CN107037096B - A kind of electrochemical sensor and its preparation method and application based on the modification of CoCuCdTCPP coordination polymer - Google Patents
A kind of electrochemical sensor and its preparation method and application based on the modification of CoCuCdTCPP coordination polymer Download PDFInfo
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Abstract
The invention discloses a kind of electrochemical sensors and its preparation method and application based on the modification of CoCuCdTCPP coordination polymer.The electrochemical sensor is made of the suspended drop-coated of CoCuCdTCPP coordination polymer in electrode surface；The CoCuCdTCPP coordination polymer includes bimetallic CuCdTCPP and CoCdTCPP coordination polymer and three metal system CuCoCdTCPP coordination polymers.CoCuCdTCPP coordination polymer in the present invention applies to be for the first time in electrochemical sensing, since the electrochemical sensor that there are CoCuCdTCPP coordination polymer multiple metal active centres modified electrodes to be formed effectively can steadily detect nitrous acid and sodium hydrogen peroxide, response time is short, high sensitivity, and at low cost, preparation is simple.
Description
Technical field
The invention belongs to fields of nano material application, and in particular to it is a kind of based on CoCuCdTCPP coordination polymer modification
Electrochemical sensor and its preparation method and application.
Background technique
In nearest 30 years, the development speed of metal-organic framework materials be it is surprising, only just report within 2002
Nearly 1500 structures.In fact, increasing by one within the quantity of the 3-dimensional metal organic framework material of report every 3.9 years since 1978
Times, all metal-organic framework materials (including one-dimensional, two and three dimensions materials) doubles for quantity every 5.7 years.And
The growth rate of Cambridge database (CSD) is to double for every 9.3 years.Metal-organic framework materials growth explanation beyond imagination
Its importance in scientific research and technology.The special physicochemical property of this kind of material make they gas storage with separate,
Heterogeneous catalysis, magnetics, the fields such as polymeric optical and sensing suffer from potential utility value.Moreover, as MOFs is in film
The development of the research directions such as inner surface modification and nano particle preparation, this kind of very high material of controllability more have as general
Logical material is able to the potential quality applied.
External at present and domestic many research groups are all in the design, synthesis and function of metal-organic framework materials of throwing oneself into
It can develop, and achieve remarkable research results.These researchers set out from different perspectives, by developing new ligand, adopt
With new method, many structure novels, metal-organic framework materials of good performance are synthesized, to recognize metal-organic framework materials
Synthesising law established certain basis, however, design for this kind of material function and exploitation are also far from enough.
Porphyrin (Porphyrin) is a kind of large biological molecule for having most important effect in many bioprocess, people
Synthesized many miscellaneous Porphyrin and its derivatives, and study the natural body based on Porphyrin Molecule as model
System, the research of porphyrin material is also very active, they are often in anticancer drug, catalyst, semiconductor, superconductor, electronics material
Material, nuclear magnetic resonance image reinforcing agent, nonlinear optical material and DNA- are combined or the fields such as cleavage reagent have a wide range of applications.
Especially in catalytic field, since metalloporphyrin is simulation catalase, peroxidase and cytochromes that can be appropriate
The biological model of the protein such as P450, therefore metalloporphyrin also can be applied to bio-sensing.Metalloporphyrin has goodization
Learn and thermal stability, be readily synthesized and property stablize, these characteristics make metalloporphyrin become receive come it is non-in material self assembles
Often noticeable one kind constructs module.From early stage the 1990s, people begin to construct MOFs function using porphyrin unit
It can material.The article of the metal active centres detection small molecule using MOFs, but the bimetallic of different metal proportion has been reported
The research of system sensing capabilities is less, and three metal systems have not been reported.
Nitrogen source of the nitrite as green plants is to be widely present in most common nitrogenous compound in human environment,
It is also common additive and preservative in food industry.But nitrite can be acted on hemoglobin, Fe2+It is oxidized
At Fe3+, ferrihemoglobin is formed, the normal function of carrying oxygen and discharge oxygen is lost, leads to histanoxia, especially maincenter
Neural anoxic is more sensitive, eventually leads to " blue mass formed by blood stasis ", and nitrite can also react to form carcinogenic nitrous with amine substance
Amine.Due to its potential toxic side effect, the World Health Organization defines that the concentration of Determination of Nitrite in Drinking Water ion is 3mg/mL.
In recent years, the underground water in China 90% has suffered from different degrees of pollution, wherein 30% is due to NO3-N and NO2-N
It is exceeded.Therefore, it carries out sensitive to nitrite and quickly detects and have become conservation of nature environment and guarantee public's health
Critically important research work, to drinking water and food safety monitoring and ahead of time find the etiological cause of the disease with important scientific meaning, also for
Building novel sensor proposes the requirement more updated.
Traditional detection method mainly includes chromatography, chemiluminescence, spectrophotometry and electrochemical assay etc..Its
In, electrochemical process because have many advantages, such as instrument is simple, analysis speed is fast, high sensitivity and stability it is high due to rapidly become research heat
Point.In reported system, the active material that is introduced into combination electrode of first choice is noble metal Au, Ag, Pd and CoNi alloy etc., this
The disadvantages of certainly will leading to higher electrode cost, potential to bioactive substance nanometer toxicity.It is influenced less on detection effect
Under the premise of, replace precious metal that certainly will become trend with cheap metal Cu, Fe and oxide, this will more be conducive to sensor
Commercialization expand.
Aqueous hydrogen peroxide solution is commonly called as hydrogen peroxide, is a kind of widely used traditional inorganic chemical product.1818, by
French chemist Thenard is reacted by dilute sulfuric acid with barium peroxide, prepares hydrogen peroxide for the first time in the lab.Peroxidating
Hydrogen has important application in light industry, electronic technology, health care, the numerous areas such as environmental project, to hydrogen peroxide it is accurate,
Quickly detection has important in inhibiting in scientific practice.Therefore, all kinds of H2O2The research of sensor is always sensor field
It is popular.H is applied to there are many method at present2O2Quantitative detection, such as spectrophotometry, analysis by titration, fluorescence analysis
Method, chemoluminescence method etc..But these methods take time and effort, and reagent cost is higher.And electrochemical process detects H2O2It is then relatively simple
Just, fast, and repeatability is high, as a result reliably.
