CN104990972B - Electrochemical sensor based on bimetallic porphyrin coordination polymer and preparation method thereof - Google Patents
Electrochemical sensor based on bimetallic porphyrin coordination polymer and preparation method thereof Download PDFInfo
- Publication number
- CN104990972B CN104990972B CN201510264704.4A CN201510264704A CN104990972B CN 104990972 B CN104990972 B CN 104990972B CN 201510264704 A CN201510264704 A CN 201510264704A CN 104990972 B CN104990972 B CN 104990972B
- Authority
- CN
- China
- Prior art keywords
- bimetallic
- cotcpp
- electrochemical sensor
- coordination polymer
- porphyrin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
Abstract
A kind of electrochemical sensor based on bimetallic porphyrin coordination polymer, in basal electrode surface modification bimetallic porphyrin coordination polymer or the compound of bimetallic porphyrin coordination polymer/CNT, described bimetallic porphyrin coordination polymer is the coordination polymer that Co, Cu and four (to carboxyl phenyl) porphyrins are self-assembly of, wherein metal Co and four N at porphyrin center are coordinated, each Ni metal is coordinated with the oxygen in four carboxyls respectively, and double coordination occurs for each carboxyl and two Ni metals.The electrochemical sensor of the present invention is amperometric sensor, bimetallic active with uniqueness, metal active position Cu plays the role of electro-catalysis to the reduction process of hydrogen peroxide, metal active position Co plays the role of electro-catalysis to the oxidizing process of nitrite simultaneously, and the incorporation of CNT is remarkably improved its electric sensing capabilities.
Description
Technical field
The present invention relates to a kind of electrochemical sensor, more particularly to a kind of electricity based on bimetallic porphyrin coordination polymer
Chemical sensor and preparation method thereof, described electrochemical sensor are a kind of difunctional electrochemical sensor.
Background technology
Coordination polymer is a kind of organic and inorganic that metal ion or cluster are formed by connecting with organic ligand by coordinate bond
Hybrid material, it is widely used in catalysis, gas storage and separation, optics because of its stability, multifunctionality, Modulatory character etc.
Many aspects such as material, magnetic material (referring to：(a) SR Batten, SM Neville, DR Turner, Coordination
Polymers：Design, Analysis and Application, 2008. (b) Chemical Society Reviews, 38
(2009).).But using coordination polymer as elctro-catalyst be used for fax sense research also seldom (referring to：(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.CoII/
ZnII-(L-Tyrosine)Magnetic Metal-Organic Frameworks.European Journal of
Inorganic Chemistry.)。
Metal-porphyrin coordination polymer is because it has biocompatibility using metalloporphyrin as part, is urged bionical
Be applied in change (referring to：(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 a kind of conjugation cycle compound for having and stablizing pi bond, therefore has light, electricity, catalysis, bionical grade side
Face property (referring to：(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 has splendid application prospect
Functional material, all there are potential advantages in electrochemistry and biological association area.
There is not been reported for electrochemical sensor based on metal-porphyrin coordination polymer.It is related to important biomolecule process
The detection of material (such as hydrogen peroxide) and nitrite in food is always the important class of analytical chemistry (including Electroanalytical Chemistry)
Topic.Electrochemical Detection is using electro-catalysis of the active sites to reduction process and utilizes electro-catalysis of the active sites to oxidizing process,
And utilize the different material of different active sites electro-catalysis difunctional electrochemical sensor report it is less (referring to：(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 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 C112 (48),
18984-18990.)。
The content of the invention
It is an object of the invention to provide a kind of electrochemical sensor based on bimetallic porphyrin coordination polymer and its preparation
Method.
To achieve 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, including basal electrode, it is characterised in that institute
The basal electrode surface modification bimetallic porphyrin coordination polymer stated or bimetallic porphyrin coordination polymer/CNT are answered
Compound；
Described bimetallic porphyrin coordination polymer is meso-5,10,15,20- tetra--(to carboxyl phenyl) porphyrin bimetallics
Coordination polymer (CoTCPP-Cu), it is that bimetallic Co, Cu match somebody with somebody with what four-(to carboxyl phenyl) porphyrins (TCPP) were self-assembly of
Position polymer, has following structure
In formula, CoTCPP is four-(to carboxyl phenyl) Cob altporphyrins；
Wherein metal Co and four N at four-(to carboxyl phenyl) porphyrin center are coordinated, and each Ni metal is respectively with coming
From the oxygen coordination in the carboxyl of four four-(to carboxyl phenyl) porphyrin, double coordination occurs for each carboxyl and two Ni metals.
