CN115608355A - Preparation method and application of two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet - Google Patents
Preparation method and application of two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet Download PDFInfo
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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Abstract
The invention discloses a preparation method and application of a two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet, and belongs to the technical field of inorganic catalytic materials. Preparation of Ni-TCPP (Fe) by surfactant-assisted method, using NaBH 4 In situ reduction of HAuCl 4 And then obtaining the 2D AuNPs/Ni-TCPP (Fe) ultrathin nanosheet, wherein the nanosheet has the advantages of larger contact area, more contact active sites and faster electron transmission capability. AuNPs/Ni-TCPP (Fe) nanosheets having excellent H 2 O 2 Decomposition catalytic performance, stability and anti-interference performance of KCl, ascorbic acid, sucrose, uric acid and D-fructose, lower detection limit (LOD =0.97 mu M), higher sensitivity, linear response range of 5 mu M-0.1mM, higher catalytic selectivity and high reproducibility. The electrochemical catalytic activity is good in practical samples of milk, beer, pear juice and human serum.
Description
Technical Field
The invention belongs to the technical field of inorganic catalytic materials, and particularly relates to a preparation method and application of a 2D AuNPs/Ni-TCPP (Fe) nanosheet.
Background
H 2 O 2 (hydrogen peroxide and hydrogen peroxide) is widely applied to the fields of food, environment, chemistry and chemical engineering, biological medicine, clinical medical treatment and the like as an important oxidant. Such as in the food field H 2 O 2 The production equipment can be comprehensively washed, so that the sterilization effect is achieved; can be used as disinfectant, antistaling agent, and antiseptic in fruit, milk, and meat product. In biomedicine, H 2 O 2 Is used as a marker for detecting diseases such as tumor. And H 2 O 2 The important role in biological systems, such as H in glucose oxidation and uric acid oxidation 2 O 2 Are present as by-products. However H 2 O 2 It also induces many diseases such as cancer, gene mutation of DNA, diabetes, cerebral stroke, arteriosclerosis, etc., and thus it is said that H is a disease 2 O 2 Is crucial.
Due to the discovery of graphene, 2D synthetic nano-flakes have also gradually appeared in the public vision in recent years, wherein 2D-MOF materials have proved to be an effective catalyst and received much attention due to their ultra-thin characteristics compared to 3D-MOF, such that they have larger contact area, more contact active sites and faster electron transport capability.
H 2 O 2 The detection is usually carried out by using an enzyme method reagent, however, the enzyme method has the defects of high price, easy inactivation in aqueous solution, unstable property and the like. Therefore, the development and preparation of non-enzymatic electrochemical sensors are necessary, so as to achieve the purposes of low cost, low energy consumption, simple and convenient operation, simple equipment, sensitive reaction, good stability and capability of being carried outMicroanalysis and real-time detection.
Disclosure of Invention
In order to overcome the technical defects, the invention provides a simple and environment-friendly method for preparing a large amount of two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets, and the method prepares Ni-TCPP (Fe) by a surfactant-assisted method and utilizes NaBH 4 In situ reduction of HAuCl 4 And then obtaining the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet. The new type H 2 O 2 Decomposition catalyst, using NaBH 4 In situ reduction of HAuCl 4 The two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet has larger contact area, more contact active sites and faster electron transmission capability, so that the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet has excellent electrochemical catalytic performance.
According to the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet, diffraction peaks exist at 22.3 degrees, 38.0 degrees, 44.1 degrees, 64.5 degrees and 77.4 degrees in XRD; c content 54.2wt%, N content 1.1wt%, O content 38.5wt%, ni content 2.7wt%, fe content 2.5wt%, au content 1wt%.
The preparation method of the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet mainly comprises two steps, the preparation principle is shown in figure 1, and the preparation method specifically comprises the following steps:
step S1: preparation of Ni-TCPP (Fe) nanosheet
Mixing NiCl 2 ·6H 2 Completely dissolving O, pyrazine and polyvinylpyrrolidone (PVP) in an EtOH/DMF mixed solution to obtain a solution 1; TCPP (Fe) is dissolved in the mixed solution of EtOH/DMF to obtain a solution 2; mixing the solution 1 and the solution 2, and then carrying out ultrasonic treatment to obtain a solution 3, and transferring the solution 3 into a reaction kettle for heating reaction; after the reaction is finished, cooling, centrifugally drying the solution 3, and fully grinding to obtain Ni-TCPP (Fe) powder;
step S2: preparation of AuNPs/Ni-TCPP (Fe) nanosheet
HAuCl is added 4 Adding into Ni-TCPP (Fe) nanometer sheet water solution, ultrasonic mixing, adding NaBH 4 Obtaining a solution 4 in the aqueous solution; and centrifugally drying the solution 4, and fully grinding to obtain AuNPs/Ni-TCPP (Fe) powder.
