CN107698624B - A kind of application of multi-functional nickel complex based on organic ligand and its method for synthesizing carbon paste electrode and carbon paste electrode - Google Patents
A kind of application of multi-functional nickel complex based on organic ligand and its method for synthesizing carbon paste electrode and carbon paste electrode Download PDFInfo
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Abstract
The application of a kind of multi-functional nickel complex based on organic ligand and its method for synthesizing carbon paste electrode and carbon paste electrode, the molecular formula of the complex are as follows: [Ni (L) (H2O)4]·(2,5-TPD)；[Ni2(L)2(1,3‑BDC)2(H2O)4]·5H2O；It by complex graphite powder, is ground, is subsequently dispersed in atoleine using agate mortar, it is ground, is encapsulated into quartz glass tube with agate mortar, carbon paste one end is wiped flat with template, the other end is connected with the copper rod for being connected with 6~11 strands of copper wires, obtains complex carbon paste electrode.Synthetic method is simple, can effectively monitor three kinds of hydrogen peroxide, nitrite anions and chloramphenicol pollutants.Meanwhile carbon paste working electrode can simply and rapidly be updated, and with good stability, the research and development of the working electrode have great importance to the detection of pollutant.
Description
Technical field
The invention belongs to Electroanalytical Chemistry materials synthesis field, in particular to a kind of multi-functional nickel based on organic ligand is matched
Close the application of object and its method and carbon paste electrode for synthesizing carbon paste electrode.
Background technique
Hydrogen peroxide (H2O2), aqueous solution is commonly called as hydrogen peroxide, is a kind of strong oxidizer.Hydrogen peroxide has strong corrosion
Property, sucking the product steam or mist has intense irritation to respiratory tract.Although the hydrogen peroxide toxicity of low concentration is smaller, by
It can release oxygen in its own decomposition, therefore be listed in and easily make quick-fried dangerous material.Hydrogen peroxide can be dissolved each other with water with any ratio, be fitted
It for wound disinfection and environment, food sterilization etc., can exist in the environment within a certain period of time, to bands such as safety in production, lives
Carry out huge hidden danger.Therefore, new easy detection means is developed with important practical significance.
Nitrite anions (NO2 –) be the toxic atomic group of a kind of pair of human body, the salt being made of nitrite anions and metallic element
Do nitrite.Nitrite is extremely toxic substance, and 0.2~0.5 gram of adult's intake can cause to be poisoned, and 3 grams can be lethal.Nitrous
Hydrochlorate while still a kind of carcinogen, it was found that the being positively correlated property of nitrite amount of cancer of the esophagus and patient's intake.It is main
Nitrite is sodium nitrite and potassium nitrite, and a certain number of substances are had in stale fruit or vegetables, are given
Human lives bring security risk.Therefore, new easy detection means is developed with important practical significance.
Chloramphenicol (Cp) is a kind of antibiotic, has the function of inhibiting bacteria and diminishing inflammation.However, a large amount of due to antibiotics
It using, part antibiotic is lost in environment, and in long-term environment is evolved, part bacterium evolves corresponding immunologic mechanism,
Lead to the failure of antibiotic.Currently, our antibiotics environmental pollutions are quite serious.Therefore, new easy detection is developed
Means have important practical significance.
Although above-mentioned three kinds of pollutants have corresponding detection means, if developing a kind of material can effectively supervise
Above-mentioned three kinds of pollutants are surveyed, the feasibility and operability of analysis detection will be greatly improved.It has a very important significance.
Summary of the invention
It the technical problem to be solved in the present invention is to provide a kind of multi-functional nickel complex based on organic ligand and its is used for
Synthesize carbon paste electrode method and carbon paste electrode application, synthetic method is simple, can effectively monitor hydrogen peroxide, nitrite anions with
And three kinds of pollutants of chloramphenicol.Meanwhile carbon paste working electrode can simply and rapidly be updated, and have good stabilization
Property.The research and development of the working electrode have great importance to the detection of pollutant.