Described basal electrode is preferably glass-carbon electrode.
Described CNT includes single-walled carbon nanotube (SWNTs) and multi-walled carbon nanotube (MWNTs).
Described electrochemical sensor is prepared using following methods：
CoTCPP-Cu ultrasonic disperses are formed into suspension in deionized water, the hanging drop is applied to basal electrode table
Face, dry；Again in electrode surface drop coating nafion solution, dry, producing described electrochemical sensor, (CoTCPP-Cu is modified
Electrode, it is denoted as electrochemical sensor-I)；
Or drop coating carbon nano tube suspension and dried first on basal electrode, then described CoTCPP-Cu is hanged
Supernatant liquid drop coating is in the electrode surface and airing；Again in electrode surface drop coating nafion solution, dry, described electrochemistry is made
Sensor (CoTCPP-Cu/CNTs modified electrodes, is denoted as electrochemical sensor-II).
Described electrochemical sensor is based on bimetallic porphyrin coordination polymer CoTCPP-Cu, is amperometric sensor.Carbon
The incorporation of nanotube is remarkably improved its electric sensing capabilities.
Electrochemical sensor of the present invention has unique bimetallic active, and metal active position Cu is to hydrogen peroxide
Reduction process plays the role of electro-catalysis, while metal active position Co plays the role of electro-catalysis to the oxidizing process of nitrite.
Beneficial effects of the present invention：According to the electrochemical sensor based on metal-porphyrin coordination polymer of the present invention, tool
There is the bimetallic electro catalytic activity of uniqueness, there is good electrocatalysis characteristic to materials such as hydrogen peroxide and nitrite, be one
The difunctional electrochemical sensor of kind.In order to further improve the performance of sensor, by metalloporphyrin coordination polymer and CNTs shapes
Into composite, electrochemical sensor-II is prepared for, the incorporation of CNT is remarkably improved its electric sensing capabilities.The present invention
Electrochemical sensor be used for electrochemical analysis techniques, can solve hydrogen peroxide, nitrite in current food, environment and industry
Detection speed present in detection is slow, cost is high, and the problems such as complex operation, the sensor has that detection speed is fast, high sensitivity,
The features such as cost is low.
With reference to specific embodiment, the present invention will be described in detail.Protection scope of the present invention is not with specific implementation
Mode is limited, but is defined in the claims.
Brief description of the drawings
Fig. 1 is CoTCPP-Cu XRD spectra, includes the XRD spectra (using circle markings) of planar structure, the XRD of interlamellar spacing
Spectrogram (with square mark).
Fig. 2 is CoTCPP (a) and CoTCPP-Cu (b) infrared spectrogram (FTIR).
Fig. 3 is TCPP (a), CoTCPP (b) and CoTCPP-Cu (c) ultraviolet (UV) spectrogram.
Fig. 4 is CoTCPP-Cu transmission electron microscope picture (A) and scanning electron microscope (SEM) photograph (B).
Fig. 5 electrochemical sensors-I cyclic voltammogram, scheme A：(a) bare glassy carbon electrode, no hydrogen peroxide；(b) naked glass carbon
Electrode, 0.5mmolL-1Hydrogen peroxide；(c) electrochemical sensor-I, no hydrogen peroxide；(d) electrochemical sensor-I,
0.5mmolL-1Hydrogen peroxide；Scheme B：(a) bare glassy carbon electrode, no natrium nitrosum；(b) bare glassy carbon electrode, 0.25mmolL-1Nitrous
Sour sodium；(c) electrochemical sensor-I, no natrium nitrosum；(d) electrochemical sensor-I, 0.25mmolL-1Natrium nitrosum.
Fig. 6 (A) electrochemical sensor-I to hydrogen peroxide constant potential -0.25V current-responsive figure, illustration be electric current ring
Tackle concentration of hydrogen peroxide mapping；(B) electrochemical sensor-I to natrium nitrosum constant potential 0.85V current-responsive figure, insert
Figure is that current-responsive is mapped to natrium nitrosum concentration.
