CN104990972A - Bismetalloporphyrin coordination polymer-based electrochemical sensor and making method thereof - Google Patents
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Abstract
A bismetalloporphyrin coordination polymer-based electrochemical sensor is obtained through modifying the surface of a substrate electrode by a bismetalloporphyrin coordination polymer or a bismetalloporphyrin coordination polymer/carbon nanotube complex, and the bismetalloporphyrin coordination polymer is a coordination polymer formed through self-assembling Co, Cu and tetra-(p-carboxylphenyl)porphyrin, wherein metallic Co coordinates with four N atoms in the center of porphyrin, all metallic Cu atoms coordinate with oxygen atoms from four carboxyl groups, and double coordination is carried out between every carboxyl group and two metallic Cu atoms. The electrochemical sensor is a current sensor, has unique bimetallic activity, the metallic active site Cu has an electrocatalysis effect on the reduction process of hydrogen peroxide, the metallic active site Co has an electrocatalysis effect on the oxidation process of nitrite, and carbon nanotubes are mixed to greatly improve the electrosensing performance of the sensor.
Description
Technical field
The present invention relates to a kind of electrochemical sensor, particularly relate to a kind of electrochemical sensor based on bimetallic porphyrin coordination polymer and preparation method thereof, described electrochemical sensor is a kind of difunctional electrochemical sensor.
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 CubicPrussian 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.EuropeanJournal of Inorganic Chemistry.).
Metal-porphyrin coordination polymer is because it has biocompatibility using metalloporphyrin as part, be applied in bionic catalysis (see: (a) Liu, J.Y., et al., Comparative study on heme-containing enzyme-like catalyticactivities of water-soluble metalloporphyrins.Journal of Molecular Catalysis a-Chemical, 2002.179 (1-2), 27-33. (b) Vago, M., et al., Metalloporphyrin electropolymerization:electrochemicalquartz 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 assembledfrommetalloporphyrins.Nature Materials, 2002.1 (2), 118-121. (b) Shultz, A.M., et al., A CatalyticallyActive, Permanently Microporous MOF with Metalloporphyrin Struts.Journal of the AmericanChemical Society, 2009.131 (12), 4204-4205. (c) Sheldon, R.A., Metalloporphyrins in CatalyticOxidations.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.Electrochemical Detection comprises and utilizes active sites to the electro-catalysis of reduction process and utilize active sites to the electro-catalysis of oxidizing process, and the difunctional electrochemical sensor report of the material utilizing different active sites electro-catalysis different is 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-7H4PW18O62 center dot 18H (2) O as a bifuctional hydrogen peroxide electrocatalyst forbiosensors.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/BiosensingProperties of MnO (2) Nanomaterials for H (2) O (2)/Choline.Journal of Physical Chemistry C112 (48), 18984-18990.).
Summary of the invention
The object of this invention is to provide a kind of electrochemical sensor based on bimetallic porphyrin coordination polymer and preparation method thereof.
For achieving the above object, the technical solution adopted in the present invention is as follows:
Based on an electrochemical sensor for bimetallic porphyrin coordination polymer, comprise basal electrode, it is characterized in that, 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.
Described basal electrode is preferably glass-carbon electrode.
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.
Electrochemical sensor of the present invention has unique bimetallic active, and the metal active position reduction process of Cu to hydrogen peroxide has the effect of electro-catalysis, and the oxidizing process of metal active position Co to nitrite has the effect of electro-catalysis simultaneously.
Beneficial effect of the present invention: according to the electrochemical sensor based on metal-porphyrin coordination polymer of the present invention, there is unique thermometal electro catalytic activity, having good electrocatalysis characteristic to the material such as hydrogen peroxide and nitrite, is the difunctional electrochemical sensor of one.In order to improve the performance of sensor further, metalloporphyrin coordination polymer and CNTs being formed compound substance, has prepared electrochemical sensor-II, mixing of carbon nano-tube can significantly improve its electric sensing capabilities.Electrochemical sensor of the present invention is used for electrochemical analysis techniques, can 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, it is fast that this sensor has detection speed, 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 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 CoTCPP (a) and CoTCPP-Cu (b).
