CN115608355B - Preparation method and application of two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets - Google Patents
Preparation method and application of two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets Download PDFInfo
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
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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
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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. The Ni-TCPP (Fe) is prepared by a surfactant auxiliary method, the NaBH 4 is utilized to reduce HAuCl 4 in situ, and then the 2D AuNPs/Ni-TCPP (Fe) ultrathin nanosheets are obtained, and the nanosheets have larger contact area, more contact active sites and faster electron transport capacity. The AuNPs/Ni-TCPP (Fe) nanosheets have excellent H 2O2 decomposition catalytic performance, stability and interference resistance to 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 of the modified polyester is good in milk, beer, pear juice and human serum practical samples.
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 2O2 (hydrogen peroxide ) is widely used as an important oxidant in the fields of food, environment, chemical industry, biological medicine, clinical medicine and the like. For example, in the food field H 2O2, the production equipment can be comprehensively washed to achieve the sterilization effect; can be used as disinfectant, antistaling agent, antiseptic, etc. in fruit, milk, and meat products. In biological medicine, H 2O2 is used as a marker for detecting diseases such as tumors. And H 2O2 plays a vital role in biological systems, H 2O2 is present as a by-product in some clinical medicine, such as glucose oxidation, uric acid oxidation. However, H 2O2 also induces many diseases such as cancer, gene mutation of DNA, diabetes, cerebral stroke, arteriosclerosis, etc., and is thus of great importance for the detection of H 2O2.
2D synthetic nanoflakes have also gradually emerged in the public view in recent years due to the discovery of graphene, wherein a larger contact area, more contact active sites and faster electron transport capability have been proved to be an effective catalyst due to the ultra-thin nature of 2D-MOF materials compared to 3D-MOF.
H 2O2 is usually detected by using an enzymatic reagent, however, the enzymatic method has the defects of high price, easy inactivation in aqueous solution, unstable property and the like. Therefore, the development and preparation of the non-enzymatic electrochemical sensor are very necessary, so that the non-enzymatic electrochemical sensor can be used for achieving the purposes of low cost, less energy consumption, simple and convenient operation, simple equipment, sensitive reaction, good stability, capability of performing micro-analysis and capability of detecting in real time.
Disclosure of Invention
In order to overcome the technical defects, the invention solves the technical problems of providing a simple and environment-friendly method for preparing a large amount of two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets, wherein the method is used for preparing Ni-TCPP (Fe) by a surfactant auxiliary method, reducing HAuCl 4 in situ by NaBH 4, and further obtaining the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets. The novel H 2O2 decomposition catalyst adopts NaBH 4 to reduce HAuCl 4 in situ to prepare a two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet, has larger contact area, more contact active sites and faster electron transmission capacity, and therefore has excellent electrochemical catalytic performance.
The two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets have diffraction peaks at 22.3 degrees, 38.0 degrees, 44.1 degrees, 64.5 degrees and 77.4 degrees by XRD; 54.2wt% of C, 1.1wt% of N, 38.5wt% of O, 2.7wt% of Ni, 2.5wt% of Fe and 1wt% of Au.
The preparation method of the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets mainly comprises two steps, wherein the preparation principle is shown in figure 1, and the preparation method specifically comprises the following steps:
Step S1: preparation of Ni-TCPP (Fe) nanosheets
Completely dissolving NiCl 2·6H2 O, pyrazine and polyvinylpyrrolidone PVP in a EtOH/DMF mixed solution to obtain a solution 1; dissolving TCPP (Fe) in a EtOH/DMF mixed solution to obtain a solution 2; mixing the solution 1 and the solution 2, performing ultrasonic treatment, and transferring the obtained 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) nanosheets
Adding HAuCl 4 into the Ni-TCPP (Fe) nanosheet aqueous solution, performing ultrasonic treatment on the mixture, and adding the mixture into the NaBH 4 aqueous solution to obtain a solution 4; and (3) centrifugally drying the solution 4, and fully grinding to obtain AuNPs/Ni-TCPP (Fe) powder.
Further, in the step S1 of the technical scheme, the volume ratio of the mixed solution DMF/EtOH is 3:1.
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 the above technical step S1, after centrifugation, the solid is washed with absolute ethanol at least 3 times.
Further, the drying in the technical proposal is carried out at 60 ℃ by adopting a blast drier.
Further, in the above technical scheme step S1, after centrifugation, the solid is washed 3 times with high purity water.
The invention also provides application of the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets to preparation of non-enzymatic electrochemical biosensors.
Further, in the above technical scheme, the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets are used as an H 2O2 decomposition catalyst (the principle of detecting H 2O2 by using an electrochemical platform is shown in figure 3).
Furthermore, 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, low in cost, low in energy consumption, simple and convenient to operate, simple in equipment, sensitive in reaction, good in stability, capable of performing micro-analysis and real-time detection, environment-friendly, free from 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 2O2 decomposition catalyst, which adopts NaBH 4 to reduce HAuCl 4 in situ to prepare a 2D AuNPs/Ni-TCPP (Fe) nanosheet, and has larger contact area, more contact active sites and faster electron transmission capability.
3. The two-dimensional AuNPs/Ni-TCPP (Fe) nano-sheet has excellent H 2O2 decomposition catalytic performance, stability, KCl resistance, bad blood acid resistance, sucrose resistance, uric acid resistance, D-fructose interference resistance, lower detection limit (LOD=0.97 mu M), higher sensitivity, 5 mu M-0.1mM linear response range, higher catalytic selectivity and high reproducibility. Shows excellent electrochemical catalytic activity in milk, beer, pear juice and human serum practical samples.
Drawings
FIG. 1 is a schematic diagram of AuNPs/Ni-TCPP (Fe) nanosheets preparation;
FIG. 2 is a view of an AuNPs/Ni-TCPP (Fe) nanosheets transmission electron microscope;
FIG. 3 is a schematic diagram of AuNPs/Ni-TCPP (Fe) detection of H 2O2 using an electrochemical platform;
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 is a graph of GC/AuNPs/Ni-TCPP (Fe) electrode current response versus H 2O2 concentration.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
A: preparation of 2D Ni-TCPP (Fe) nanosheets (Synthesis method assisted by surfactant)
24.5Mg of NiCl 2·6H2 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 dissolved completely and as a homogeneous 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 was completely dissolved and made into a homogeneous solution (solution 2).
Solution 1 and solution 2 were then mixed and after 15min of ultrasound of the mixed solution (solution 3), solution 3 was transferred to a suitable reaction vessel and reacted for 24h at 80 ℃.
After solution 3 cooled to room temperature, the resulting product was centrifuged at 9000r.p.m for 10 min and washed with absolute ethanol at least three times. The obtained product was put into a blast drying oven at 60 ℃ for 6 hours, cooled to room temperature, and then put into a mortar for full grinding, thus obtaining Ni-TCPP (Fe) nanosheets (X-ray diffraction is shown in figure 4).
B: preparation of AuNPs/Ni-TCPP (Fe) nanosheets
After 1mL of HAuCl 4 (10 mM) was added to 100mL of an aqueous Ni-TCPP (Fe) nanosheet (0.1 mg/mL), the mixture was stirred for 15min, and then 250. Mu.L of cold fresh NaBH 4 aqueous solution (0.1M) was added to give solution 4.
Step S5: solution 4 was centrifuged at 10000r.p.m for 10min and washed 3 times with high purity water. The obtained product is placed in a blast drying oven at 60 ℃ for 6 hours, cooled to room temperature, and then sufficiently ground to obtain AuNPs/Ni-TCPP (Fe) powder (namely nano-sheets, see figure 2 for a transmission electron microscope and figure 4 for X-ray diffraction).
Example 1
AuNPs/Ni-TCPP (Fe) powder (1 mg.mL -1) is uniformly mixed with a certain amount of 5wt% Nafion and absolute ethyl alcohol (absolute ethyl alcohol: nafion=10:1), and ultrasonic treatment is carried out for at least 30min, so that uniform suspension is obtained. And transferring 10 mu L of the prepared suspension liquid onto a clean glass carbon electrode by using a liquid transferring gun, drying under an infrared lamp, and thus completing the preparation of the working electrode. All electrochemical tests used a three electrode system. In the amperometric response (i-t) test, the working electrode was a 3mm diameter glassy carbon electrode coated with a volume and concentration of active material (prepared suspension above), the reference and counter electrodes were Ag/AgCl and Pt filaments, respectively, and the electrolyte was diluted 10-fold with 0.1 mol-L -1 PBS (ph=7.4) to a scan voltage of 100mV at test.
Example 2
AuNPs/Ni-TCPP (Fe) powder (1 mg.mL -1) is uniformly mixed with a certain amount of 5wt% Nafion and absolute ethyl alcohol (absolute ethyl alcohol: nafion=10:1), and ultrasonic treatment is carried out for at least 30min, so that uniform suspension is obtained. And transferring 10 mu L of the prepared suspension liquid onto a clean glass carbon electrode by using a liquid transferring gun, drying under an infrared lamp, and thus completing the preparation of the working electrode. All electrochemical tests used a three electrode system. In the amperometric response (i-t) test, the working electrode was a 3mm diameter glassy carbon electrode coated with a volume and concentration of active material (prepared suspension above), the reference and counter electrodes were Ag/AgCl and Pt filaments, respectively, and the electrolyte was a 10-fold beer mixed solution diluted with 0.1mol·l -1 PBS (ph=7.4), and the scan voltage was 100mV in the test.
Example 3
AuNPs/Ni-TCPP (Fe) powder (1 mg.mL -1) is uniformly mixed with a certain amount of 5wt% Nafion and absolute ethyl alcohol (absolute ethyl alcohol: nafion=10:1), and ultrasonic treatment is carried out for at least 30min, so that uniform suspension is obtained. And transferring 10 mu L of the prepared suspension liquid onto a clean glass carbon electrode by using a liquid transferring gun, drying under an infrared lamp, and thus completing the preparation of the working electrode. All electrochemical tests used a three electrode system. In the ampere response (i-t) test, the working electrode is a glassy carbon electrode with a diameter of 3mm coated with a certain volume and a certain concentration of active substances (the prepared suspension), the reference electrode and the counter electrode are Ag/AgCl and Pt wires respectively, the electrolyte is diluted with 0.1 mol.L -1 PBS (pH=7.4) to obtain a 10-time pure pear juice mixed solution, and the scanning voltage is 100mV in the test.
Example 4
AuNPs/Ni-TCPP (Fe) powder (1 mg.mL -1) is uniformly mixed with a certain amount of 5wt% Nafion and absolute ethyl alcohol (absolute ethyl alcohol: nafion=10:1), and ultrasonic treatment is carried out for at least 30min, so that uniform suspension is obtained. And transferring 10 mu L of the prepared suspension liquid onto a clean glass carbon electrode by using a liquid transferring gun, drying under an infrared lamp, and thus completing the preparation of the working electrode. All electrochemical tests used a three electrode system. In the amperometric response (i-t) test, the working electrode was a 3mm diameter glassy carbon electrode coated with a volume and concentration of active material (the suspension prepared above), the reference electrode and counter electrode were Ag/AgCl and Pt filaments, respectively, and the electrolyte was diluted 30-fold with 0.1 mol-L -1 PBS (ph=7.4) to a scan voltage of 100mV at test.
FIGS. 5 and 6 show AuNPs/Ni-TCPP (Fe) ampere responses and linear correlation diagrams. According to fig. 5,6 and signal to noise ratio (S/n=3), the detection limit of the GCE/AuNPs/Ni-TCPP (Fe) non-enzymatic electrochemical biosensor was 0.97 μm, the linear range was 5 μm-0.1mM, the linear correlation coefficient, and R 2 was 0.9999.
Table 1 shows the application of GC/AuNPs/Ni-TCPP (Fe) electrodes in milk, beer, pear juice and human serum environments with different concentrations. Examples 1, 2, 3 and 4 were tested for recovery rates of 97.5% -101%, 98.1% -103.3%, 98.4% -102.8% and 90.8% -107% respectively, with relative standard deviations of less than 4%.
TABLE 1
While the basic principles, principal features and advantages of the present invention have been described in the foregoing examples, it will be appreciated by those skilled in the art that the present invention is not limited by the foregoing examples, but is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the scope of the invention, which is defined by the appended claims.
Claims (10)
1. The two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets are characterized in that: diffraction peaks exist in the nano-sheet XRD at 22.3 degrees, 38.0 degrees, 44.1 degrees, 64.5 degrees and 77.4 degrees; 54.2wt% of C, 1.1wt% of N, 38.5wt% of O, 2.7wt% of Ni, 2.5wt% of Fe and 1wt% of Au.
2. The method for preparing the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets according to claim 1, comprising the steps of:
Step S1: preparation of Ni-TCPP (Fe) nanosheets
Completely dissolving NiCl 2·6H2 O, pyrazine and polyvinylpyrrolidone PVP in a EtOH/DMF mixed solution to obtain a solution 1; dissolving TCPP (Fe) in a EtOH/DMF mixed solution to obtain a solution 2; mixing the solution 1 and the solution 2, performing ultrasonic treatment, and transferring the obtained 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) nanosheets
Adding HAuCl 4 into the Ni-TCPP (Fe) nanosheet aqueous solution, performing ultrasonic treatment on the mixture, and adding the mixture into the NaBH 4 aqueous solution to obtain a solution 4; and (3) centrifugally drying the solution 4, and fully grinding to obtain the AuNPs/Ni-TCPP (Fe) nanosheets.
3. The method for preparing the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets according to claim 1, wherein the method comprises the following steps: in the step S1, the volume ratio of the mixed solution DMF/EtOH is 3:1.
4. The method for preparing the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets according to claim 1, wherein the method comprises the following steps: in the step S1, the heating reaction temperature is 70-90 ℃ and the reaction time is 20-30 hours.
5. The method for preparing the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets according to claim 1, wherein the method comprises the following steps: in step S1, after centrifugation, the solid is washed at least 3 times with absolute ethanol.
6. The method for preparing the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets according to claim 1, wherein the method comprises the following steps: drying is carried out at 60 ℃ by adopting a blast drier.
7. The method for preparing the two-dimensional AuNPs/Ni-TCPP (Fe) nanosheets according to claim 1, wherein the method comprises the following steps: in step S1, after centrifugation, the solid was washed 3 times with high purity water.
8. Use of the two-dimensional AuNPs/Ni-TCPP (Fe) nanoplatelets as in claim 1 in a non-enzymatic electrochemical biosensor.
9. The use of two-dimensional AuNPs/Ni-TCPP (Fe) nanoplatelets in a non-enzymatic electrochemical biosensor according to claim 8, wherein: the nano-sheets act as H 2O2 decomposition catalysts.
10. The use of two-dimensional AuNPs/Ni-TCPP (Fe) nanoplatelets in the preparation of a non-enzymatic electrochemical biosensor according to claim 9, wherein: the nano-sheet is used as an H 2O2 decomposition catalyst in the detection of milk, beer, pear juice and human serum samples.
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