Fig. 7 electrochemical sensors-II cyclic voltammogram, scheme A：(a) Glassy Carbon Electrode Modified with Multi-wall Carbon Nanotubes, no peroxide
Change hydrogen；(b) Glassy Carbon Electrode Modified with Multi-wall Carbon Nanotubes, 0.5mmolL-1Hydrogen peroxide；(c) electrochemical sensor-II, no peroxide
Change hydrogen；(d) electrochemical sensor-II, 0.5mmolL-1Hydrogen peroxide；Scheme B：(a) Glassy Carbon Electrode Modified with Multi-wall Carbon Nanotubes, nothing
Natrium nitrosum；(b) Glassy Carbon Electrode Modified with Multi-wall Carbon Nanotubes, 0.5mmolL-1Natrium nitrosum；(c) electrochemical sensor-II, nothing
Natrium nitrosum；(d) electrochemical sensor-II, 0.5mmolL-1Natrium nitrosum.
For Fig. 8 (A) electrochemical sensor-II to hydrogen peroxide in constant potential -0.25V current-responsive figure, illustration is electric current
Response is mapped to concentration of hydrogen peroxide；(B) electrochemical sensor-II to natrium nitrosum constant potential 0.85V current-responsive figure,
Illustration is that current-responsive is mapped to natrium nitrosum concentration.
Embodiment
Technical solutions according to the invention are further described in detail below by specific embodiment, but are necessary
Point out that following examples are served only for the description to the content of the invention, do not form limiting the scope of the invention.
It is that a kind of bimetallic porphyrin is matched somebody with somebody according to the electrochemical sensor based on bimetallic porphyrin coordination polymer of the present invention
Position polymer CoTCPP-Cu modified electrodes, i.e., in basal electrode surface modification bimetallic porphyrin coordination polymer CoTCPP-Cu
(electrochemical sensor-I)；Either a kind of CoTCPP-Cu/MWNTs modified electrodes, i.e., first with carbon nano tube modified described base
Hearth electrode, then in 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 bimetallics
Coordination polymer (CoTCPP-Cu), it is that bimetallic Co, Cu match somebody with somebody with what four-(to carboxyl phenyl) porphyrins (TCPP) were self-assembly of
Position polymer, wherein metal Co and four N at four-(to carboxyl phenyl) porphyrin center are coordinated, each Ni metal respectively with
Double coordination occurs for the oxygen coordination in the carboxyl from four four-(to carboxyl phenyl) porphyrin, each carboxyl and two Ni metals；
There is following structure
In formula, CoTCPP is four-(to carboxyl phenyl) Cob altporphyrins.
Described meso-5,10,15,20- tetra--(to carboxyl phenyl) porphyrin bimetallic coordination polymers can be used with lower section
It is prepared by method：
CoTCPP and mantoquita are dissolved in DMF respectively, and the copper salt solution prepared is added in CoTCPP solution, adds acid
Solution, obtains the mixed solution that red floccule separates out, CoTCPP in mixed solution：Mantoquita: sour mol ratio is 1: 4~40
: 100~400；The mixed solution is heated and carries out solvent thermal reaction, is rested in 50~100 DEG C of baking oven 2~12 days, is produced
Thing washing, dry, you can obtain the powdered bimetallic coordination polymer of aubergine.
The components such as the crystallization water or solvent molecule can be included in coordination polymer prepared by the above method.
Described electrochemical sensor is prepared using following methods：
CoTCPP-Cu ultrasonic disperses are formed into suspension in deionized water, the hanging drop is applied to basal electrode table
Face, dry；Again in electrode surface drop coating nafion solution, dry, electrochemical sensor-I is made；
Or drop coating carbon nano tube suspension and dried first on basal electrode, then described CoTCPP-Cu is hanged
Supernatant liquid drop coating is in the electrode surface and airing；Again in electrode surface drop coating nafion solution, dry, electrochemical sensing is made
Device-II.
Using its electro catalytic activity of cyclic voltammetry, show that described electrochemical sensor has unique bimetallic
Activity, metal active position Cu plays the role of electro-catalysis to the reduction process of hydrogen peroxide, while active sites Co is to nitrite
Oxidizing process plays the role of electro-catalysis, therefore available for the detection to hydrogen peroxide and nitrite.