The technical solution of the invention is as follows:
One kind being based on the multi-functional nickel complex of organic ligand, and the molecular formula of the complex is as follows:
[Ni(L)(H2O)4]·(2,5-TPD)(1)；
[Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O(2)；
Wherein, bis- (4- methylene pyridine) benzene-Isosorbide-5-Nitrae-diformamides of L N, N'-, 2,5-TPD 2,5- thiophenedicarboxylic acid
Root, 1,3-BDC 1,3- phthalic acid root；
The specific synthesis step of nickel complex is as follows:
By NiCl2·6H2O, bis- (4- methylene pyridine) benzene-Isosorbide-5-Nitrae-diformamides and 2 of N, N'-, 5- thiophenedicarboxylic acid add
Enter deionized water；20min~60min is stirred at room temperature and forms suspended mixture, the N, N'- bis- (4- methylene pyridines)
Benzene-Isosorbide-5-Nitrae-diformamide and 2, the molar ratio of 5- thiophenedicarboxylic acid are 1:1~1:2, the N, N'- bis- (4- methylene pyridines)
Benzene -1,4- diformamide and NiCl2·6H2The molar ratio of O be 1:1~1:3, bis- (4- methylene pyridine) benzene -1 of the N, N'-,
The molar ratio of 4- diformamide and deionized water is 1:2800~1:8300, and the NaOH solution tune pH for being 1.0mol/L with concentration is
4.2~6.8, it pours into autoclave and is warming up to 110 DEG C~130 DEG C with 5 DEG C/h heating rate, keep the temperature 48h under hydrothermal condition
~120h cools to room temperature with the rate of temperature fall of 5 DEG C/h and obtains pink colour bulk crystals, with deionized water and ethyl alcohol alternately cleaning 3
Secondary~5 times, naturally dry, obtains product [Ni (L) (H at room temperature2O)4]·(2,5-TPD)(1)。
By NiCl2·6H2O, bis- (4- methylene pyridine) benzene-Isosorbide-5-Nitrae-diformamides and 1 of N, N'-, 3- phthalic acid are added
Deionized water；20min~60min is stirred at room temperature and forms suspended mixture, bis- (4- methylene pyridine) benzene-of the N, N'-
Isosorbide-5-Nitrae-diformamide and 1, the molar ratio of 3- phthalic acid are 1:1~1:2, bis- (4- methylene pyridine) benzene-Isosorbide-5-Nitrae-of the N, N'-
Diformamide and NiCl2·6H2The molar ratio of O is 1:1~1:3, bis--two formyls of (4- methylene pyridine) benzene-Isosorbide-5-Nitrae of the N, N'-
The molar ratio of amine and deionized water is 1:2800~1:8300, the NaOH solution tune pH for being 1.0mol/L with concentration is 4.1~
7.0, pour into autoclave and be warming up to 110 DEG C~130 DEG C with 5 DEG C/h heating rate, under hydrothermal condition keep the temperature 48h~
120h cools to room temperature with the rate of temperature fall of 5 DEG C/h and obtains pink colour bulk crystals, with deionized water and ethyl alcohol alternately cleaning 3 times
~5 times, naturally dry, obtains product [Ni at room temperature2(L)2(1,3-BDC)2(H2O)4]·5H2O(2)。
A method of for the multi-functional nickel complex based on organic ligand for synthesizing carbon paste electrode, expression formula is as follows:
1-CPE, 2-CPE
Wherein, 1 is complex [Ni (L) (H2O)4] (2,5-TPD), 2 be complex [Ni2(L)2(1,3-BDC)2
(H2O)4]·5H2O, CPE are carbon paste electrode；
The specific synthesis step of the multi-functional nickel complex material carbon paste working electrode is as follows:
By nickel complex [Ni (L) (H of above-mentioned synthesis2O)4] (2,5-TPD) or [Ni2(L)2(1,3-BDC)2
(H2O)4]·5H2O weighs 50 milligrams, 1~2 gram of graphite powder, grinds 2~4 hours using agate mortar, it is subsequently dispersed 1~
In 1.5 milliliters of atoleine, with agate mortar continuously grinding 1~2 hour.It is encapsulated into 0.5 centimetre of diameter, 1 millimeter of wall thickness, length
In the quartz glass tube of 5 centimetres of degree, carbon paste one end is wiped with template and is put down, and the other end is connected with the copper rod for being connected with 6~11 strands of copper wires.
It is a kind of based on organic ligand multi-functional nickel complex synthesis carbon paste electrode as hydrogen peroxide, nitrite anions with
And the application of the electroanalysis detection of chloramphenicol.