In the prior art, some disadvantages are still remained by NHP electrochemical sensor prepared by precious metal material.First
H2O2Reduction is highly dependent on available electrode surface area, and the noble metal actives area such as Pt, Ag of monomer is still limited, and works as
It is easy for causing electrode surface saturation when ion concentration is excessive, so that sensor performance rapid drawdown；Secondly, studies have found that, Pt is repaired
Electrode is adornd in high concentration Cl-In there are failure phenomenons；Finally, price is also a key factor, under present condition, noble metal is repaired
There is also many problems for the recycling and reusing of decorations electrode material, therefore exploitation uses cheap materials and prepares NHP electrochemical sensor
Just become a new hot spot.The transistion metal compounds such as Cu, Mn, Co are common energy storage materials, are urged in fuel cell
Also have in terms of agent and answers extensively.Therefore naturally it is used for H2O2The preparation research of electrochemical sensor compares the materials such as Pt, Ag,
Cu, Mn, Co class material price are more cheap, are easy to obtain, effect on environment is also smaller.Viewpoint generally acknowledged at present is, material
Specific surface area is bigger, is more conducive to the raising of electron transfer rate, to promote the electro-catalysis effect of material, therefore prepares each
The hot spot that there is kind the material of large specific surface area pattern just to become the field, and around transistion metal compound at present
Through the nanoparticle for developing various patterns.Generally speaking, transistion metal compound is a kind of more excellent H2O2Detect material
Material has many advantageous advantages in preparation NHP electrochemical sensor, but also still there are some challenges.Cu, Mn class
Closing object, stability is poor in acid condition, limits the use scope of sensor to a certain extent.
Summary of the invention
Goal of the invention: in view of the problems of the existing technology, the present invention provides one kind to be based on CoCuCdTCPP polycomplexation
Close the electrochemical sensor of object modification.The electrochemical sensor based on the modification of CoCuCdTCPP coordination polymer to nitrous acid and
Sodium hydrogen peroxide also has apparent electrocatalysis, effectively can steadily detect nitrous acid and sodium hydrogen peroxide, and detect
High sensitivity and cheap.
The present invention also provides a kind of preparation methods of electrochemical sensor based on the modification of CoCuCdTCPP coordination polymer
And application.
Technical solution: to achieve the goals above, a kind of as described in the present invention to be based on CoCuCdTCPP coordination polymer
The electrochemical sensor of modification, which is characterized in that be made of the suspended drop-coated of CoCuCdTCPP coordination polymer in electrode surface；
The CoCuCdTCPP coordination polymer includes bimetallic CuCdTCPP and CoCdTCPP coordination polymer and three metal systems
CuCoCdTCPP coordination polymer.
Wherein, described bimetallic CuCdTCPP coordination polymer Cu, Cd, TCPP, which feed intake, (feeds intake and refers in preparation process and be added
Substance amount) molar ratio be 1:3:1,1:1:1 or 3:1:1.It feeds intake and refers to the amount for the substance being added in preparation process.
The molar ratio that described bimetallic CoCdTCPP coordination polymer Co, Cd, TCPP feed intake is 1:3:1,1:1:1 or 3:1:
1。
The molar ratio that described three metals CoCuCdTCPP coordination polymer Co, Cu, Cd, TCPP feed intake is 4/3:4/3:4/3:
1。
Wherein, the electrode is the glass-carbon electrode (MWCNTs/GCE) that glass-carbon electrode (GCE) or multi-walled carbon nanotube are modified.
The preparation method of electrochemical sensor of the present invention based on the modification of CoCuCdTCPP coordination polymer, including
Following steps:
(1) glass-carbon electrode polishing cloth is polishing to mirror surface, and ultrasonic cleaning is dried spare after taking-up；
(2) CoCuCdTCPP coordination polymer is dissolved in secondary distilled water, ultrasonic disperse, obtained suspension；
(3) it by suspended drop-coated to step (1) treated glassy carbon electrode surface, is placed to dry at room temperature, then polymerizeing
Object surface is added dropwise naphthols nafion solution and fixes (naphthol solution that general selection mass fraction is 1%), and air dries at room temperature
It is spare, polymer/glass-carbon electrode is made；
(4) multi-walled carbon nanotube (MWCNTs) of step (1) treated glassy carbon electrode surface drop coating carboxylated, repeats
Polymer/MWCNTs/ glass-carbon electrode is made in the process of step (3).
Wherein, glass-carbon electrode described in step (1) is cleaned by ultrasonic in secondary distilled water and ethyl alcohol.
It is of the present invention based on CoCuCdTCPP coordination polymer modification electrochemical sensor detection hydrogen peroxide and
Application in sodium nitrite.
Three gold medals used in electrochemical sensor of the present invention based on the modification of CoCuCdTCPP coordination polymer
Category system CuCoCdTCPP coordination polymer.
The present invention, which provides a series of metal coordinating polymers with different proportion bimetallic and three metals, has electrification
Learn the organic coordination polymer (MOFs) in activated centre, i.e. different proportion CuCdTCPP, CoCdTCPP and three metal systems
Synthesis, characterization and the chemical property detection of CuCoCdTCPP.
According to metal (Cu, Co, Cd) and ligand (H2TCPP) feed ratio, the polymer that different feed ratios are synthesized are abridged
For Cu1Cd3TCPP1, Cu2Cd2TCPP1, Cu3Cd1TCPP1, Co1Cd3TCPP1, Co2Cd2TCPP1, Co3Cd1TCPP1, Cu4/3Cd4/ 3Co4/3TCPP1(the corresponding metal of the ratio between subscript and ligand H2TCPP feeds intake the ratio between the amount of substance)；It is easier in order to express, this
The abbreviation of substance is corresponding in 7 simplifies Cu1Cd3TCPP, Cu2Cd2TCPP, Cu3Cd1TCPP, Co1Cd3TCPP1, Co2Cd2TCPP,
Co3Cd1TCPP, CuCoCdTCPP.The coordination of the series be polymer include 6 kinds of bimetallic Cu1Cd3TCPP, Cu1Cd1TCPP,
Cu3Cd1TCPP, Co1Cd3TCPP, Co1Cd1TCPP, Co3Cd1TCPP coordination polymer, except Cu1Cd3TCPP and
Co1Cd3TCPP is outside reported substance, remaining ratio be it is of the invention new and at different proportion coordination polymer.It should
Contain three Ni metal CoCdTCPP coordination polymers in system, possesses multiple metal active centres and three Ni metal CoCdTCPP
Coordination polymer is newly synthesized coordination polymer.