Bimetallic coordination polymer [the Cu of embodiment 12(Co-TCPP)(H2O)2]·0.5DMF·5H2O(CoTCPP-Cu)
Preparation
CoTCPP 3mg (0.01mmol) are weighed, DMF 3mL is added and is allowed to dissolve；Weigh excessive Cu (NO simultaneously3)2.3H2O 100mg (0.4mmol), add DMF 2mL and be allowed to dissolve.By the above-mentioned Cu (NO prepared3)2Solution is added to CoTCPP
In solution, HNO is added while stirring3(1M) 1~4mL, finally obtain the mixed solution that red floccule separates out.This is mixed
Solution heating carries out solvent thermal reaction, stands 5 days in 65~100 DEG C of baking ovens, obtains aubergine powder.Filtering, is used respectively
DMF、H2O and EtOH washings, and dry at room temperature.
CoTCPP synthesis can refer to document：(a) Lindsey, J.S., H.C.Hsu, and I.C.Schreiman,
SYNTHESIS OF 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 bimetallic 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), calculate layer
Spacing is 1.0nm.Infrared and ultraviolet spectrogram (Fig. 2,3) shows that Co is coordinated with the N in porphyrin cavity, and Cu is sent out with carboxylic acid
Raw coordination.CoTCPP-Cu is in 1726cm-1C=O stretching vibration absworption peak disappears in place-COOH, and explanation-COOH all matches somebody with somebody
Position, in 1435cm-1And 950cm-1The O-H vibration absorption peaks for locating carboxyl are disappeared, and further explanation-COOH is coordinated completely.
1604、1404cm-1It is antisymmetry Vas (COO-) and symmetrical Vs (COO-) stretching vibration of carboxylic acid ion, 1604 and 1404cm-1Difference is equal to 200cm-1, carboxyl may in a manner of bidentate with Cu (II) be coordinated.If Fig. 3 is ultraviolet spectrogram, (a) is that TCPP exists
Absorption spectrum in DMF, occurs a strong peak S band at 420nm, four low energy of appearance at 515,549,590 and 646nm
Q bands.(b) it is absorption spectrums of the CoTCPP in DMF, because metal ion Co and the N in porphyrin ring are coordinated so that S bands
Red shift is to 433nm, and four Q bands become two, and at 548 and 595nm, reductions of the Q with absworption peak is because porphyrin part
Belong to D2hPoint group, complex belong to D4hPoint group.(c) it is absorption spectrums of the Cu-CoTCPP in DMF, S bands are blue shifted to 419nm,
Q bands are reduced to one simultaneously, because the carboxyl O carried on metalloporphyrin ring and Cu (II) is coordinated, improve coordination polymerization
The symmetry of thing molecule.The change explanation coordination polymer of uv-vis spectra is the coordination polymerization using CoTCPP as construction unit
Thing.As can be seen that described CoTCPP-Cu is into a width of for 100-200nm debris accumulations from SEM with TEM electron microscopes (Fig. 4)
0.1-2 μm, a length of 0.5-3 μm of irregular granules.
Electrochemical sensor-the I of embodiment 2 preparation
(1) polishing and cleaning of bare glassy carbon electrode
Glass-carbon electrode is clean and ultrasonic one minute with secondary deionized water, then the alumina powder with a diameter of 0.3um
Polishing five minutes, the slurry polished on cloth and electrode is cleaned with secondary deionized water, and by glass-carbon electrode be put in it is secondary go from
Ultrasound one minute in sub- water, polishing is with after cleaning, finally drying up glass-carbon electrode standby repeatedly.
(2) electrode modification
5mg CoTCPP-Cu ultrasonic disperses are formed into suspension in 400 μ L deionized waters, by the 6 μ L suspension drop coatings
In the glassy carbon electrode surface that step (1) obtains, dry；Again in the μ L 1%nafion solution of electrode surface drop coating 2, dry, produce
CoTCPP-Cu modified electrodes, it is denoted as electric transducer-I.
Electrochemical sensor-the I of embodiment 3 is used for the detection of hydrogen peroxide
Measure in pH=7 PBS electrolyte bare electrode and electrochemical sensor-I respectively under with or without hydrogen peroxide
C-V curve, as shown in fig. 5, a is naked GCE, and b is that naked GCE adds 0.5mmolL-1H2O2, a and b comparative descriptions are naked
GCE is to H2O2Do not respond to.C-d is the H that electrochemical sensor-I adds various concentrations respectively2O20 and 0.5mmol L-1, with
The addition of hydrogen peroxide, the response of reduction current gradually strengthen, and illustrate that reduction of the electrochemical sensor-I to hydrogen peroxide has
Electrocatalysis.