The beneficial effects of the present invention are:
(1) nickel complex [Ni (L) (H2O)4] (2,5-TPD) (1) have one-dimentional structure；[Ni2(L)2(1,3-BDC)2
(H2O)4]·5H2O (2) has two-dimensional slice structure；
(2) bis- (4- methylene pyridine) benzene-organic amine ligands of Isosorbide-5-Nitrae-diformamide of N, N'- have biggish size, when it
After metallic ion coordination, there is better Space Expanding space, this provides the useful space for the utilization of metal active centres；
Containing there are two methylene in ligand, the diversity of the coordination flexibility and spatial orientation of ligand is not only enriched, but also be hydrophobic
Property detected components it is effective combine provide convenience；The introducing of amide group in ligand can increase the hydrophily of complex, from
And the nickel complex of synthesis is made to wait water-soluble carcinogenic substance or antibiotic the affinity enhancing of detectable substance, improve inspection
The sensitivity of survey.The preparation of carbon paste electrode has convenient more new capability, improves the service efficiency of electrode.It can carry out to having
The multi-functional detection for causing the chloramphenicol of the hydrogen peroxide of quick-fried property, the nitrite anions of carcinogenicity and antibiotics, can be used as one
The environmental monitoring material that kind has good prospects.
Detailed description of the invention
Fig. 1 is the x-ray diffractogram of powder of complex 1 of the invention；
Fig. 2 is the x-ray diffractogram of powder of complex 2 of the invention；
Fig. 3 is the infrared spectrogram of complex 1 of the invention；
Fig. 4 is the infrared spectrogram of complex 2 of the invention；
Fig. 5 is the thermal stability figure of complex 1 and 2 of the invention；
Fig. 6 is the coordination context diagram of complex 1 of the invention；
Fig. 7 is the one-dimentional structure figure of complex 1 of the invention；
Fig. 8 is the coordination context diagram of complex 2 of the invention；
Fig. 9 is the two-dimensional structure figure of complex 2 of the invention；
Figure 10 is that the carbon paste electrode difference of complex 1 of the invention sweeps cyclic voltammogram under speed；
Figure 11 is electro-catalysis also original image of the carbon paste electrode to hydrogen peroxide of complex 1 of the invention；
Figure 12 is electro-catalysis also original image of the carbon paste electrode to nitrite anions of complex 1 of the invention；
Figure 13 is electro-catalysis also original image of the carbon paste electrode to chloramphenicol of complex 1 of the invention.
Figure 14 is that the carbon paste electrode difference of complex 2 of the invention sweeps cyclic voltammogram under speed；
Figure 15 is electro-catalysis also original image of the carbon paste electrode to hydrogen peroxide of complex 2 of the invention；
Figure 16 is electro-catalysis also original image of the carbon paste electrode to nitrite anions of complex 2 of the invention；
Figure 17 is electro-catalysis also original image of the carbon paste electrode to chloramphenicol of complex 2 of the invention；
Figure 18 is nickel complex carbon paste working electrode structure schematic diagram of the invention；
1- copper rod in figure, 2- copper wire, 3- quartz glass tube, 4- nickel complex carbon paste, 5- sulfuric acid paper layer.
Specific embodiment
Embodiment 1 synthesizes [Ni (L) (H2O)4] (2,5-TPD), wherein bis- (4- methylene pyridine) benzene -1 of L N, N'-,
4- diformamide, structural formula are as follows:2,5-TPD is 2,5- thiophenedicarboxylic acid root
By 0.1mmol NiCl2·6H2Bis- (4- methylene pyridine) benzene -1,4- diformamides of O, 0.10mmol N, N'-,
0.1mmol 2,5- thiophenedicarboxylic acid and 5mL H2O is added sequentially in 25mL beaker, and 20min is stirred at room temperature, and is hanged
Mixture is floated, after the pH to 4.2 that suspended mixture is reconciled with the NaOH solution of 1mol/L, is transferred to the autoclave of 25mL
In, 110 DEG C are warming up to the rate of heat addition of 5 DEG C/h, 48h is kept the temperature under hydrothermal condition, is cooled the temperature to the rate of temperature fall of 5 DEG C/h
Room temperature obtains pink colour bulk crystals, and with deionized water and ethyl alcohol alternately cleaning 3 times, naturally dry, obtains [Ni (L) at room temperature
(H2O)4] (2,5-TPD), yield 45%, XRD diffracting spectrum as shown in Figure 1, its coordination context diagram as shown in fig. 6, its
One-dimentional structure figure is as shown in Figure 7.
As shown in figure 18, by nickel complex [Ni (L) (H2O)4] (2,5-TPD) weigh 50 milligrams, 1 gram of high purity graphite powder,
2 hours are ground using agate mortar, are subsequently dispersed in 1 milliliter of atoleine, it is small with agate mortar continuously grinding 1
When.Be encapsulated into 0.5 centimetre of diameter, 1 millimeter of wall thickness, in the quartz glass tube that 5 centimetres of length, carbon paste one end wiped with template it is flat,
The other end is connected with the copper rod for being connected with 6-11 strands of copper wires, and the present embodiment obtains [Ni (L) (H by taking 6 strands of copper wires as an example2O)4]·(2,
5-TPD) carbon paste working electrode.