With document (Smythe N C, Butler D P, Moore C E, et al.A heterobimetallic
Metal-organic framework with tunable reactive metal sites:synthesis,
Characterization, and reactivity. [J] .Dalton Transactions, 2012, hereinafter referred to as document 1) in
(the Et of synthesis2NH2)[Cd(H2O)][H2TCPP]·4DEF·H2O (is abbreviated as 1 (CCDC- in the chemical substance document
865035) its molecule), is abbreviated as CdTCPP in the present invention.By solvent structure totally 7 kinds of metal coordinating polymers,
It coincide with the XRD of CdTCPP.Cadmium (II) ion is seven coordinations in CdTCPP coordination polymer, three carboxylate radicals in mesoporphyrin
Six oxygen are provided, water provides an oxygen.Each Cd2+Three TCPP molecules are connected, coordinate bond forms the triangular pyramid type of distortion.Equally
, each free radical Porphyrin Molecule is connected to three Cd2+Ion creates the vertex of a T shape, and in apex, tetrabasic carboxylic acid matches constitution
Sonization.Resulting two-dimensional surface has protonated carboxylic acid in bottom and top.Adjacent two-dimensional surface utilizes matter between layers
π-pi accumulation that sonization carboxylic acid is formed is fixed together.Distance between layers is aboutThe frame has anion
Charge is by diethyl cation balance.Maximum pore in polymerThe DEF of intramolecular, water and Et2NH2+ account for structure cell
The 42% of total volume.
Species metal content in order to prove different feed ratio synthesis is different, strictly controls when measuring the XRD of this 7 kinds of substances
Variable processed, the other conditions controlled other than sample are identical, and in order to reach this condition, all samples are in wavelengthIt is measured under conditions of scanning speed 4s/step, 0.02 °/step, and in order to make environmental variance as far as possible,
We concentrate the XRD measurement of a series of substance in 2 hours and complete, and pass through the comparison at the peak XRD, it has been found that bimetallic system
In with Cd percentage composition reduction, diffraction maximum moves to right, and 2 θ values increase, and interlamellar spacing reduces, this is because Ni metal2+(73pm)、
Co2+(65pm) radius ratio Cd2+(95pm) small reason, the offset at peak prove that we have synthesized the polycomplexation of different metal ratio
Close object.Wherein the coordination polymer width is a length of 4um of 2 mL or so.It is clean to dry the suspension for being made into 5mg/mL, ultrasound 30
6 mL drop coatings are gone on the electrode after minute, dry the naphthol solution that 2 mL mass fractions of drop are 1% later.Meanwhile in order to improve
Performance first modifies 6 mL concentration on glass-carbon electrode and is the multi-walled carbon nanotube (MWCNTs) of 5 mg/mL, then the outstanding of MOFs is added dropwise
The naphthol solution that 2 mL mass fractions are 1% is finally added dropwise in turbid.Electrode is made according to the above method with 7 kinds of synthesized MOFs
Sodium nitrite and hydrogen peroxide are detected, sensitivity can match different and different, but response time with metal
Very short, sensitivity is relatively high, there is certain application value in terms of electrochemical sensing.
The electrochemical sensor that Cu1Cd1TCPP is modified in bimetallic system in the present invention detects sodium nitrite sensitive
Degree is up to 418 mAMcm-2, the electrochemical sensor of Cu1Cd1TCPP modification is to the sensitivity highest of hydrogen peroxide
413.83 mA·M·cm-2.Three metal system Cu1Co1Cd1TCPP modification is on glass-carbon electrode to hydrogen peroxide and sodium nitrite
Also there is apparent electrocatalysis, sensitivity is respectively 266.25mAMcm-2、369.04 mA·M·cm-2。
The utility model has the advantages that compared with prior art, the present invention has the advantage that
1, all CoCuCdTCPP coordination polymers of the present invention apply to be for the first time in electrochemical sensing.Due to
There is CoCuCdTCPP coordination polymer multiple metal active centres modification electrochemical sensor can detecte to sodium nitrite
With two kinds of substances of hydrogen peroxide, and there is higher sensitivity.
2, in the prior art to the preferred active material being introduced into combination electrode of sodium nitrite detection be noble metal Au, Ag,
The disadvantages of Pt etc., this certainly will cause electrode cost higher, nanometer toxicity potential to bioactive substance, polycomplexation of the invention
The electrochemical sensor for closing object modification is cheap to the metal price in sodium nitrite detection sensitivity height and polymer.
3, all CoCuCdTCPP coordination polymers (MOFs) of the present invention are with good stability in strong acid and strong base,
Inspection of the made electrode to hydrogen peroxide, overcome transistion metal compound under acid or alkaline conditions stability difference
Problem has widened the use scope of sensor.
4, the CoCuCdTCPP coordination polymer in the present invention and the electricity based on the modification of CoCuCdTCPP coordination polymer
Chemical sensor preparation is simple, at low cost, and effectively effectively can steadily detect nitrous acid and sodium hydrogen peroxide, rings
Short between seasonable, sensitivity is all high, there is certain application value in terms of electrochemical sensing.CoCuCdTCPP coordination of the present invention simultaneously
Three Ni metal 1Cd1Co1TCPP coordination polymers in polymer are newly synthesized coordination polymers.