Electrochemical Detection is carried out to hydrogen peroxide using electrochemical sensor-I, shown in accompanying drawing 6A, electricity is detected in -0.25V
Under position, what electrochemical sensor-I was responded in PBS (0.1M, pH=7) solution to the continuous hydrogen peroxide that various concentrations are added dropwise
Current-time curvel, illustration are the response current of hydrogen peroxide and the calibration curve of concentration, and detection 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 are 23.5mA mol-1L cm-2。
Electrochemical sensor-the I of embodiment 4 is used for the detection of nitrite
As shown in fig. 5b, it is bare electrode and electrochemical sensor-the I C-V curve under with or without natrium nitrosum respectively,
With the addition of natrium nitrosum, electrochemical sensor-I CoIII/CoIIThe response of oxidation current gradually strengthens, and illustrates electrochemistry
Oxidations of the sensor-I to nitrite has electrocatalysis.It is continuous to be added dropwise not under 0.85V constant voltages shown in accompanying drawing 6B
With the nitrite of concentration, the current-time curvel that electrochemical sensor-I responds to nitrite is obtained, illustration is nitrous acid
The response current of sodium and the calibration curve of concentration, detection are limited to 5.0 × 10-6M (S/N=3), the range of linearity are 3.5 × 10-5-
5.5×10-3M, sensitivity are 15.32mA mol-1L cm-2。
Electrochemical sensor-the II of embodiment 5 preparation
(1) polishing and cleaning of bare glassy carbon electrode：With the step of above-described embodiment 1 (1)
(2) electrode modification
The multi-walled carbon nanotube hanging drop that 6 μ L concentration are 5mg/mL is applied to the glassy carbon electrode surface that step (1) obtains,
Dry；The μ L concentration of drop coating 6 is 12.5mg/mL CoTCPP-Cu suspension again, is dried；Finally in the μ L 1% of electrode surface drop coating 2
Nafion solution, dries, and produces CoTCPP-Cu/MWNTs modified electrodes, is denoted as electric transducer-II.
Electrochemical sensor-the II of embodiment 6 is used for the detection of hydrogen peroxide
As shown in accompanying drawing 7A and 8A, electrochemical sensor-II has obvious reduction electro catalytic activity to hydrogen peroxide,
Hydrogen peroxide is continuously added dropwise under -0.25V constant potentials and obtains the current time song that electrochemical sensor-II responds to hydrogen peroxide
The calibration curve of line and response current and concentration, detection sensitivity bring 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), its electro-catalysis hydrogen-peroxide reduction
Performance be improved significantly.
Electrochemical sensor-the II of embodiment 7 is used for the detection of nitrite
Accompanying drawing 7B is bare electrode and electrochemical sensor-II in the C-V curve with or without nitrite.Accompanying drawing 8B be
Natrium nitrosum is continuously added dropwise under 0.85V current potential and obtains current-time curvel and response current and the calibration curve of concentration, detects
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 greatly improve.
Claims (4)
1. a kind of electrochemical sensor based on bimetallic porphyrin coordination polymer, including basal electrode, it is characterised in that described
Basal electrode surface modification bimetallic porphyrin coordination polymer or bimetallic porphyrin coordination polymer/CNT it is compound
Thing；
Described bimetallic porphyrin coordination polymer is meso-5, and 10,15,20- tetra--(to carboxyl phenyl) porphyrin bimetallic is coordinated
Polymer, CoTCPP-Cu is designated as, is the coordination polymerization that bimetallic Co, Cu and four-(to carboxyl phenyl) porphyrins are self-assembly of
Thing, there is following structure
In formula, CoTCPP is four-(to carboxyl phenyl) Cob altporphyrins；
Wherein metal Co and four N at four-(to carboxyl phenyl) porphyrin center are coordinated, each Ni metal respectively with from four
Double coordination occurs for the oxygen coordination in the carboxyl of individual four-(to carboxyl phenyl) porphyrins, each carboxyl and two Ni metals.
2. the electrochemical sensor according to claim 1 based on bimetallic porphyrin coordination polymer, it is characterised in that institute
The basal electrode stated is glass-carbon electrode.
3. a kind of preparation method of the electrochemical sensor based on bimetallic porphyrin coordination polymer of claim 1,
Characterized in that, described method comprises the following steps：
A) CoTCPP-Cu ultrasonic disperses are formed into suspension in deionized water, the hanging drop are applied to basal electrode surface,
Dry；Again in electrode surface drop coating nafion solution, dry, produce described electrochemical sensor；Or
B) drop coating carbon nano tube suspension and dried first on basal electrode, then by described CoTCPP-Cu hanging drops
It is coated in the electrode surface and airing；Again in electrode surface drop coating nafion solution, dry, described electrochemical sensing is made
Device.