Embodiment 2 synthesizes [Ni (L) (H2O)4] (2,5-TPD), wherein bis- (4- methylene pyridine) benzene -1 of L N, N'-,
4- diformamide, 2,5-TPD 2,5- thiophenedicarboxylic acid root
By 0.2mmol NiCl2·6H2Bis- (4- methylene pyridine) benzene -1,4- diformamides of O, 0.10mmol N, N'-,
0.15mmol 2,5- thiophenedicarboxylic acid and 10mL H2O is added sequentially in 25mL beaker, and 40min is stirred at room temperature, and is obtained
Suspended mixture after the pH to 5.5 for reconciling suspended mixture with the NaOH solution of 1mol/L, is transferred to the autoclave of 25mL
In, 120 DEG C are warming up to the rate of heat addition of 5 DEG C/h, 96h is kept the temperature under hydrothermal condition, is cooled the temperature to the rate of temperature fall of 5 DEG C/h
Room temperature obtains pink colour bulk crystals, and with deionized water and ethyl alcohol alternately cleaning 4 times, naturally dry, obtains [Ni (L) at room temperature
(H2O)4] (2,5-TPD), yield 75%, XRD diffracting spectrum as shown in Figure 1, its coordination context diagram as shown in fig. 6, its
One-dimentional structure figure is as shown in Figure 7.
By nickel complex [Ni (L) (H2O)4] (2,5-TPD) weigh 50 milligrams, 1.5 grams of high purity graphite powder, using agate
It 3 hours of mortar grinder, is subsequently dispersed in 1.2 milliliters of atoleine, with 1.5 hours of agate mortar continuously grinding.Envelope
It is attached to 0.5 centimetre of diameter, 1 millimeter of wall thickness, in the quartz glass tube that 5 centimetres of length, carbon paste one end wipes flat, the other end with template
It is connected with the copper rod for being connected with 8 strands of copper wires, obtains [Ni (L) (H2O)4] (2,5-TPD) carbon paste working electrode.
Embodiment 3 synthesizes [Ni (L) (H2O)4] (2,5-TPD), wherein bis- (4- methylene pyridine) benzene -1 of L N, N'-,
4- diformamide, 2,5-TPD 2,5- thiophenedicarboxylic acid root
By 0.3mmol NiCl2·6H2Bis- (4- methylene pyridine) benzene -1,4- diformamides of O, 0.10mmol N, N'-,
0.2mmol 2,5- thiophenedicarboxylic acid and 15mL H2O is added sequentially in 25mL beaker, and 60min is stirred at room temperature, and is hanged
Mixture is floated, after the pH to 6.8 that suspended mixture is reconciled with the NaOH solution of 1mol/L, is transferred to the autoclave of 25mL
In, 130 DEG C are warming up to the rate of heat addition of 5 DEG C/h, 120h is kept the temperature under hydrothermal condition, is dropped temperature with the rate of temperature fall of 5 DEG C/h
To room temperature, pink colour bulk crystals are obtained, with deionized water and ethyl alcohol alternately cleaning 5 times, naturally dry, obtains [Ni (L) at room temperature
(H2O)4] (2,5-TPD), yield 55%, XRD diffracting spectrum as shown in Figure 1, its coordination context diagram as shown in fig. 6, its
One-dimentional structure figure is as shown in Figure 7.
By nickel complex [Ni (L) (H2O)4] (2,5-TPD) weigh 50 milligrams, it 2 grams of high purity graphite powder, is ground using agate
Alms bowl grinds 4 hours, is subsequently dispersed in 1.5 milliliters of atoleine, with 2 hours of agate mortar continuously grinding.It is encapsulated into
0.5 centimetre of diameter, 1 millimeter of wall thickness, in the quartz glass tube that 5 centimetres of length, carbon paste one end wipes flat, the other end and company with template
There is the copper rod of 11 strands of copper wires to be connected, obtains [Ni (L) (H2O)4] (2,5-TPD) carbon paste working electrode.