Detailed description of the invention
Fig. 1 is closed a series of electron microscope of CoCuCdTCPP coordination polymers of preparation by present example 1；
Fig. 2 is closed a series of XRD diagram of CoCuCdTCPP coordination polymers of preparation by present example 1, wherein
CdTCPP is the base peak that 1 (CCDC-865035) is synthesized in Literature 1；
Fig. 3 is the 1-Cu (CCDC- synthesized in Cu1Cd3TCPP, Co1Cd3TCPP and document 1 of the invention synthesized
865036), the comparison of the base peak of 1-Co (CCDC-865037)；
Fig. 4 is that 3CuCdTCPP of embodiment of the present invention series of peaks belongs to coordination polymer peak ownership；
Fig. 5 is that 3CoCdTCPP of embodiment of the present invention series of peaks belongs to coordination polymer peak ownership；
Fig. 6 is that 3CuCoCdTCPP of embodiment of the present invention series of peaks belongs to coordination polymer peak ownership；
Fig. 7 is that polymer-modified glass-carbon electrode responds the CV of sodium nitrite；
Fig. 8 is response of the polymer-modified glass-carbon electrode to hydrogen peroxide CV；
Fig. 9 is GCE, coordination polymer/GCE, MWCNTs/GCE, coordination polymer/MWCNTs/GCE pH=7's
CV curve in the electrolyte solution of 0.1mol/L compares, wherein a Cu1Cd3TCPP, b Cu1Cd1TCPP, c are
Cu3Cd1TCPP, d Co1Cd3TCPP, e Co1Cd1TCPP, f Co3Cd1TCPP, g CuCoCdTCPP；
Figure 10 is MWCNTs/GCE, coordination polymer/MWCNTs/GCE whether there is or not the 0.1mol/L's of sodium nitrite pH=7
CV curve in electrolyte solution compares, and wherein a is Cu1Cd3TCPP, and b Cu1Cd1TCPP, c Cu3Cd1TCPP, d are
Co1Cd3TCPP, e Co1Cd1TCPP, f Co3Cd1TCPP, g CuCoCdTCPP；
Figure 11 is MWCNTs/GCE, coordination polymer/MWCNTs/GCE whether there is or not the 0.1mol/L's of hydrogen peroxide pH=7
CV curve in electrolyte solution compares, and wherein a is Cu1Cd3TCPP, and b Cu1Cd1TCPP, c Cu3Cd1TCPP, d are
Co1Cd3TCPP, e Co1Cd1TCPP, f Co3Cd1TCPP, g CuCoCdTCPP；
Figure 12 is the selection that present example 4CuCdTCPP series detects best current potential to sodium nitrite, and not on year-on-year basis
The comparison of example detection sensitivity；
Figure 13 is the selection that present example 5CuCdTCPP series detects best current potential to hydrogen peroxide, and not on year-on-year basis
The comparison of example detection sensitivity；
Figure 14 is the selection that present example 6CoCdTCPP series detects best current potential to sodium nitrite, and not on year-on-year basis
The comparison of example detection sensitivity；
Figure 15 is the selection that present example 7CoCdTCPP series detects best current potential to hydrogen peroxide, and not on year-on-year basis
The comparison of example detection sensitivity；
Figure 16 is the best current potential selection that present example 8Cu1Co1Cd1TCPP detects sodium nitrite, and best
To the detection of sodium nitrite under current potential；
Figure 17 is the best current potential selection that present example 9Cu1Co1Cd1TCPP detects hydrogen peroxide, and best
To the detection of sodium nitrite under current potential；
Figure 18 is that 10 bimetallic different proportion coordination polymer of the embodiment of the present invention rolls over the sensitivity that sodium nitrite detects
Line chart；
Figure 19 is that 10 bimetallic different proportion coordination polymer of the embodiment of the present invention rolls over the sensitivity that hydrogen peroxide detects
Line chart.
Specific embodiment
Below in conjunction with drawings and examples, the invention will be further described.
Based on the electrochemical sensor and its preparation method and application of CoCuCdTCPP coordination polymer modification, including it is following
Step:
Step 1: synthesis metal TCPP coordination polymer, including Cu1Cd3TCPP, Cu2Cd2TCPP, Cu3Cd1TCPP,
Co1Cd3TCPP1, Co2Cd2TCPP, Co3Cd1TCPP, CuCoCdTCPP；
Step 2: by the coordination polymer modified electrode of synthesis: synthesis metal TCPP coordination polymer is dissolved in secondary steaming
In distilled water, ultrasonic disperse, obtained suspension；Suspended drop-coated is polishing to mirror surface to by polishing cloth, in secondary distilled water
It is cleaned by ultrasonic in ethyl alcohol, glassy carbon electrode surface of drying that treated is placed to dry, then naphthalene is added dropwise in polymer surfaces at room temperature
Phenol solution is fixed, and air dries spare, obtained polymer/glass-carbon electrode at room temperature；If glassy carbon electrode surface after treatment is first
The MWCNTs multi-wall carbon nano-tube of drop coating carboxylated, then naphthol solution is added dropwise in polymer surfaces and fixes, air dries at room temperature
It is spare, polymer/MWCNTs/ glass-carbon electrode is made.
Step 3: the electrode of modification is placed in three-electrode system, electricity is detected by cyclic voltammetric in the range of -1-1V
Chemical property and to be added measured object catalytic action；
Step 4: being responded according to C-V, surveys I-T and find best current potential；
5th: measured object being detected under best current potential, compares sensitivity.
Embodiment 1
Ligand H2TCPP synthesis:
160mL propionic acid is heated to boiling, then successively rapidly joins pyrroles (1.38mL, 20mmol) into solvent and to first
Acyl group methyl benzoate (3.28g, 20mmol), reaction reflux 2h.It is down to room temperature later, stands cool overnight.It will be mixed after reaction
It closes object to filter, and is washed with dehydrated alcohol colourless to filtrate, it is H that drying, which obtains darkviolet solid,2TCPP-OMe crude product.It uses again
Method (the CHCl of recrystallization3: methanol=1:3) obtain pure H2TCPP-OMe。
Will and H2TCPP-OMe or (904mg, 0.1mmol), which are dissolved in 30mL tetrahydro, barks and mutters in solution, then into reaction system
It is added 30mL NaOH aqueous solution (0.1M), 50 DEG C are reacted 48 hours.It cools down later, revolving removes tetrahydrofuran, and at room temperature
Adjusting solution ph with 0.1M HCl (aq) is 2 or so.Buchner funnel filters to obtain aubergine solid, dry product H2TCPP。
Synthesize a series of CoCuCdTCPP coordination polymers:
1. the synthesis of Cu1Cd3TCPP
Weigh 80mg H2TCPP,54mg CdCl2And 13.4mgCuCl2It is dissolved in DEF (6mL), H2O (0.3mL), will mix
Liquid is added in the reaction kettle of 25mL, is then placed in baking oven, 150 degrees Celsius of reaction 2d, obtains aubergine powder, filter and with DMF,
H2O, EtOH is washed to filtrate in colourless, is dried in 50 degrees Celsius of baking oven.Change in synthetic method, with reaction kettle generation
For sealed glass tube, more convenient operation.
2. the synthesis of Cu1Cd1TCPP
Weigh 80mg H2TCPP,36mg CdCl2And 26.8mgCuCl2It is dissolved in DEF (6mL), H2O (0.3mL), will mix
Liquid is added in the reaction kettle of 25mL, is then placed in baking oven, 150 degrees Celsius of reaction 2d, obtains aubergine powder, filter and with DMF,
H2O, EtOH is washed to filtrate in colourless, is dried in 50 degrees Celsius of baking oven.
3. the synthesis of Cu3Cd1TCPP
Weigh 80mg H2TCPP,18mg CdCl2And 40.2mgCuCl2It is dissolved in DEF (6mL), H2O (0.3mL), will mix
Liquid is added in the reaction kettle of 25mL, is then placed in baking oven, 150 degrees Celsius of reaction 2d, obtains aubergine powder, filter and with DMF,
H2O, EtOH is washed to filtrate in colourless, is dried in 50 degrees Celsius of baking oven.
4. the synthesis of Co1Cd3TCPP
Weigh 80mg H2TCPP,54mg CdCl2And 13mgCoCl2It is dissolved in DEF (6mL), H2O (0.3mL), by mixed liquor
It is added in the reaction kettle of 25mL, is then placed in baking oven, 150 degrees Celsius of reaction 2d obtain aubergine powder, filter and with DMF, H2O、
EtOH is washed to filtrate in colourless, is dried in 50 degrees Celsius of baking oven.
5. the synthesis of Co1Cd1TCPP
Weigh 80mg H2TCPP,36mg CdCl2And 26mgCoCl2It is dissolved in DEF (6mL), H2O (0.3mL), by mixed liquor
It is added in the reaction kettle of 25mL, is then placed in baking oven, 150 degrees Celsius of reaction 2d obtain aubergine powder, filter and with DMF, H2O、
EtOH is washed to filtrate in colourless, is dried in 50 degrees Celsius of baking oven.
6. the synthesis of Co3Cd1TCPP
Weigh 80mg H2TCPP,18mgCdCl2And 39mgCoCl2It is dissolved in DEF (6mL), H2O (0.3mL), by mixed liquor plus
Into the reaction kettle of 25mL, it is then placed in baking oven, 150 degrees Celsius of reaction 2d obtain aubergine powder, filter and with DMF, H2O、
EtOH is washed to filtrate in colourless, is dried in 50 degrees Celsius of baking oven.
7. the synthesis of Cu1Co1Cd1TCPP series
Weigh 80mg H2TCPP,24mgCdCl2、18mgCuCl2And 17mgCoCl2It is dissolved in DEF (6mL), H2O (0.3mL),
Mixed liquor is added in the reaction kettle of 25mL, baking oven is then placed in, 150 degrees Celsius of reaction 2d obtain aubergine powder, and filtering is used in combination
DMF, H2O, EtOH are washed to filtrate in colourless, are dried in 50 degrees Celsius of baking oven.
Above-mentioned 7 kinds of CoCuCdTCPP coordination polymer electron microscopes are as shown in Figure 1, XRD diagram is as shown in Figure 2, wherein synthesis
Cu1Cd3TCPP, Co1Cd3TCPP are as shown in Figure 3 compared with the base peak of 1-Cu, 1-Co for synthesizing in document 1.
Embodiment 2
The GCE and MWCNTs/GCE of coordination polymer modification
Glass-carbon electrode (GCE, diameter 3mm) is polished through nylon polishing cloth, then with 0.3 μm, 0.05 μm of Al2O3It is polished to
Then mirror surface is cleaned by ultrasonic 1min in secondary distilled water and ethyl alcohol, dries after taking-up spare.It prepared by the embodiment 3 of 5mg
Polymer is dissolved in 1mL secondary distilled water, ultrasonic disperse, obtains the suspension of 5mg/mL.With liquid-transfering gun by the suspended drop of 6 μ L
The glassy carbon electrode surface that is coated onto that treated, is placed to dry, then 2 μ L mass fraction, 1% naphthols is added dropwise in polymer surfaces at room temperature
(nafion) fixed, air dries spare, obtained polymer/GCE at room temperature.
The MWCNTs of 6 μ L 5mg/mL carboxylated of glassy carbon electrode surface drop coating after treatment, after room temperature is dried, then
With 6 μ L 5mg/mL coordination polymer suspension of liquid-transfering gun drop coating, last 2 μ L mass fraction 1%nafion of drop coating is fixed, in room
Spare, obtained polymer/MWCNTs/GCE is dried under temperature.
Embodiment 3
A series of electrochemical properties of coordination polymers are had studied using cyclic voltammetry (CV), are compared pH=7's
0.1molL-1Bare electrode and coordination polymer/GCE CV curve in PBS electrolyte solution.Within the scope of -1.0 to 1.0V, naked electricity
Do not occur redox peaks extremely, and coordination polymer/GCE electric current in this potential range increases, and the oxidation of metal occurs also
Parent peak.
Peak of the CuCdTCPP series (Fig. 4) at E=-0.79 is labeled as peak 1, is attributed to Cd (II)/Cd oxidation peak；?
0.95 peak occurred is labeled as peak 2, is attributed to Cu (II)/Cu (I)；Peak 3 is labeled as in the redox peaks that -0.1V or so occurs
With 3 ', it is attributed to the redox peaks of porphyrin complexing Cu (II)/Cu (I)；It is labeled as peak 4 in the reduction peak that -0.9V occurs below,
It is attributed to Cd (II)/Cd reduction peak.
It is labeled as peak 1 at peak of the CoCdTCPP serial (Fig. 5) at E=-0.79, is attributed to Cd (II)/Cd oxidation peak；
It is labeled as peak 2 at the peak that 0.8 occurs, is attributed to Co (III)/Co (II), peak 3 is labeled as in the reduction peak that -0.25V occurs, belongs to
Co (III)/Co (II) is complexed for porphyrin, the peak occurred after -0.8V is labeled as peak 4, is attributed to Cd (II)/Cd reduction peak.
In three Ni metal CoCdTCPP systems (Fig. 6), the peak at E=-0.79 is labeled as peak 1, is attributed to Cd (II)/Cd
Oxidation peak；It is labeled as peak 2 at the peak that 0.8 occurs, is attributed to Co (III)/Co (II)；Since the current potential of copper is relatively high, in cobalt
Fail to observe under interference and, is labeled as peak 3 in the reduction peak that -0.25V occurs, is attributed to porphyrin complexing Co (III)/Co (II)；
The peak of copper is disturbed, does not mark.The peak occurred after -0.8V is labeled as peak 4, is attributed to Cd (II)/Cd reduction peak.
From figure 7 it can be seen that CV curve of the bare electrode in the PBS solution of no sodium nitrite be without peak, when be added 2.5 ×
10-4mol/LNaNO2Afterwards, bare electrode electric current has increase slightly at -1.For the electrode for having modified coordination polymer,
When addition 2.5 × 10-4mol/LNaNO2Afterwards, there is apparent increase at the peak Cu (II)/Cu (I), Co (III)/Co (II), this shows
The active sites of copper, cobalt are to sodium nitrite with catalytic action in coordination polymer.
From figure 8, it is seen that CV curve of the bare electrode in the PBS solution of no hydrogen peroxide be without peak, when being added 5 × 10- 4mol/LH2O2Afterwards, the CV curve of bare electrode is without significant change.The electrode for having modified coordination polymer, when addition 5 × 10-4mol/
LH2O2, Cd (II)/Cd reduction peak, porphyrin complexing Co (III)/Co (II) reduction peak significantly increase, illustrate that cadmium, cobalt activity are
There is catalytic action to hydrogen peroxide.
Under normal conditions, the performance of sensor can be improved by the way that multi-walled carbon nanotube is added, because carbon nanotube can be with
Improve the electric conductivity and sensitivity of modified electrode, the property of different ratio mwcnts/GCE modified electrode.As shown in figure 9, passing through
The PBS for comparing different ratio coordination polymer/MWCNTs/GCE and coordination polymer/GCE in PH=7.0 supports electrolytic solution
CV curve can be seen that coordination polymerization/MWCNTs/GCE current value and be significantly greater than coordination polymer/GCE current value, explanation
MWCNTs can reduce the impedance of electrode and improve the electric conductivity of electrode with the sensitivity of sensor.As shown in Figure 10 and Figure 11,
Coordination polymer/MWCNTs/GCE modification electrode is had studied respectively and without coordination polymer modification containing only multi-wall carbon nano-tube
Difference of the pipe MWCNTs/GCE to the response of sodium nitrite and hydrogen peroxide, after 0.5mmol/L sodium nitrite (Figure 10) is added,
In -1V-1V, the bright electric current of coordination polymer/MWCNTs/GCE CV chart is significantly increased, illustrate coordination polymer/
MWCNTs/GCE has electrocatalysis, and response pctential and coordination polymer/GCE that multi-walled carbon nanotube is not added to sodium nitrite
It is identical to the current potential of sodium nitrite response, but CV curve of the MWCNTs/GCE in the PBS whether there is or not sodium nitrite be without significant change,
Know MWCNTs/GCE sodium nitrite without apparent catalytic action.Similarly, after 0.5mmol/L hydrogen peroxide (Figure 11) is added,
In -1V-1V, the bright electric current of coordination polymer/MWCNTs/GCE CV chart is significantly increased, and response pctential and multi wall is not added
The current potential that coordination polymer/GCE of carbon nanotube responds hydrogen peroxide is essentially identical, illustrates coordination polymer/MWCNTs/
GCE has electrocatalysis to hydrogen peroxide, but CV curve of the MWCNTs/GCE in the PBS whether there is or not hydrogen peroxide becomes without obvious
Change, it is known that MWCNTs/GCE is to hydrogen peroxide without apparent catalytic action.The above result shows that multi-walled carbon nanotube only improves
The electric conductivity of electrode, promotes the electron transmission of electrode surface, and what it is to hydrogen peroxide and sodium nitrite its catalytic action is this
The synthesized coordination polymer of invention.
Embodiment 4
As shown in figure 12, in order to obtain best effort current potential, 0.65V, 0.7V, 0.75V under different potentials are studied respectively,
Cu1Cd3TCPP/MWCNTs/GCE, Cu1Cd1TCPP/MWCNTs/GCE, Cu3Cd1TCPP/ under 0.8V, 0.85V current potential
Comparison of the MWCNTs/GCE to the electrocatalytic oxidation sensitivity of sodium nitrite.Figure 12 a, b, c five steps respectively represent difference
Coordination polymer/MWCNTs/GCE of ratio contains 0.1mmol/L, 0.3mmol/L, 0.6mmol/L under different voltages respectively,
The time current curve of the sodium nitrite of 1mmol/L, 1.5mmol/L.D is coordination polymer/MWCNTs/GCE of different proportion
It to the time current curve of sodium nitrite detection under best current potential, observes for convenience, the different systems on same time point
In the sodium nitrite concentration that contains it is identical, since 200s, at interval of 50s, 2 μ L, 2 μ L, 2 μ L, 4 μ are successively added into system
L, the sodium nitrite of 4 μ L, 4 μ L, 6 μ L, 6 μ L, 6 μ L, 8 μ L, 8 μ L, 8 μ L, 10 μ L, 10 μ L, 10 μ L 0.2mol/L.Pass through figure
12.a can be seen that Cu1Cd3TCPP/MWCNTs/GCE is 0.7V to the best current potential that sodium nitrite detects；Figure 12 .b can be seen
The best current potential that Cu1Cd1TCPP/MWCNTs/GCE detects sodium nitrite out is 0.7V；Figure 12 .c can see Cu3Cd1TCPP/
The best current potential that MWCNTs/GCE detects sodium nitrite is 0.7V；Figure 12 .d different proportion CuCdTCPP/MWCNTs/ at 0.7V
GCE detects the performance of sodium nitrite, makes standard curve by Figure 12 d, show that Cu1Cd3TCPP sensitivity is 226.47mA
M·cm-2, linearly dependent coefficient 0.99988.Cu1Cd1TCPP sensitivity is 418mAMcm-2, linearly dependent coefficient is
0.99648, Cu3Cd1TCPP sensitivity is 118.68mAMcm-2, linearly dependent coefficient 0.9998.