Further, in step S1 of the above technical solution, the mixed solution DMF/EtOH is 3:1 by volume ratio.
Further, in the step S1 of the technical scheme, the heating reaction temperature is 70-90 ℃, and the reaction time is 20-30 hours.
Further, in step S1 of the above technical scheme, after centrifugation, the solid is washed with absolute ethanol at least 3 times.
Furthermore, the drying in the technical scheme is carried out at 60 ℃ by adopting a blast drier.
Further, in step S1 of the above technical scheme, after centrifugation, the solid was washed 3 times with high-purity water.
The invention also provides application of the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet in preparation of a non-enzymatic electrochemical biosensor.
Further, in the technical scheme, the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet is used as H 2 O 2 Decomposition catalyst (detection of H by electrochemical platform) 2 O 2 See fig. 3 for the principle).
Further, in the technical scheme, the nano sheet can be used for detecting milk, beer, pear juice and human serum samples.
The invention has the beneficial effects that:
1. the electrochemical sensor prepared by the invention is non-enzymatic, has the advantages of low cost, low energy consumption, simple and convenient operation, simple equipment, sensitive reaction, good stability, capability of microanalysis and real-time detection, environmental protection and capability of getting rid of the defects brought by enzyme, such as high price, easy inactivation in aqueous solution, unstable property and the like.
2. The invention provides a novel H 2 O 2 Decomposition catalyst, using NaBH 4 In situ reduction of HAuCl 4 The 2D AuNPs/Ni-TCPP (Fe) nanosheet has larger contact area, more contact active sites and faster electron transport capability.
3. Two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets having excellent H 2 O 2 Decomposition catalytic performance, stability, KCl, ascorbic acid, sucrose, uric acid and D-fructose interference resistance, and low detection limit (L)OD =0.97 μ M), higher sensitivity, linear response range of 5 μ M-0.1mM, and higher catalytic selectivity and high reproducibility. The electrochemical catalytic activity is excellent in practical samples of milk, beer, pear juice and human serum.
Drawings
FIG. 1 is a schematic diagram of AuNPs/Ni-TCPP (Fe) nanosheet preparation;
FIG. 2 is a transmission electron microscope image of AuNPs/Ni-TCPP (Fe) nanosheets;
FIG. 3 is a diagram of the detection of H by AuNPs/Ni-TCPP (Fe) using an electrochemical platform 2 O 2 A schematic diagram;
FIG. 4 is an X-ray diffraction pattern of Ni-TCPP (Fe) and AuNPs/Ni-TCPP (Fe);
FIG. 5 is a graph of typical amperometric responses of a GC/AuNPs/Ni-TCPP (Fe) electrochemical biosensor;
FIG. 6 shows GC/AuNPs/Ni-TCPP (Fe) electrode current response and H 2 O 2 And (4) a concentration linear relation graph.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
A: preparation of 2D Ni-TCPP (Fe) nanosheet (surfactant-assisted synthesis method)
24.5mg of NiCl 2 ·6H 2 O (0.01 mM), 8mg of pyrazine (0.01 mM), and 0.2g of polyvinylpyrrolidone PVP were dissolved in 120mL (v/v = 1/3) of a mixed solution of ethanol and N, N-Dimethylformamide (DMF), and were completely dissolved and became a uniform solution (solution 1).
44mg of TCPP (Fe) (0.005 mM) was dissolved in 40mL (v/v = 1/3) of a mixed solution of ethanol and N, N-Dimethylformamide (DMF), and completely dissolved and became a uniform solution (solution 2).
Then, the solution 1 and the solution 2 are mixed, and after the mixed solution is subjected to ultrasonic treatment for 15min (solution 3), the solution 3 is transferred to a suitable reaction kettle and heated to 80 ℃ for reaction for 24h.
After the solution 3 was cooled to room temperature, the resulting product was centrifuged at 9000r.p.m for 10 minutes and washed with absolute ethanol at least three times. And (3) putting the obtained product into a 60 ℃ forced air drying oven for 6h, cooling to room temperature, and then putting into a mortar for full grinding to obtain the Ni-TCPP (Fe) nanosheet (X-ray diffraction is shown in figure 4).
B: preparation of AuNPs/Ni-TCPP (Fe) nanosheet
1mL of HAuCl 4 (10 mM) to 100mL of an aqueous solution of Ni-TCPP (Fe) nanoplatelets (0.1 mg/mL), the mixture was stirred for 15min, then 250. Mu.L of cold fresh NaBH was added 4 In an aqueous solution (0.1M), solution 4 was obtained.