Embodiment 4 synthesizes [Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O, wherein bis- (the 4- methylene pyrroles of L N, N'-
Pyridine) benzene-Isosorbide-5-Nitrae-diformamide, 1,3-BDC 1,3- phthalic acid root
By 0.1mmol NiCl2·6H2Bis- (4- methylene pyridine) benzene -1,4- diformamides of O, 0.10mmol N, N'-,
0.1mmol 1,3- phthalic acid and 5mL H2O is added sequentially in 25mL beaker, and 20min is stirred at room temperature, and is suspended
Mixture after the pH to 4.1 for reconciling suspended mixture with the NaOH solution of 1mol/L, is transferred in the autoclave of 25mL,
110 DEG C are warming up to the rate of heat addition of 5 DEG C/h, keeps the temperature 48h under hydrothermal condition, room is cooled the temperature to the rate of temperature fall of 5 DEG C/h
Temperature obtains pink colour bulk crystals, and with deionized water and ethyl alcohol alternately cleaning 3 times, naturally dry, obtains [Ni at room temperature2(L)2(1,3-
BDC)2(H2O)4]·5H2O, yield 45%, XRD diffracting spectrum as shown in Fig. 2, its coordination context diagram as shown in figure 8, its
Two-dimensional structure figure is as shown in Figure 9.
By nickel complex [Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O weighs 50 milligrams, 1 gram of high purity graphite powder, uses
Agate mortar grinds 2 hours, is subsequently dispersed in 1 milliliter of atoleine, with 1 hour of agate mortar continuously grinding.Envelope
It is attached to 0.5 centimetre of diameter, 1 millimeter of wall thickness, in the quartz glass tube that 5 centimetres of length, carbon paste one end wipes flat, the other end with template
It is connected with the copper rod for being connected with 6 strands of copper wires, obtains [Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O。
Embodiment 5 synthesizes [Ni (L) (H2O)4] (2,5-TPD), wherein bis- (4- methylene pyridine) benzene -1 of L N, N'-,
4- diformamide, 1,3-BDC 1,3- phthalic acid root
By 0.2mmol NiCl2·6H2Bis- (4- methylene pyridine) benzene -1,4- diformamides of O, 0.10mmol N, N'-,
0.15mmol 1,3- phthalic acid and 10mL H2O is added sequentially in 25mL beaker, and 40min is stirred at room temperature, and is hanged
Mixture is floated, after the pH to 5.3 that suspended mixture is reconciled with the NaOH solution of 1mol/L, is transferred to the autoclave of 25mL
In, 120 DEG C are warming up to the rate of heat addition of 5 DEG C/h, 96h is kept the temperature under hydrothermal condition, is cooled the temperature to the rate of temperature fall of 5 DEG C/h
Room temperature obtains pink colour bulk crystals, and with deionized water and ethyl alcohol alternately cleaning 4 times, naturally dry, obtains [Ni at room temperature2(L)2(1,
3-BDC)2(H2O)4]·5H2O, yield 72%, XRD diffracting spectrum as shown in Fig. 2, its coordination context diagram as shown in figure 8,
Its two-dimentional structure chart is as shown in Figure 9.
By nickel complex [Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O weighs 50 milligrams, 1.5 grams of high purity graphite powder, adopts
3 hours are ground with agate mortar, are subsequently dispersed in 1.2 milliliters of atoleine, it is small with agate mortar continuously grinding 1.5
When.Be encapsulated into 0.5 centimetre of diameter, 1 millimeter of wall thickness, in the quartz glass tube that 5 centimetres of length, carbon paste one end wiped with template it is flat,
The other end is connected with the copper rod for being connected with 8 strands of copper wires, obtains [Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O。
Embodiment 6 synthesizes [Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O, wherein bis- (the 4- methylene pyrroles of L N, N'-
Pyridine) benzene-Isosorbide-5-Nitrae-diformamide, 1,3-BDC 1,3- phthalic acid root
By 0.3mmol NiCl2·6H2Bis- (4- methylene pyridine) benzene -1,4- diformamides of O, 0.10mmol N, N'-,
0.2mmol 1,3- phthalic acid and 15mL H2O is added sequentially in 25mL beaker, and 60min is stirred at room temperature, and is suspended
Mixture after the pH to 7.0 for reconciling suspended mixture with the NaOH solution of 1mol/L, is transferred in the autoclave of 25mL,
130 DEG C are warming up to the rate of heat addition of 5 DEG C/h, keeps the temperature 120h under hydrothermal condition, room is cooled the temperature to the rate of temperature fall of 5 DEG C/h
Temperature obtains pink colour bulk crystals, and with deionized water and ethyl alcohol alternately cleaning 5 times, naturally dry, obtains [Ni at room temperature2(L)2(1,3-
BDC)2(H2O)4]·5H2O, yield 55%, XRD diffracting spectrum as shown in Fig. 2, its coordination context diagram as shown in figure 8, its
Two-dimensional structure figure is as shown in Figure 9.