Embodiment 5
As shown in figure 13, in order to obtain best effort current potential, different potentials -0.5V, -0.6V, -0.7V are studied respectively, -
Cu1Cd3TCPP/MWCNTs/GCE, Cu1Cd1TCPP/MWCNTs/GCE, Cu3Cd1TCPP/MWCNTs/GCE under 0.8V, -0.9V
Comparison to the electrocatalytic oxidation sensitivity of hydrogen peroxide.Figure 13 a, b, c five steps respectively represent the coordination of different proportion
Polymer/MWCNTs/GCE contains 0.1mmol/L, 0.3mmol/L, 0.6mmol/L, 1mmol/L under different voltages respectively,
The time current curve of the hydrogen peroxide of 1.5mmol/L.D figure is coordination polymer/MWCNTs/GCE of different proportion best
It to the time current curve of hydrogen peroxide detection under current potential, observes, contains in different systems on same time point for convenience
Concentration of hydrogen peroxide it is identical, since 200s, at interval of 50s, 2 μ L, 2 μ L, 2 μ L, 4 μ L, 4 μ L, 4 are successively added into system
The hydrogen peroxide of μ L, 6 μ L, 6 μ L, 6 μ L, 8 μ L, 8 μ L, 8 μ L, 10 μ L, 10 μ L, 10 μ L 0.2mol/L.It can be seen by Figure 13 .a
Cu1Cd3TCPP/MWCNTs/GCE is -0.9V to the best current potential that hydrogen peroxide detects out；Figure 13 .b can be seen that
The best current potential that Cu1Cd1TCPP/MWCNTs/GCE detects hydrogen peroxide is -0.9V；Figure 13 .c can see Cu3Cd1TCPP/
The best current potential that MWCNTs/GCE detects hydrogen peroxide is -0.9V；Figure 13 .d is in -0.9 lower different proportion CuCdTCPP/
MWCNTs/GCE detects the performance of hydrogen peroxide, makes standard curve by Figure 13 d, show that Cu1Cd3TCPP sensitivity is
276mA·M·cm-2, linearly dependent coefficient 0.99987；Cu1Cd1TCPP sensitivity is 413.83mAMcm-2, linearly
Related coefficient is 0.99733；Cu3Cd1TCPP sensitivity is 391.3mAMcm-2, linearly dependent coefficient 0.99818.
Embodiment 6
As shown in figure 14, in order to obtain best effort current potential, 0.7V, 0.75V, 0.8V, 0.85V under different potentials are studied,
Co1Cd3TCPP/MWCNTs/GCE, Co1Cd1TCPP/MWCNTs/GCE, Co3Cd1TCPP/MWCNTs/GCE couple under 0.9V current potential
The comparison figure of the electrocatalytic oxidation sensitivity of sodium nitrite, five steps of 14a, b, c respectively represent the polycomplexation of different proportion
It closes object/MWCNTs/GCE and contains 0.1mmol/L, 0.3mmol/L, 0.6mmol/L, 1mmol/L respectively under different voltages,
The time current curve of the sodium nitrite of 1.5mmol/L.D figure is coordination polymer/MWCNTs/GCE of different proportion best
It to the time current curve of sodium nitrite detection under current potential, observes, contains in different systems on same time point for convenience
Sodium nitrite concentration it is identical, since 200s, at interval of 50s, 2 μ L, 2 μ L, 2 μ L, 4 μ L, 4 μ L, 4 are successively added into system
The sodium nitrite of μ L, 6 μ L, 6 μ L, 6 μ L, 8 μ L, 8 μ L, 8 μ L, 10 μ L, 10 μ L, 10 μ L0.2mol/L.It can be seen by Figure 14 .a
Co1Cd3TCPP/MWCNTs/GCE is 0.9V to the best current potential that sodium nitrite detects out；Figure 14 .b can be seen that
The best current potential that Co1Cd1TCPP/MWCNTs/GCE detects sodium nitrite is 0.8V；Figure 14 .c can see Co3Cd1TCPP/
The best current potential that MWCNTs/GCE detects sodium nitrite is 0.85V, Figure 14 .d different proportion CoCdTCPP/ under best current potential
MWCNTs/GCE detects the performance of sodium nitrite, makes standard curve by Figure 14 d, show that Co1Cd3TCPP sensitivity is
230.66mA·M·cm-2, linearly dependent coefficient 0.99925.Co1Cd1TCPP sensitivity is 350.95mAMcm-2, line
It is 282.9mAMcm that property related coefficient, which is 0.9997, Co3Cd1TCPP sensitivity,-2, linearly dependent coefficient 0.99979.
Embodiment 7
As shown in figure 15, in order to obtain best effort current potential, -0.1V, -0.2V, -0.3V under different potentials are studied respectively, -
0.4V, -0.5V, Co1Cd3TCPP/MWCNTs/GCE, Co1Cd1TCPP/MWCNTs/GCE, Co3Cd1TCPP/ under -0.6V current potential
Comparison of the MWCNTs/GCE to the electrocatalytic oxidation sensitivity of hydrogen peroxide.Five steps of 15a, b, c respectively represent not on year-on-year basis
Coordination polymer/MWCNTs/GCE of example contains 0.1mmol/L, 0.3mmol/L, 0.6mmol/L under different voltages respectively,
The time current curve of the hydrogen peroxide of 1mmol/L, 1.5mmol/L.D figure is coordination polymer/MWCNTs/ of different proportion
GCE, to the time current curve of hydrogen peroxide detection, is observed for convenience under best current potential, not androgynous on same time point
The concentration of hydrogen peroxide contained in system is identical, and since 200s, at interval of 50s, 2 μ L, 2 μ L, 2 μ L, 4 are successively added into system
The hydrogen peroxide of μ L, 4 μ L, 4 μ L, 6 μ L, 6 μ L, 6 μ L, 8 μ L, 8 μ L, 8 μ L, 10 μ L, 10 μ L, 10 μ L 0.2mol/L.Pass through figure
15.a can be seen that the best electricity -0.4V that Co1Cd3TCPP/MWCNTs/GCE detects hydrogen peroxide；Figure 15 .b can be seen that
Co1Cd1TCPP/MWCNTs/GCE is that -0.5V, Figure 15 c can see Co3Cd1TCPP/ to the best current potential that hydrogen peroxide detects
The best current potential that MWCNTs/GCE detects hydrogen peroxide is -0.2V.Figure 15 .d different proportion CoCdTCPP/ under best current potential
MWCNTs/GCE detects the performance of hydrogen peroxide, makes standard curve by Figure 15 d, show that Co1Cd3TCPP sensitivity is
188.84mA·M·cm-2, linearly dependent coefficient 0.999979.Co1Cd1TCPP sensitivity is 228.23mAMcm-2,
Linearly dependent coefficient is that 0.99994, Co3Cd1TCPP sensitivity is 211mAMcm-2, linearly dependent coefficient 0.99392.