Fig. 3 is ultraviolet (UV) spectrogram of TCPP (a), CoTCPP (b) and CoTCPP-Cu (c).
Fig. 4 is transmission electron microscope picture (A) and the scanning electron microscope (SEM) photograph (B) of 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.
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; Solvent thermal reaction is carried out in the heating of described mixed solution, in the baking oven resting on 50 ~ 100 DEG C 2 ~ 12 days, product washing, dry, thermometal coordination polymer described in amaranth flour powder can be obtained.
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 unique bimetallic active, the metal active position reduction process of Cu to hydrogen peroxide has the effect of electro-catalysis, the oxidizing process of active sites Co to nitrite has the effect of electro-catalysis simultaneously, therefore can be used for the detection to hydrogen peroxide and nitrite.
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.Solvent thermal reaction is carried out in the heating of this mixed solution, in 65 ~ 100 DEG C of baking ovens, 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, SYNTHESISOF TETRAPHENYLPORPHYRINS UNDER VERYMILD 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) is 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 used for the detection of hydrogen peroxide
To be determined 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 the reduction of electrochemical sensor-I to hydrogen peroxide has electrocatalysis.
Electrochemical sensor-I is adopted to carry out Electrochemical Detection to hydrogen peroxide, shown in accompanying drawing 6A, under-0.25V detects current potential, electrochemical sensor-I is at PBS (0.1M, pH=7) in solution to the current-time curvel of hydrogen peroxide response dripping continuously variable concentrations, illustration is the response current of hydrogen peroxide and the calibration curve of concentration, detects and is limited to 2.5 × 10
-6m (S/N=3), the range of linearity is 7.0 × 10
-5-4.7 × 10
-3m (R=0.996), sensitivity is 23.5mA mol
-1l cm
-2.
Embodiment 4 electrochemical sensor-I is used for the detection of nitrite
As shown in fig. 5b, for bare electrode and electrochemical sensor-I to have or respectively without the C-V curve under sodium nitrite, along with adding of sodium nitrite, the Co of electrochemical sensor-I
iII/ Co
iIthe response of oxidation current strengthens gradually, illustrates that the oxidation of electrochemical sensor-I to nitrite has electrocatalysis.Shown in accompanying drawing 6B, under 0.85V constant voltage, drip the nitrite of variable concentrations continuously, obtain the current-time curvel that electrochemical sensor-I responds nitrite, illustration is the response current of sodium nitrite and the calibration curve of concentration, detects and is limited to 5.0 × 10
-6m (S/N=3), 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 5 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 6 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, under-0.25V constant potential, drip continuously the calibration curve that hydrogen peroxide obtains current-time curvel that electrochemical sensor-II responds hydrogen peroxide and response current and concentration, detection sensitivity brings up to 147.8mAM
-1cm
-2, detection limit is reduced to 5.0 × 10
-7m (S/N=3), the range of linearity expands as 5.0 × 10
-7-6.2 × 10
-3m (R=0.999), the performance of its electro-catalysis hydrogen-peroxide reduction be improved significantly.
Embodiment 7 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 the calibration curve that sodium nitrite obtains current-time curvel and response current and concentration continuously under the current potential of 0.85V, and detection limit is reduced to 2.5 × 10
-6m (S/N=3), detection sensitivity brings up to 439mAM
-1cm
-2, the range of linearity expands as 2.5 × 10
-6-1.1 × 10
-3m (R=0.9999), the performance of its electro-catalysis nitrite-oxidizing improves greatly.
Claims (4)
1. based on an electrochemical sensor for bimetallic porphyrin coordination polymer, comprise basal electrode, it is characterized in that, 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 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 electrochemical sensor based on bimetallic porphyrin coordination polymer according to claim 1, is characterized in that, described basal electrode is glass-carbon electrode.
3. a preparation method for the described electrochemical sensor based on bimetallic porphyrin coordination polymer of claim 1, it is characterized in that, described method comprises the following steps:
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 preparation method of electrochemical sensor according to claim 3, 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; Solvent thermal reaction is carried out in described mixed solution heating, and 50 ~ 100 DEG C are reacted 2 ~ 12 days, and product washing, drying, can obtain thermometal coordination polymer described in amaranth flour powder.
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