By nickel complex [Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O weighs 50 milligrams, 2 grams of high purity graphite powder, uses
Agate mortar grinds 4 hours, is subsequently dispersed in 1.5 milliliters of atoleine, with 2 hours of agate mortar continuously grinding.
Be encapsulated into 0.5 centimetre of diameter, 1 millimeter of wall thickness, in the quartz glass tube that 5 centimetres of length, carbon paste one end wiped with template it is flat, it is another
It holds and is connected with the copper rod for being connected with 10 strands of copper wires, obtain [Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O。
The characterization of nickel functional complexes based on 1~embodiment of the embodiment of the present invention 3 and 4~embodiment of embodiment 6:
Powder diffraction characterizes complex [Ni (L) (H2O)4] (2,5-TPD) (1) and [Ni2(L)2(1,3-BDC)2
(H2O)4]·5H2O (2) Xiang Chundu.
It is collected on Rigaku Ultima IV powder x-ray diffraction and completes powder diffraction data, operation electric current is
40mA, voltage 40kV.Using copper target X-ray.Scanning constant, reception slit width are 0.1mm.Density data, which is collected, uses 2 θ/θ
Scan pattern, 5 ° to 50 ° of scanning range, scanning speed is 5 °/s, and span is 0.02 °/time.Data fitting uses Cerius2 journey
Sequence, the conversion of mono-crystalline structures powder diffraction spectrum analog use Mercury 1.4.1.As depicted in figs. 1 and 2, based on organic ligand
The powder x-ray diffraction spectrogram of multi-functional nickel complex and the XRD spectra of fitting coincide substantially, show that complex is pure phase.
Complex [Ni (L) (H2O)4] (2,5-TPD) (1) and [Ni2(L)2(1,3-BDC)2(H2O)4]·5H2The IR Characterization of O (2).
[Ni (L) (H as shown in Figure 3 and Figure 42O)4] (2,5-TPD) (1) and [Ni2(L)2(1,3-BDC)2(H2O)4]·
5H2Exist in O (2) and comes from N, bis- (4- methylene pyridine) benzene -1,4- diformamides of N'-, 2,5- thiophenedicarboxylic acid root, 1,3- benzene
The apparent characteristic absorption peak such as carboxyl, amide groups, the pyridyl group of diformazan acid group.
Thermogravimetric characterizes complex [Ni (L) (H2O)4] (2,5-TPD) (1) and [Ni2(L)2(1,3-BDC)2(H2O)4]·
5H2The stability of O (2).
Thermal stability is completed using PE-Pyris Diamond S-II thermal analyzer, 10 DEG C/min of the rate of heat addition, temperature model
Enclose 20 DEG C~800 DEG C.Fig. 5 shows that the decomposition temperature scope for the complex that the present invention synthesizes is 150 DEG C~450 DEG C.
Crystal structure determination:
The monocrystalline of suitable size is chosen with microscope, uses Bruker SMART APEX II diffractometer (graphite at room temperature
Monochromator, Mo-Ka) collect diffraction data.Scanning modeDiffraction data carries out absorption correction using SADABS program.Data
Reduction and structure elucidation use SAINT and SHELXTL program to complete respectively.Least square method determines whole non-hydrogen atom coordinates,
And hydrogen atom position is obtained with theoretical hydrogenation method.Refine is carried out to crystal structure using least square method.Fig. 6~Fig. 7 is shown
The basic coordination situation and expansion structure of the multi-functional nickel complex based on organic ligand synthesized in 1~embodiment of embodiment 3.
Fig. 8~Fig. 9 shows the basic coordination of the multi-functional nickel complex based on organic ligand synthesized in 4~embodiment of embodiment 6
Situation and expansion structure.The partial parameters of its crystallography point diffraction data collection and structure refinement are as shown in table 1:
Table 1
Multi-functional nickel complex carbon paste material working electrode [Ni (L) (H2O)4] (2,5-TPD) (1-CPE) and [Ni2
(L)2(1,3-BDC)2(H2O)4]·5H2The preparation of O (2-CPE)
[Ni(L)(H2O)4] (2,5-TPD) carbon paste working electrode (1-CPE) and [Ni2(L)2(1,3-BDC)2
(H2O)4]·5H2Specific step is as follows for the Electrochemical Detection performance test experiment of O carbon paste working electrode (2-CPE):
[Ni (L) (H prepared by embodiment 1- embodiment 32O)4] (2,5-TPD) carbon paste working electrode (1-CPE) or real
Apply [Ni prepared by 4- embodiment 62(L)2(1,3-BDC)2(H2O)4]·5H2O carbon paste working electrode (2-CPE), platinum electrode with
And saturation potassium chloride reference electrode is respectively put into 0.01M H2SO4+0.5M Na2SO4In mixed solution, at room temperature to above-mentioned mixed
Close in solution and be passed through argon gas, and keep 30 minutes with dissolved oxygen of going out.In the potential range of+700~-100mV, nickel cooperation
There is 1 pair of apparent oxidationreduction peak on object modified electrode.Figure 10 and Figure 14 gives 1-CPE and 2-CPE and sweeps under speed in difference
Cyclic voltammogram.When sweep speed 400mV/s is gradually increased to by 20mV/s when, with sweep speed increase, cathode spike potential is gradually to just
Direction is mobile, and anode spike potential is gradually mobile to negative direction.Electric current is shown in Figure 10 and Figure 14 illustration with the variation relation for sweeping speed, is surveying
Fixed sweeps in fast range, cathode peak and anodic peak current and sweeps rapid-result linear relationship, this shows that this oxidation-reduction process is table
Face control process.