Embodiment 8
Shown in Figure 16, in order to obtain best effort current potential, different potentials 0.65V, 0.7V, 0.75V, 0.8V are studied respectively,
Comparison of the CuCoCdTCPP/MWCNTs/GCE to the electrocatalytic oxidation sensitivity of sodium nitrite under 0.85V, 0.9V current potential.Scheme a's
Five steps represent CuCoCdTCPP/MWCNTs/GCE and contain 0.1mmol/L, 0.3mmol/L respectively under different voltages,
The time current curve of the sodium nitrite of 0.6mmol/L, 1mmol/L, 1.5mmol/L.B figure is CuCoCdTCPP/MWCNTs/
The time current curve that GCE detects sodium nitrite under best current potential, since 200s, at interval of 50s, successively into system
2 μ L, 2 μ L, 2 μ L, 4 μ L, 4 μ L, 4 μ L, 6 μ L, 6 μ L, 6 μ L, 8 μ L, 8 μ L, 8 μ L, 10 μ L, 10 μ L, 10 μ L 0.2mol/L are added
Sodium nitrite.Figure 16 .a shows that CuCoCdTCPP/MWCNTs/GCE is 0.8V to the best current potential of the detection of sodium nitrite, passes through
Figure 16 .b makes standard curve, and Co1Cu1Cd1TCPP sensitivity is 266.25mAMcm under best current potential-2, linearly related
Coefficient is 0.99982.
Embodiment 9
As shown in figure 17, in order to obtain best effort current potential, respectively study different potentials under -0.2V, -0.3V, -0.4, -
0.5V, -0.6V, -0.7V, -0.8V, electrocatalytic oxidation of the CuCoCdTCPP/MWCNTs/GCE to hydrogen peroxide under -0.9V current potential
The comparison of sensitivity.Five steps of Figure 17 a represent CuCoCdTCPP/MWCNTs/GCE and contain respectively under different voltages
The time current curve of the hydrogen peroxide of 0.1mmol/L, 0.3mmol/L, 0.6mmol/L, 1mmol/L, 1.5mmol/L.B figure is
CuCoCdTCPP/MWCNTs/GCE is under best current potential to the time current curve of hydrogen peroxide detection, since 200s, every
Every 50s, 2 μ L, 2 μ L, 2 μ L, 4 μ L, 4 μ L, 4 μ L, 6 μ L, 6 μ L, 6 μ L, 8 μ L, 8 μ L, 8 μ L, 10 μ L, 10 are successively added into system
The hydrogen peroxide of μ L, 10 μ L 0.2mol/L.17a shows that CuCoCdTCPP/MWCNTs/GCE is most preferably electric to the detection of hydrogen peroxide
Position is -0.9V, makes standard curve by Figure 17 .b, and CoCuCdTCPP sensitivity is 369.04mAM under best current potential
cm-2, linearly dependent coefficient 0.99977.
Embodiment 10
Table 3 summarizes table for embodiment 4-9 the data obtained, according to bimetallic sensitivity data, draws Figure 18 and 19,
Figure 18, the amount score of metallics when X-axis feeds intake for Cu/Co, Y-axis are under best current potential to the sensitive of sodium nitrite detection
Degree, Figure 19, the amount score of metallics when X-axis feeds intake for Cu/Co, Y-axis are the spirits under best current potential to hydrogen peroxide detection
Sensitivity.
The series coordination polymer after improving electric conductivity and sensitivity, can detecte having modified multi-walled carbon nanotube
Hydrogen peroxide and sodium nitrite, therefore the series coordination polymer is the sensor of bi-functional.Seven kinds of coordination polymers are to mistake
The detection of hydrogen oxide and sodium nitrite has higher sensitivity, for detection sensitivity and the evaluation data of minimum detection limit,
Detection performance most preferably Cu1Cd1TCPP/MWCNTs/GCE, it is poly- to 7 kinds of sensitivity of the detection of sodium nitrite and hydrogen peroxide
It is highest in conjunction object, respectively reach 418mAMcm-2And 413.83mAMcm-2, while in the inspection to sodium nitrite
The minimum detection limit of Cu1Cd1TCPP/MWCNTs/GCE is also minimum in survey, is 3.2 × 10-6.It can thus be seen that right
The performance of the context of detection of hydrogen peroxide and sodium nitrite, Cu1Cd1TCPP is best.
3 different proportion sensitivity of table and linearly dependent coefficient table
Claims (6)
1. a kind of electrochemical sensor based on the modification of CoCuCdTCPP coordination polymer, which is characterized in that by CoCuCdTCPP
The suspended drop-coated of coordination polymer is made in electrode surface；The CoCuCdTCPP coordination polymer includes bimetallic CuCdTCPP
With any one in CoCdTCPP coordination polymer and three metal system CuCoCdTCPP coordination polymers；Bimetallic
The molar ratio that Cu, Cd, TCPP feed intake in CuCdTCPP coordination polymer is 1:1:1；In bimetallic CoCdTCPP coordination polymer
The molar ratio of Co, Cd, TCPP are 1:1:1；Co, Cu, Cd, TCPP feed intake in three metal CoCuCdTCPP coordination polymers
Molar ratio is 4/3:4/3:4/3:1.
2. the electrochemical sensor according to claim 1 based on the modification of CoCuCdTCPP coordination polymer, the electrode
Glass-carbon electrode MWCNTs/the GCE modified for glass-carbon electrode GCE or multi-walled carbon nanotube.
3. a kind of preparation side of the electrochemical sensor as described in claim 1 based on the modification of CoCuCdTCPP coordination polymer
Method, which comprises the steps of:
(1) glass-carbon electrode polishing cloth is polishing to mirror surface, and ultrasonic cleaning is dried spare after taking-up；
(2) CoCuCdTCPP coordination polymer is dissolved in secondary distilled water, ultrasonic disperse, obtained suspension；
(3) it by suspended drop-coated to step (1) treated glassy carbon electrode surface, is placed to dry at room temperature, then in polymer table
Face is added dropwise naphthol solution and fixes, and air dries spare, obtained polymer/glass-carbon electrode at room temperature；
(4) multi-walled carbon nanotube of step (1) treated glassy carbon electrode surface drop coating carboxylated repeats the process of step (3),
Polymer/MWCNTs/GCE is made.
4. preparation method according to claim 3, which is characterized in that glass-carbon electrode described in step (1) is in second distillation
It is cleaned by ultrasonic in water and ethyl alcohol.
5. a kind of electrochemical sensor as described in claim 1 based on the modification of CoCuCdTCPP coordination polymer was detecting
Application in hydrogen oxide and sodium nitrite.
6. used in a kind of electrochemical sensor as described in claim 1 based on the modification of CoCuCdTCPP coordination polymer
Three metal system CuCoCdTCPP coordination polymers.
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