electrode system, under constant detection current potential, adopt chronoamperometry to obtain the i-t curve of hydrogen peroxide response current, drafting or linear regression obtain i-c typical curve;
Preferably, detection current potential is-0.20V ~-0.55V, and best effort current potential is-0.25V.
(3) detect
Under the condition identical with step (2), Electrochemical Detection is carried out to detection sample, reads response current, calculate concentration of hydrogen peroxide according to i-c typical curve.
According to the inventive method, detect the method for nitrite based on described electrochemical sensor, comprise the following steps:
(1) electrochemical sensor based on bimetallic porphyrin coordination polymer described in preparation;
(2) chronoamperometry (it) measures the typical curve of nitrite
Preparation nitrite standard solution, with the described electrochemical sensor based on bimetallic porphyrin coordination polymer for working electrode, platinum electrode is auxiliary electrode, saturated calomel electrode is contrast electrode composition three-electrode system, under constant detection current potential, adopt chronoamperometry to obtain the i-t curve of nitrite response current, drafting or linear regression obtain i-c typical curve;
Preferably, detection current potential is 0.70V ~ 0.95V, and best effort current potential is 0.85V.
(3) detect
Under the condition identical with step (2), Electrochemical Detection is carried out to detection sample, reads response current, calculate nitrite concentration according to i-c typical curve.
Beneficial effect of the present invention: according to the method being detected hydrogen oxide or nitrite of the present invention, based on the electrochemical sensor of metal-porphyrin coordination polymer, there is unique thermometal electro catalytic activity, be a kind of difunctional electrochemical sensor, to the material such as hydrogen peroxide and nitrite, there is good electrocatalysis characteristic.In order to improve the performance of sensor further, prepare electrochemical sensor-II by metalloporphyrin coordination polymer/CNTs compound substance.The present invention is by electrochemical sensing technology for detection hydrogen peroxide or nitrite, solve hydrogen peroxide in current food, environment and industry, nitrite detect in exist detection speed slow, cost is high, the problems such as complicated operation, has detection speed fast, highly sensitive, the features such as cost is low.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of bimetallic porphyrin coordination polymer CoTCPP-Cu, comprises the XRD spectra (by circle markings) of planar structure, the XRD spectra (using square mark) of interlamellar spacing.
Fig. 2 is the infrared spectrogram (FTIR) of bimetallic porphyrin coordination polymer CoTCPP-Cu.
Fig. 3 is ultraviolet (UV) spectrogram of bimetallic porphyrin coordination polymer CoTCPP-Cu.
Fig. 4 is transmission electron microscope picture (A) and the scanning electron microscope (SEM) photograph (B) of bimetallic porphyrin coordination polymer CoTCPP-Cu.
The cyclic voltammogram of Fig. 5 electrochemical sensor-I, figure A:(a) naked glass-carbon electrode, without hydrogen peroxide; (b) naked glass-carbon electrode, 0.5mmolL
-1hydrogen peroxide; C () electrochemical sensor-I, without hydrogen peroxide; (d) electrochemical sensor-I, 0.5mmolL
-1hydrogen peroxide; Figure B:(a) naked glass-carbon electrode, without sodium nitrite; (b) naked glass-carbon electrode, 0.25mmolL
-1sodium nitrite; C () electrochemical sensor-I, without sodium nitrite; (d) electrochemical sensor-I, 0.25mmolL
-1sodium nitrite.
Fig. 6 (A) electrochemical sensor-I is to the current-responsive figure of hydrogen peroxide at constant potential-0.25V, and illustration is that current-responsive is mapped to concentration of hydrogen peroxide; (B) electrochemical sensor-I is to the current-responsive figure of sodium nitrite at constant potential 0.85V, and illustration is that current-responsive is mapped to sodium nitrite concentration.