As shown in Figure 11 and Figure 15, when sweeping speed is 200mV/s, with hydrogen peroxide (H2O2) concentration increase, reduction peak
Electric current gradually increases, and corresponding oxidation peak current gradually decreases, and shows that hydrogen peroxide is restored by electro-catalysis.In 0~10mM range
Interior, the concentration and peak current of hydrogen peroxide have certain linear relationship.Therefore, which can effectively monitor peroxidating
The content of hydrogen.Working electrode calculates hydrogen peroxide detection limit according to peak current change intensity: with normalized peak current intensity
Intensity (I-Imin)/(Imax-Imin) is ordinate, the logarithm lg [H of concentration of hydrogen peroxide2O2] it is that abscissa is mapped, such as Figure 11
With shown in 15 illustrations.In the concentration range that hydrogen peroxide is 0~10mM, preferably (R is respectively 0.95341 He to linear relationship
0.95341), linear equation is respectively y=2.953+1.024x and y=3.580+1.249x.The intersection point of linear equation and horizontal axis
Limit value is as detected, is computed, working electrode is respectively 1.31mM and 1.36mM to the detection limit of hydrogen peroxide.I is in formula
The peak current intensity of each sample, Imin are working electrode when hydrogen peroxide is not added in 0.01M H2SO4+0.5M Na2SO4It mixes molten
Peak current intensity in liquid, Imax are the peak current intensity of working electrode when 10mM hydrogen peroxide is added.
As shown in Figure 12 and Figure 16, when sweeping speed is 200mV/s, with nitrite anions (NO2 -) concentration increase, reduction peak
Electric current gradually increases, and corresponding oxidation peak current gradually decreases, and shows that nitrite anions is restored by electro-catalysis.In 0~10mM range
Interior, the concentration and peak current of nitrite anions have certain linear relationship.Therefore, which can effectively monitor nitrous acid
The content of root.In the concentration range that nitrite anions is 0~10mM, preferably (R is respectively 0.98081 He to linear relationship
0.95916), linear equation is respectively y=3.292+1.175x and y=3.579+1.281x.The intersection point of linear equation and horizontal axis
Limit value is as detected, is computed, working electrode is respectively 1.58mM and 1.61mM to the detection limit of nitrite anions.
As shown in Figure 13 and Figure 17, when sweeping speed is 200mV/s, with the increase of chloramphenicol (Cp) concentration, reduction peak electricity
Stream gradually increases, and corresponding oxidation peak current gradually decreases, and shows that chloramphenicol is restored by electro-catalysis.Within the scope of 0~10mM, chlorine
The concentration and peak current of mycin have certain linear relationship.Therefore, which can effectively monitor the content of chloramphenicol.
Within the scope of 0~10mM, the concentration and peak current of chloramphenicol have certain linear relationship.Therefore, which can have
The content of effect monitoring chloramphenicol.In the concentration range that chloramphenicol is 0~10mM, preferably (R is respectively 0.98944 to linear relationship
With 0.91923), linear equation is respectively y=2.819+0.926x and y=3.283+1.127x.The friendship of linear equation and horizontal axis
Point is detection limit value, is computed, and working electrode is respectively 0.90mM and 1.22mM to the detection limit of chloramphenicol.
Since entire detection process belongs to surface-controlled process, it, can after working electrode surface is by mechanical damage
With by the simple and quick polishing on template from newly obtaining good working electrode surface.Therefore multinomial range estimation can be carried out
Examination.It due to the good stability of working electrode, is saved under air-proof condition, working electrode can be stablized preservation 1 year or more, therefore real
It is very high with being worth.It can be used as and update quick and convenient, the stable multi-functional electroanalysis working electrode of performance.
The above is only specific embodiments of the present invention, are not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (3)
1. one kind is based on the multi-functional nickel complex of organic ligand, it is characterized in that:
The molecular formula of the complex is as follows:
[Ni(L)(H2O)4]·(2,5-TPD)；
[Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O；
Wherein, L isN,N'-bis- (4- methylene pyridine) benzene-Isosorbide-5-Nitrae-diformamide, 2,5-TPD 2,5- thiophenedicarboxylic acid root,
1,3-BDC is 1,3- phthalic acid root；
The specific synthesis step of complex is as follows:
By NiCl2·6H2O、N,N'-bis- (4- methylene pyridine) benzene-Isosorbide-5-Nitrae-diformamide and 2,5- thiophenedicarboxylic acid, addition are gone
Ionized water；20min~60min is stirred at room temperature and forms suspended mixture, it is describedN,N'-bis- (4- methylene pyridine) benzene -1,
4- diformamide and 2, the molar ratio of 5- thiophenedicarboxylic acid is 1:1~1:2, describedN,N'-bis- (4- methylene pyridine) benzene -1,4-
Diformamide and NiCl2·6H2The molar ratio of O is 1:1~1:3, describedN,NTwo formyl of '-bis- (4- methylene pyridine) benzene -1,4-
The molar ratio of amine and deionized water is 1:2800~1:8300, the NaOH solution tune pH for being 1.0mol/L with concentration is 4.2~
6.8, pour into autoclave and be warming up to 110 DEG C~130 DEG C with 5 DEG C/h heating rate, under hydrothermal condition keep the temperature 48h~
120h cools to room temperature with the rate of temperature fall of 5 DEG C/h and obtains pink colour bulk crystals, with deionized water and ethyl alcohol alternately cleaning 3 times
~5 times, naturally dry, obtains product [Ni (L) (H at room temperature2O)4]·(2,5-TPD)；
By NiCl2·6H2O、N,N'-bis- (4- methylene pyridine) benzene-Isosorbide-5-Nitrae-diformamide and 1,3- phthalic acid, addition go from
Sub- water；20min~60min is stirred at room temperature and forms suspended mixture, it is describedN,N'-bis- (4- methylene pyridine) benzene -1,4-
Diformamide and 1, the molar ratio of 3- phthalic acid is 1:1~1:2, describedN,N'-bis- (4- methylene pyridine) benzene -1,4- diformazan
Amide and NiCl2·6H2The molar ratio of O is 1:1~1:3, describedN,N'-bis- (4- methylene pyridine) benzene -1,4- diformamide with
The molar ratio of deionized water is 1:2800~1:8300, and the NaOH solution tune pH for being 1.0mol/L with concentration is 4.1~7.0,
Enter in autoclave and be warming up to 110 DEG C~130 DEG C with 5 DEG C/h heating rate, 48h~120h is kept the temperature under hydrothermal condition, with 5
DEG C/rate of temperature fall of h cools to room temperature and obtains pink colour bulk crystals, with deionized water and ethyl alcohol alternately cleaning 3 times~5 times, room
The lower naturally dry of temperature, obtains product [Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O。
2. the method that the multi-functional nickel complex based on organic ligand is used to synthesize carbon paste electrode as described in claim 1,
It is characterized in:
Expression formula is as follows:
1-CPE, 2-CPE；
Wherein, 1 is complex [Ni (L) (H2O)4] (2,5-TPD), 2 be complex [Ni2(L)2(1,3-BDC)2(H2O)4]·
5H2O, CPE are carbon paste electrode；
The specific synthesis step of carbon paste electrode is as follows:
By nickel complex [Ni (L) (H2O)4] (2,5-TPD) or [Ni2(L)2(1,3-BDC)2(H2O)4]·5H2O weighs 50
Milligram, grinds 2~4 hours using agate mortar, is subsequently dispersed 1~1.5 milliliter of atoleine by 1~2 gram of graphite powder
In, with agate mortar continuously grinding 1~2 hour；Be encapsulated into 0.5 centimetre of diameter, 1 millimeter of wall thickness, 5 centimetres of length quartz glass
Guan Zhong, carbon paste one end are wiped with template and are put down, and the other end is connected with the copper rod for being connected with 6~11 strands of copper wires.
3. the multi-functional nickel complex based on organic ligand is used to synthesize the method synthesis of carbon paste electrode as claimed in claim 2
Carbon paste electrode hydrogen peroxide, nitrite anions and chloramphenicol electroanalysis detection in application.
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