4. the preparation method of electrochemical sensor according to claim 3, it is characterised in that described CoTCPP-Cu is adopted
Prepare using the following method：
CoTCPP and mantoquita are dissolved in DMF respectively, and copper salt solution is added in CoTCPP solution, adds acid solution, is obtained
There is a mixed solution that red floccule separates out, CoTCPP in mixed solution: mantoquita: sour mol ratio is 1: 4~40: 100~
400；The mixed solution is heated and carries out solvent thermal reaction, 50~100 DEG C are reacted 2~12 days, product washing, are dried, you can
Obtain the powdered bimetallic coordination polymer of aubergine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510264704.4A CN104990972B (en) | 2015-05-21 | 2015-05-21 | Electrochemical sensor based on bimetallic porphyrin coordination polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510264704.4A CN104990972B (en) | 2015-05-21 | 2015-05-21 | Electrochemical sensor based on bimetallic porphyrin coordination polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104990972A CN104990972A (en) | 2015-10-21 |
| CN104990972B true CN104990972B (en) | 2018-01-05 |
Family
ID=54302811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510264704.4A Expired - Fee Related CN104990972B (en) | 2015-05-21 | 2015-05-21 | Electrochemical sensor based on bimetallic porphyrin coordination polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104990972B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106158403B (en) * | 2016-07-15 | 2020-10-23 | 中山大学 | Metal coordination supermolecular grid and two-dimensional carbon composite material, and preparation method and application thereof |
| CN106324055B (en) * | 2016-10-09 | 2018-10-26 | 南京师范大学 | A kind of application of CoTPyP metalloporphyrins coordination polymer material |
| CN107170586B (en) * | 2017-05-10 | 2019-03-29 | 中山大学 | Metal coordination supramolecule grid and three-dimensional grapheme block composite material, preparation method, purposes and super capacitor electrode |
| CN109540989A (en) * | 2018-11-19 | 2019-03-29 | 清华-伯克利深圳学院筹备办公室 | A kind of sensitive electrode, preparation method and biosensor and its application using it |
| CN109709180B (en) * | 2019-03-04 | 2021-03-23 | 济南大学 | Photoinduced electrochemical method for detecting cancer cells by using self-assembled organic semiconductor material PC05 nanowire |
| CN111044587A (en) * | 2019-11-25 | 2020-04-21 | 西安医学院 | 2D porphyrin MOF nano material for electrochemical sensor and preparation method thereof |
| CN114573826B (en) * | 2022-02-28 | 2022-12-27 | 上海交通大学 | Two-dimensional metal organic framework based on isocyano coordination, preparation method and application |
| CN114878663B (en) * | 2022-06-24 | 2023-10-13 | 济南大学 | Bimetal covalent organic framework material, electrochemical luminescence sensor and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001026655A1 (en) * | 1999-10-13 | 2001-04-19 | Uab Research Foundation | Metalloporphyrin treatment of neurologic disease |
| CN103554302A (en) * | 2013-10-29 | 2014-02-05 | 广西大学 | Preparation method and application for chitosan-grafted quadri(p-carboxylphenyl) metalloporphyrin |
-
2015
- 2015-05-21 CN CN201510264704.4A patent/CN104990972B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001026655A1 (en) * | 1999-10-13 | 2001-04-19 | Uab Research Foundation | Metalloporphyrin treatment of neurologic disease |
| CN103554302A (en) * | 2013-10-29 | 2014-02-05 | 广西大学 | Preparation method and application for chitosan-grafted quadri(p-carboxylphenyl) metalloporphyrin |
Non-Patent Citations (3)
| Title |
|---|
| Cu(II)-Based MOF Immobilized on Multiwalled Carbon Nanotubes: Synthesis and Application for Nonenzymatic Detection of Hydrogen Peroxide with High Sensitivity;Echeng Zhou等;《Electroanalysis》;20140929;第26卷(第11期);第2527-2528页 * |
| 基于功能配体的金属-有机框架材料的设计合成与催化性能研究;解明华;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20120715(第07期);第63页倒数第1段，第66页倒数第1段至第68页第1段，图3-6，图3-10 * |
| 金属卟啉框架材料的设计合成及应用研究;邹超;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20130815(第08期);第118页第1段，图4.1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104990972A (en) | 2015-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104990972B (en) | Electrochemical sensor based on bimetallic porphyrin coordination polymer and preparation method thereof | |