Step S5: the solution 4 was centrifuged at 10000r.p.m for 10min and washed with high-purity water 3 times. And placing the obtained product in a 60 ℃ forced air drying oven for 6h, cooling to room temperature, and then fully grinding to obtain AuNPs/Ni-TCPP (Fe) powder (namely nanosheets, see 2,X ray diffraction in a transmission electron microscope as shown in figure 4).
Example 1
AuNPs/Ni-TCPP (Fe) powder (1 mg. ML) -1 ) This was mixed with an amount of 5wt% nafion and absolute ethanol (absolute ethanol: nafion = 10). 10 mu L of the prepared suspension is transferred by a liquid transfer gun and dropped on a clean glassy carbon electrode, and the glassy carbon electrode is dried under an infrared lamp, so that the preparation of the working electrode is finished. All electrochemical tests used a three-electrode system. When an ampere response (i-t) test is carried out, the working electrode is a glassy carbon electrode with the diameter of 3mm, a certain volume and a certain concentration of active substances (the prepared suspension liquid) are coated on the glassy carbon electrode, the reference electrode and the counter electrode are respectively Ag/AgCl and Pt wires, and 0.1 mol.L of electrolyte is adopted -1 The 10 fold dilution of illite milk mixed solution in PBS (pH = 7.4) with a sweep voltage of 100mV when tested.
Example 2
AuNPs/Ni-TCPP (Fe) powder (1 mg. ML) -1 ) This was mixed with an amount of 5wt% nafion and absolute ethanol (absolute ethanol: nafion = 10). 10 mu L of the prepared suspension is transferred by a liquid transfer gun and dropped on a clean glassy carbon electrode, and the glassy carbon electrode is dried under an infrared lamp, so that the working electrode is prepared. All electrochemical tests used a three-electrode system. When an ampere response (i-t) test is carried out, a working electrode is a glassy carbon electrode with the diameter of 3mm, a certain volume and a certain concentration of active substances (the prepared suspension liquid) are coated on the glassy carbon electrode, a reference electrode and a counter electrode are respectively Ag/AgCl and Pt wires, and 0.1 mol.L of electrolyte is adopted -1 The beer mixed solution was diluted 10-fold with PBS (pH = 7.4) and the scanning voltage was 100mV at the time of the test.
Example 3
AuNPs/Ni-TCPP (Fe) powder (1 mg. ML) -1 ) This was mixed with an amount of 5wt% nafion and absolute ethanol (absolute ethanol: nafion = 10). 10 mu L of the prepared suspension is transferred by a liquid transfer gun and dropped on a clean glassy carbon electrode, and the glassy carbon electrode is dried under an infrared lamp, so that the preparation of the working electrode is finished. All electrochemical tests used a three-electrode system. When an ampere response (i-t) test is carried out, a working electrode is a glassy carbon electrode with the diameter of 3mm, a certain volume and a certain concentration of active substances (the prepared suspension liquid) are coated on the glassy carbon electrode, a reference electrode and a counter electrode are respectively Ag/AgCl and Pt wires, and 0.1 mol.L of electrolyte is adopted -1 The 10-fold dilution of the pure pear juice mixed solution in PBS (pH = 7.4) gave a sweep voltage of 100mV when tested.
Example 4
AuNPs/Ni-TCPP (Fe) powder (1 mg. ML) -1 ) This was mixed with an amount of 5wt% nafion and absolute ethanol (absolute ethanol: nafion = 10). 10 mu L of the prepared suspension is transferred by a liquid transfer gun and dropped on a clean glassy carbon electrode, and the glassy carbon electrode is dried under an infrared lamp, so that the preparation of the working electrode is finished. All electrochemical tests used a three-electrode system. When an ampere response (i-t) test is carried out, the working electrode is a glassy carbon electrode with the diameter of 3mm, a certain volume and a certain concentration of active substances (the prepared suspension liquid) are coated on the glassy carbon electrode, the reference electrode and the counter electrode are respectively Ag/AgCl and Pt wires, and 0.1 mol.L of electrolyte is adopted -1 The human serum mixed solution was diluted 30-fold with PBS (pH = 7.4) and the scan voltage was 100mV at the time of the test.
FIGS. 5 and 6 are graphs showing the Ampere response and linearity of AuNPs/Ni-TCPP (Fe). Calculated from FIG. 5, FIG. 6 and the signal-to-noise ratio (S/N = 3), GCE/AuNPs-The detection limit of the Ni-TCPP (Fe) non-enzymatic electrochemical biosensor is 0.97 mu M, the linear range is 5 mu M-0.1mM, and the linear correlation coefficient, R 2 Is 0.9999.
Table 1 shows the application of GC/AuNPs/Ni-TCPP (Fe) electrodes in different concentrations of milk, beer, pear juice and human serum environments. The recovery tests of the examples 1, 2, 3 and 4 show that the recovery rates are 97.5-101%, 98.1-103.3%, 98.4-102.8% and 90.8-107%, and the relative standard deviation is less than 4%.
TABLE 1
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (10)
1. The two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet is characterized in that: diffraction peaks of the nanosheet XRD exist at 22.3 degrees, 38.0 degrees, 44.1 degrees, 64.5 degrees and 77.4 degrees; c54.2 wt%, N1.1 wt%, O38.5 wt%, ni 2.7wt%, fe 2.5wt%, and Au 1wt%.
2. The method of preparing two-dimensional AuNPs/Ni-TCPP (Fe) nanoplates of claim 1, comprising the steps of:
step S1: preparation of Ni-TCPP (Fe) nanosheet
Mixing NiCl 2 ·6H 2 Completely dissolving O, pyrazine and polyvinylpyrrolidone (PVP) in an EtOH/DMF mixed solution to obtain a solution 1; TCPP (Fe) is dissolved in the mixed solution of EtOH/DMF to obtain a solution 2; mixing the solution 1 and the solution 2, and then carrying out ultrasonic treatment to obtain a solution 3, and transferring the solution 3 into a reaction kettle for heating reaction; after the reaction is finished and cooledCentrifugally drying the solution 3, and fully grinding to obtain Ni-TCPP (Fe) powder;
step S2: preparation of AuNPs/Ni-TCPP (Fe) nanosheet
Adding HAuCl 4 Adding into Ni-TCPP (Fe) nanometer sheet water solution, ultrasonic mixing, adding NaBH 4 Obtaining a solution 4 in the aqueous solution; and (4) centrifugally drying the solution 4, and fully grinding to obtain the AuNPs/Ni-TCPP (Fe) nanosheet.
3. The method for preparing two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets of claim 1, wherein: in step S1, the volume ratio of DMF/EtOH is 3:1.
4. The method for preparing two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets of claim 1, wherein: in the step S1, the heating reaction temperature is 70-90 ℃, and the reaction time is 20-30 hours.
5. The method for preparing two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets of claim 1, wherein: in step S1, after centrifugation, the solid is washed with absolute ethanol at least 3 times.
6. The method for preparing two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets of claim 1, wherein: drying is carried out at 60 ℃ by adopting a blast drier.
7. The method for preparing two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets of claim 1, wherein: in step S1, after centrifugation, the solid was washed 3 times with high purity water.
8. Use of two-dimensional AuNPs/Ni-TCPP (Fe) nanoplates as defined in claim 1 in non-enzymatic electrochemical biosensors.
9. The use of two-dimensional AuNPs/Ni-TCPP (Fe) nanoplates as defined in claim 8 in a non-enzymatic electrochemical biosensor, wherein: nanosheets as H 2 O 2 Decomposition catalystAn oxidizing agent.
10. The use of two-dimensional AuNPs/Ni-TCPP (Fe) nanoplates as defined in claim 9 in non-enzymatic electrochemical biosensors, wherein: nanosheet used as H in detection of milk, beer, pear juice and human serum samples 2 O 2 A decomposition catalyst.
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| CN109267093A (en) * | 2018-10-09 | 2019-01-25 | 苏州大学 | Ultra-thin Ni-Fe-MOF nanometer sheet and its preparation method and application |
| CN109939740A (en) * | 2019-04-09 | 2019-06-28 | 大连理工大学 | A kind of preparation method and application of the two-dimensional nano piece of load gold nano particle |
| CN114487061A (en) * | 2022-01-05 | 2022-05-13 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Electrochemical biosensor based on metal organic framework hybrid nanosheet and method for detecting content of lactic acid in sweat by using electrochemical biosensor |
| CN114957684A (en) * | 2022-05-10 | 2022-08-30 | 陕西科技大学 | TCPP (Ni) -Co electrode material and preparation method thereof |
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| CN109267093A (en) * | 2018-10-09 | 2019-01-25 | 苏州大学 | Ultra-thin Ni-Fe-MOF nanometer sheet and its preparation method and application |
| CN109939740A (en) * | 2019-04-09 | 2019-06-28 | 大连理工大学 | A kind of preparation method and application of the two-dimensional nano piece of load gold nano particle |
| CN114487061A (en) * | 2022-01-05 | 2022-05-13 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Electrochemical biosensor based on metal organic framework hybrid nanosheet and method for detecting content of lactic acid in sweat by using electrochemical biosensor |
| CN114957684A (en) * | 2022-05-10 | 2022-08-30 | 陕西科技大学 | TCPP (Ni) -Co electrode material and preparation method thereof |
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