The cyclic voltammogram of Fig. 7 electrochemical sensor-II, figure A:(a) Glassy Carbon Electrode Modified with Multi-wall Carbon Nanotubes, without hydrogen peroxide; (b) Glassy Carbon Electrode Modified with Multi-wall Carbon Nanotubes, 0.5mmolL
-1hydrogen peroxide; C () electrochemical sensor-II, without hydrogen peroxide; (d) electrochemical sensor-II, 0.5mmolL
-1hydrogen peroxide; Figure B:(a) Glassy Carbon Electrode Modified with Multi-wall Carbon Nanotubes, without sodium nitrite; (b) Glassy Carbon Electrode Modified with Multi-wall Carbon Nanotubes, 0.5mmolL
-1sodium nitrite; C () electrochemical sensor-II, without sodium nitrite; (d) electrochemical sensor-II, 0.5mmolL
-1sodium nitrite.
Fig. 8 (A) electrochemical sensor-II is to the current-responsive figure of hydrogen peroxide at constant potential-0.25V, and illustration is that current-responsive is mapped to concentration of hydrogen peroxide; (B) electrochemical sensor-II is to the current-responsive figure of sodium nitrite at constant potential 0.85V, and illustration is that current-responsive is mapped to sodium nitrite concentration.
Fig. 9 electrochemical sensor-II is detected the anti-interference of hydrogen oxide (A) and sodium nitrite (B) respectively.
Embodiment
Below by specific embodiment, technical solutions according to the invention are further described in detail, but are necessary to point out that following examples are only for the description to summary of the invention, do not form limiting the scope of the invention.
According to the electrochemical sensor based on bimetallic porphyrin coordination polymer of the present invention, a kind of bimetallic porphyrin coordination polymer CoTCPP-Cu modified electrode, namely at basal electrode finishing bimetallic porphyrin coordination polymer CoTCPP-Cu (electrochemical sensor-I); Or a kind of CoTCPP-Cu/MWNTs modified electrode, namely first with carbon nano tube modified described basal electrode, then at electrode face finish bimetallic porphyrin coordination polymer CoTCPP-Cu (electrochemical sensor-II).
Described bimetallic porphyrin coordination polymer is meso-5,10,15,20-tetra--(to carboxyl phenyl) porphyrin thermometal coordination polymer (CoTCPP-Cu), it is the coordination polymer that thermometal Co, Cu and four-(to carboxyl phenyl) porphyrin (TCPP) self assembly is formed, there is coordination in four N at wherein metal Co and four-(to carboxyl phenyl) porphyrin center, each Ni metal respectively with the oxygen coordination in the carboxyl from four four-(to carboxyl phenyl) porphyrin, each carboxyl and two Ni metal generation double coordinations; Namely there is following structure
In formula, CoTCPP is four-(to carboxyl phenyl) Cob altporphyrin.
Described meso-5,10,15,20-tetra--(to carboxyl phenyl) porphyrin thermometal coordination polymer following methods can be adopted to prepare:
CoTCPP and mantoquita are dissolved in DMF respectively, the copper salt solution prepared is joined in CoTCPP solution, add acid solution again, obtain the mixed solution that red floccus is separated out, CoTCPP in mixed solution: mantoquita: the mol ratio of acid is 1: 4 ~ 40: 100 ~ 400; Described mixed solution is heated to 50 ~ 100 DEG C and carries out solvent thermal reaction 2 ~ 12 days, product washing, drying, can obtain thermometal coordination polymer described in amaranth flour powder.
The component such as water of crystallization or solvent molecule can be comprised in coordination polymer prepared by said method.
Described electrochemical sensor adopts following methods preparation:
CoTCPP-Cu ultrasonic disperse is formed suspending liquid in deionized water, this hanging drop is applied to basal electrode surface, dries; Drip at electrode surface again and be coated with nafion solution, dry, obtained electrochemical sensor-I;
Or, first drip on basal electrode and be coated with carbon nano tube suspension and dry, then described CoTCPP-Cu hanging drop is coated in described electrode surface and airing; Drip at electrode surface again and be coated with nafion solution, dry, obtained electrochemical sensor-II.
Adopt its electro catalytic activity of cyclic voltammetry, show that described electrochemical sensor has the difunctional electrochemical catalysis of unique redox thermometal active, and can be used for the Electrochemical Detection to hydrogen peroxide and nitrite.
Be detected the method for hydrogen oxide based on described electrochemical sensor, comprise the following steps:
(1) Hydrogen peroxide standard solution is prepared
Prepare the Hydrogen peroxide standard solution of one group of variable concentrations.
(2) cyclic voltammetry is detected hydrogen oxide
In the PBS electrolyte of pH=7, with the glass-carbon electrode of naked glass-carbon electrode or modification for working electrode, platinum electrode is auxiliary electrode, and saturated calomel electrode is contrast electrode, in current potential-1.0 ~ 1.0V, with sweep velocity 100mV s
-1carry out cyclic voltammetry scan.Bare electrode and electrochemical sensor to have or without the CV curve under hydrogen peroxide, comparative descriptions sensor is to H respectively
2o
2whether there is response.When the increase of electric current along with concentration of hydrogen peroxide increases, illustrate that electrochemical sensor can be applicable to be detected hydrogen oxide.
(3) chronoamperometry (i-t) is detected hydrogen oxide
Electrochemical sensor is adopted to carry out Electrochemical Detection to hydrogen peroxide, under-0.25V detects current potential, electrochemical sensor-I is at PBS (0.1M, pH=7) in solution to after the hydrogen peroxide dripping continuously variable concentrations and different amount, the electric current of response increases gradually and namely obtains i-t curve, with concentration corresponding to the electric current being greater than noise signal 3 times for minimum detectability, drawn the range of linearity of detection by i-c typical curve, sensitivity.
Adopt identical Cleaning Principle, under current potential is detected in-0.20 and-0.55V, obtain i-t curve and i-c typical curve, to sum up experiment can obtain best effort current potential is-0.25V.
(4) detect
When detecting sample, by reading the size of electric current, establishing criteria curve just can calculate the size of contained detected material concentration of hydrogen peroxide in sample.
Detect the method for nitrite based on described electrochemical sensor, comprise the following steps:
(1) sodium nitrite standard solution is prepared
Prepare the sodium nitrite standard solution of one group of variable concentrations.
(2) cyclic voltammetry detects nitrite
In the PBS electrolyte of pH=7, with the glass-carbon electrode of naked glass-carbon electrode or modification for working electrode, platinum electrode is auxiliary electrode, and saturated calomel electrode is contrast electrode, in current potential-1.0 ~ 1.0V, with sweep velocity 100mV s
-1carry out cyclic voltammetry scan.Bare electrode and electrochemical sensor to have or without the CV curve in the electrolyte solution of nitrite, whether comparative descriptions sensor has response to nitrite respectively.Response current has increase then to illustrate, and electrochemical sensor can be applicable to detect nitrite.
(3) chronoamperometry (it) detects nitrite
Electrochemical sensor-I is adopted to carry out Electrochemical Detection to hydrogen peroxide, under 0.85V detects current potential, electrochemical sensor is at PBS (0.1M, pH=7) in solution, the electric current responded after dripping continuously the nitrite solution of variable concentrations and different amount is increased gradually and namely obtain i-t curve, with concentration corresponding to the electric current being greater than noise signal 3 times for minimum detectability, the range of linearity of detection is drawn, sensitivity by i-c typical curve.
(4) detect
When detecting sample, by reading the size of electric current, establishing criteria curve just can calculate the size of contained detected material nitrite concentration in sample.
Embodiment 1 thermometal coordination polymer [Cu
2(Co-TCPP) (H
2o)
2] 0.5DMF5H
2the preparation of O (CoTCPP-Cu)
Take CoTCPP 3mg (0.01mmol), add DMF 3mL and make it to dissolve; Take excessive Cu (NO simultaneously
3)
2.3H
2o 100mg (0.4mmol), adds DMF 2mL and makes it to dissolve.By the above-mentioned Cu (NO prepared
3)
2solution joins in CoTCPP solution, adds HNO while stirring
3(1M) 1 ~ 4mL, finally obtains the mixed solution that red floccus is separated out.This mixed solution is placed in 65 ~ 100 DEG C of baking ovens and leaves standstill 5 days, obtain aubergine powder.Filter, use DMF, H respectively
2o and EtOH washs, and at room temperature dries.
The synthesis of CoTCPP can refer to document: (a) Lindsey, J.S., H.C.Hsu, and I.C.Schreiman, SYNTHESIS OF TETRAPHENYLPORPHYRINS UNDER VERY MILD CONDITIONS.Tetrahedron Letters, 1986.27 (41): 4969-4970. (b) Kumar, A., et al., One-pot general synthesis of metalloporphyrins.Tetrahedron Letters, 2007.48 (41): 7287-7290.
Obtained thermometal coordination polymer CoTCPP-Cu, XRD spectrum (Fig. 1) display plane architectural feature peak (110), (320), (400), (330), (440) and (550)/(710), interlamellar spacing characteristic peak (001), (002) and (004), calculating interlamellar spacing is 1.0nm.Infrared and ultraviolet spectrogram (Fig. 2,3) shows, the N in Co and porphyrin cavity coordination occurs, Cu and carboxylic acid generation coordination.CoTCPP-Cu is at 1726cm
-1in place-COOH, the stretching vibration absorption peak of C=O disappears, and-COOH all coordinations is described, at 1435cm
-1and 950cm
-1the O-H vibration absorption peak of place's carboxyl disappears, and further illustrates-COOH coordination completely.1604,1404cm
-1antisymmetry Vas (COO-) and symmetrical Vs (COO-) stretching vibration of carboxylic acid ion, 1604 and 1404cm
-1difference equals 200cm
-1, carboxyl may with bidentate mode and Cu (II) coordination.If Fig. 3 is ultraviolet spectrogram, (a) TCPP absorption spectrum in DMF, is with at the strong peak S of 420nm place appearance one, is with in 515,549,590 and the low-energy Q of 646nm place appearance four.B () is the absorption spectrum of CoTCPP in DMF, because coordination occurs the N in metallic ion Co and porphyrin ring, make S be with red shift to 433nm, four Q bands become two, appear at 548 and 595nm place, and Q is with the minimizing of absorption peak to be because porphyrin part belongs to D
2hpoint group, complex belongs to D
4hpoint group.C () is the absorption spectrum of Cu-CoTCPP in DMF, S band is blue shifted to 419nm, and simultaneously Q band is reduced to one, this is because on metalloporphyrin ring with carboxyl O and Cu (II) coordination, improve the symmetry of coordination polymer molecule.It take CoTCPP as the coordination polymer of structural unit that the change of uv-vis spectra illustrates that coordination polymer is.As can be seen from SEM and TEM Electronic Speculum figure (Fig. 4), described CoTCPP-Cu is 100-200nm debris accumulation Cheng Kuanwei 0.1-2 μm, the irregular granules that length is 0.5-3 μm.
The preparation of embodiment 2 electrochemical sensor-I
(1) polishing of naked glass-carbon electrode and cleaning
Glass-carbon electrode secondary deionized water is cleaned and ultrasonic one minute, polish five minutes with the alumina powder that diameter is 0.3um again, powder slurry secondary deionized water on polishing cloth and electrode is cleaned, and glass-carbon electrode to be put in secondary deionized water ultrasonic one minute, repeatedly polish and after cleaning, finally glass-carbon electrode dried up for subsequent use.
(2) electrode modification
The CoTCPP-Cu ultrasonic disperse of 5mg is formed suspending liquid in 400 μ L deionized waters, 6 these hanging drops of μ L is applied to the glassy carbon electrode surface that step (1) obtains, dries; Drip painting 2 μ L 1%nafion solution at electrode surface again, dry, obtain CoTCPP-Cu modified electrode, be denoted as electric transducer-I.
Embodiment 3 electrochemical sensor-I is applied to the cyclic voltammetry scan that hydrogen peroxide detects
(1) Hydrogen peroxide standard solution is prepared
Get 30% superoxol 84 μ L, and be diluted to 4mL. and be namely mixed with 0.2mol L
-1superoxol, other concentration is by same procedure preparation.
(2) cyclic voltammogram of hydrogen peroxide detection
In the PBS electrolytic solution of pH=7, bare electrode and electrochemical sensor-I to have or without the C-V curve under hydrogen peroxide, as shown in fig. 5, a is naked GCE, b is that naked GCE adds 0.5mmolL respectively
-1h
2o
2, the naked GCE of a and b comparative descriptions is to H
2o
2not response.C-d is the H that electrochemical sensor-I adds variable concentrations respectively
2o
20 and 0.5mmol L
-1, along with adding of hydrogen peroxide, the response of reduction current strengthens gradually, illustrates that electrochemical sensor-I has reduction electro catalytic activity to hydrogen peroxide.
Embodiment 4 electrochemical sensor-I detects the optimization of Hydrogen Peroxide
Different sense potential can have an impact to detection, is determined by chronoamperometry (it).
Adopt electrochemical sensor-I to carry out Electrochemical Detection to hydrogen peroxide, shown in accompanying drawing 6A, under-0.25V detects current potential, electrochemical sensor-I in PBS (0.1M, pH=7) solution to dripping variable concentrations (0.01mol L continuously
-1, 0.02mol L
-1, 0.2mol L
-1) and different amount hydrogen peroxide after the electric current that responds increase gradually and namely obtain it curve, with concentration corresponding to the electric current being greater than noise signal 3 times for minimum detectability, the experiment repeating more than 5 times draws, the minimum detectability of said method is 2.5 × 10
-6m, in accompanying drawing 6A, illustration is the response current of hydrogen peroxide and the calibration curve of concentration, and linear equation is: Y=-1.01848-2.01421X, show that the range of linearity of above-mentioned detection is 7.0 × 10
-5-4.7 × 10
-3m (R=0.996), sensitivity is 23.5mA mol
-1l cm
-2.
Adopt identical Cleaning Principle, under-0.20V detects current potential, the testing result obtained is: minimum detectability is 4.0 × 10
-5m, the range of linearity is 4.4 × 10
-4-7.3 × 10
-3m, sensitivity is 3.5mA mol
-1l cm
-2; Simultaneously when detection current potential is-0.55V, the testing result obtained is: minimum detectability is 7.5 × 10
-6m, the range of linearity is 7.5 × 10
-6-3.71 × 10
-3m, sensitivity is 23.5mAmol
-1lcm
-2.
To sum up experiment can obtain best effort current potential is-0.25V.
Embodiment 5 electrochemical sensor-I is used for the detection of nitrite
(1) sodium nitrite standard solution is prepared
Take the sodium nitrite powder of 0.1399g, then the secondary deionized water adding 2.028mL is dissolved, and is namely mixed with 0.2mol L
-1, other concentration is by the preparation of identical method.
(2) electrochemical sensor-I detects the cyclic voltammogram of nitrite
As shown in fig. 5b, for bare electrode and electrochemical sensor-I to have or respectively without the CV curve under sodium nitrite, naked glass-carbon electrode is without the cyclic voltammetric in the PBS electrolyte of nitrite, (a), naked glass-carbon electrode is at 0.5mmolL for curve
-1cyclic voltammetric (curve b) in the PBS electrolyte of nitrite, electrochemical sensor-I is without the cyclic voltammetric (curve c) during nitrite, and electrochemical sensor-I is at 0.5mmolL
-1cyclic voltammetric (curve d) in the PBS electrolyte of nitrite, Co
iII/ Co
iIthe response of oxidation current strengthens gradually, illustrates that electrochemical sensor-I has oxidation electro catalytic activity to nitrite.
Embodiment 6 electrochemical sensor-I detects the it curve of nitrite
Shown in accompanying drawing 6B, under 0.85V constant voltage, drip variable concentrations (0.01mol L continuously
-1, 0.02mol L
-1, 0.2mol L
-1) and the different nitrite measured, the current-time curvel that electrochemical sensor-I responds nitrite can be obtained, illustration is the response current of sodium nitrite and the calibration curve of concentration, with concentration corresponding to the electric current being greater than noise signal 3 times for minimum detectability, the experiment repeating more than 5 times draws, the minimum detectability of said method is 5.0 × 10
-6from typical curve (Y=0.33214+0.72838X), M, show that the range of linearity is 3.5 × 10
-5-5.5 × 10
-3m, sensitivity is 15.32mA mol
-1l cm
-2.
The preparation of embodiment 7 electrochemical sensor-II
(1) polishing of naked glass-carbon electrode and cleaning: with above-described embodiment 1 step (1)
(2) electrode modification
The multi-walled carbon nano-tubes hanging drop being 5mg/mL by 6 μ L concentration is applied to the glassy carbon electrode surface that step (1) obtains, and dries; Drip the CoTCPP-Cu suspending liquid that painting 6 μ L concentration is 12.5mg/mL again, dry; Finally drip painting 2 μ L 1%nafion solution at electrode surface, dry, obtain CoTCPP-Cu/MWNTs modified electrode, be denoted as electric transducer-II.
Embodiment 8 electrochemical sensor-II is used for the detection of hydrogen peroxide
As shown in accompanying drawing 7A and 8A, electrochemical sensor-II has hydrogen peroxide and significantly reduces electro catalytic activity, drips variable concentrations (0.01mol L under-0.25V constant potential continuously
-1, 0.02mol L
-1, 0.2mol L
-1) and the hydrogen peroxide of different amount obtain the current-time curvel that electrochemical sensor-II responds hydrogen peroxide, with concentration corresponding to the electric current being greater than noise signal 3 times for minimum detectability, the experiment repeating more than 5 times draws, the minimum detectability of said method is 5.0 × 10
-7m; Illustration is the calibration curve of response current and concentration, and typical curve is Y=-0.56706-11.86815X, and the range of linearity expands as 5.0 × 10
-7-6.2 × 10
-3m (R=0.999), detection sensitivity brings up to 147.8mAM
-1cm
-2, the activity of its electro-catalysis hydrogen-peroxide reduction be improved significantly.
Embodiment 9 electrochemical sensor-II is used for the detection of nitrite
Accompanying drawing 7B is bare electrode and electrochemical sensor-II to be had or without the C-V curve of nitrite.Accompanying drawing 8B drips variable concentrations (0.01mol L continuously under the current potential of 0.85V
-1, 0.02mol L
-1, 0.2mol L
-1) and the sodium nitrite of different amount obtain current-time curvel with concentration corresponding to the electric current being greater than noise signal 3 times for minimum detectability, the experiment repeating more than 5 times draws, the minimum detectability of said method is 2.5 × 10
-6m; Illustration is the calibration curve of response current and concentration, and the equation of typical curve is Y=0.33214+0.72838X, show that the range of linearity expands as 2.5 × 10
-6-1.1 × 10
-3m (R=0.9999), the activity of its electro-catalysis nitrite-oxidizing improves greatly.
The high selectivity of embodiment 10 electrochemical sensor-II
When being detected hydrogen oxide, as shown in figure 9, H is added successively in PBS electrolyte environment
2o
2(0.5mmol), AA (0.5mmol), Glu (0.5mmol), DA (0.5mmol), UA (0.5mmol), H
2o
2(0.5mmol) detect without interruption, illustrate that electrochemical sensor has high selectivity in the detection of hydrogen peroxide.Simultaneously as shown in figure 9b, in PBS electrolyte environment, add KNO successively at detection nitrite
3(0.5mmol), Zn (Ac)
2(0.5mmol), MgCl
2(0.5mmol), UA (0.5mmol), Glu (0.5mmol) time, detect be not interfered, illustrate that electrochemical sensor has high selectivity in the detection of nitrite.
Claims (8)
1. the electrochemical sensor based on bimetallic porphyrin coordination polymer is detected the method for hydrogen oxide or nitrite, it is characterized in that, described method, using the electrochemical sensor based on bimetallic porphyrin coordination polymer as working electrode, adopts chronoamperometry to be detected hydrogen oxide or nitrite;
The described electrochemical sensor based on bimetallic porphyrin coordination polymer, comprises basal electrode, described basal electrode finishing bimetallic porphyrin coordination polymer or the compound of bimetallic porphyrin coordination polymer/carbon nano-tube; Described bimetallic porphyrin coordination polymer is meso-5,10,15,20-tetra--(to carboxyl phenyl) porphyrin thermometal coordination polymer, be designated as CoTCPP-Cu, be the coordination polymer that thermometal Co, Cu and four-(to carboxyl phenyl) porphyrin (TCPP) self assembly is formed, there is following structure
In formula, CoTCPP is four-(to carboxyl phenyl) Cob altporphyrin;
There is coordination in four N at wherein metal Co and four-(to carboxyl phenyl) porphyrin center, each Ni metal respectively with the oxygen coordination in the carboxyl from four four-(to carboxyl phenyl) porphyrin, each carboxyl and two Ni metal generation double coordinations.
2. the method being detected hydrogen oxide or nitrite according to claim 1, is characterized in that, in described electrochemical sensor, described basal electrode is glass-carbon electrode, and described carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
3. the method being detected hydrogen oxide or nitrite according to claim 1, is characterized in that, described electrochemical sensor adopts following methods preparation:
A) CoTCPP-Cu ultrasonic disperse is formed suspending liquid in deionized water, this hanging drop is applied to basal electrode surface, dries; Drip at electrode surface again and be coated with nafion solution, dry, obtain described electrochemical sensor; Or
B) first on basal electrode, drip painting carbon nano tube suspension and dry, then described CoTCPP-Cu hanging drop being coated in described electrode surface and airing; Drip at electrode surface again and be coated with nafion solution, dry, obtained described electrochemical sensor.
4. the method being detected hydrogen oxide or nitrite according to claim 1, is characterized in that, described CoTCPP-Cu adopts following methods preparation:
CoTCPP and mantoquita are dissolved in DMF respectively, are joined by copper salt solution in CoTCPP solution, then add acid solution, obtain the mixed solution that red floccus is separated out, CoTCPP in mixed solution: mantoquita: the mol ratio of acid is 1: 4 ~ 40: 100 ~ 400; Described mixed solution is heated to 50 ~ 100 DEG C and carries out solvent thermal reaction 2 ~ 12 days, product washing, drying, can obtain thermometal coordination polymer described in amaranth flour powder.
5., according to the arbitrary described method being detected hydrogen oxide or nitrite of Claims 1-4, it is characterized in that, described method is detected hydrogen oxide, comprises the following steps:
(1) electrochemical sensor based on bimetallic porphyrin coordination polymer described in preparation;
(2) chronoamperometry measures the typical curve of hydrogen peroxide
Preparation Hydrogen peroxide standard solution, with the described electrochemical sensor based on bimetallic porphyrin coordination polymer for working electrode, platinum electrode is auxiliary electrode, saturated calomel electrode is contrast electrode composition three-electrode system, under constant detection current potential, adopt chronoamperometry to obtain the i-t curve of hydrogen peroxide response current, drafting or linear regression obtain i-c typical curve;
(3) detect
Under the condition identical with step (2), Electrochemical Detection is carried out to detection sample, reads response current, calculate concentration of hydrogen peroxide according to i-c typical curve.
6. the method being detected hydrogen oxide or nitrite according to claim 5, is characterized in that, described detection current potential is-0.20V ~-0.55V.
7., according to the arbitrary described method being detected hydrogen oxide or nitrite of Claims 1-4, it is characterized in that, described method detects nitrite, comprises the following steps:
(1) electrochemical sensor based on bimetallic porphyrin coordination polymer described in preparation;
(2) chronoamperometry measures the typical curve of nitrite
Preparation nitrite standard solution, with the described electrochemical sensor based on bimetallic porphyrin coordination polymer for working electrode, platinum electrode is auxiliary electrode, saturated calomel electrode is contrast electrode composition three-electrode system, under constant detection current potential, adopt chronoamperometry to obtain the i-t curve of nitrite response current, drafting or linear regression obtain i-c typical curve;
(3) detect
Under the condition identical with step (2), Electrochemical Detection is carried out to detection sample, reads response current, calculate nitrite concentration according to i-c typical curve.
8. the method being detected hydrogen oxide or nitrite according to claim 7, is characterized in that, described detection current potential is 0.70V ~ 0.95V.
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