| CN104897765B (en) | The method of electrochemical sensor detection hydrogen peroxide and nitrite based on bimetallic porphyrin coordination polymer | |
| Lopa et al. | A base-stable metal-organic framework for sensitive and non-enzymatic electrochemical detection of hydrogen peroxide | |
| Liu et al. | One-step synthesis of porphyrinic iron-based metal-organic framework/ordered mesoporous carbon for electrochemical detection of hydrogen peroxide in living cells | |
| Duan et al. | A three-dimensional conductive molecularly imprinted electrochemical sensor based on MOF derived porous carbon/carbon nanotubes composites and prussian blue nanocubes mediated amplification for chiral analysis of cysteine enantiomers | |
| Yang et al. | Electrochemical chiral interface based on the Michael addition/Schiff base reaction of polydopamine functionalized reduced graphene oxide | |
| Zhu et al. | In situ growth of copper oxide-graphite carbon nitride nanocomposites with peroxidase-mimicking activity for electrocatalytic and colorimetric detection of hydrogen peroxide | |
| Liang et al. | 3D graphene/hydroxypropyl-β-cyclodextrin nanocomposite as an electrochemical chiral sensor for the recognition of tryptophan enantiomers | |
| Zuo et al. | An electrochemical biosensor for determination of ascorbic acid by cobalt (II) phthalocyanine–multi-walled carbon nanotubes modified glassy carbon electrode | |
| Gong et al. | Microperoxidase-11@ PCN-333 (Al)/three-dimensional macroporous carbon electrode for sensing hydrogen peroxide | |
| Liu et al. | Hydrogen peroxide biosensor based on the direct electrochemistry of myoglobin immobilized on silver nanoparticles doped carbon nanotubes film | |
| Sun et al. | Direct electrochemistry and electrocatalysis of hemoglobin on chitosan-room temperature ionic liquid-TiO2-graphene nanocomposite film modified electrode | |
| Yan et al. | Synergetic catalysis based on the proline tailed metalloporphyrin with graphene sheet as efficient mimetic enzyme for ultrasensitive electrochemical detection of dopamine | |
| Bhardwaj et al. | A three-phase copper MOF-graphene-polyaniline composite for effective sensing of ammonia | |
| Yang et al. | TiO2-CuCNFs based laccase biosensor for enhanced electrocatalysis in hydroquinone detection | |
| Liu et al. | Functionalized single-walled carbon nanohorns for electrochemical biosensing | |
| Lei et al. | Microwave-assisted synthesis of hemin–graphene/poly (3, 4-ethylenedioxythiophene) nanocomposite for a biomimetic hydrogen peroxide biosensor | |
| Wang et al. | A copper (II) phthalocyanine-based metallo-covalent organic framework decorated with silver nanoparticle for sensitively detecting nitric oxide released from cancer cells | |
| Yang et al. | Nanorods of a new metal–biomolecule coordination polymer showing novel bidirectional electrocatalytic activity and excellent performance in electrochemical sensing | |
| Tiwari et al. | Electro-oxidation of phenyl hydrazine on a modified electrode constructed using nanocomposite of ruthenium terpyridyl complex, multiwalled carbon nanotubes and nafion | |
| Sakthinathan et al. | Reduced graphene oxide/gold tetraphenyl porphyrin (RGO/Au–TPP) nanocomposite as an ultrasensitive amperometric sensor for environmentally toxic hydrazine | |
| Guler et al. | A novel nonenzymatic hydrogen peroxide amperometric sensor based on Pd@ CeO2-NH2 nanocomposites modified glassy carbon electrode | |
| Chen et al. | Electrochemistry and electrocatalysis of myoglobin immobilized in sulfonated graphene oxide and Nafion films | |
| Gong et al. | One-step preparation of a composite consisting of graphene oxide, Prussian blue and chitosan for electrochemical sensing of hydrogen peroxide | |
| Shi et al. | A multiwalled carbon nanotube/tetra-β-isoheptyloxyphthalocyanine cobalt (ii) composite with high dispersibility for electrochemical detection of ascorbic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180105 Termination date: 20200521 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |