CN113447559B - Ultrathin high-stability black phosphorus nanocomposite and preparation method and application thereof - Google Patents
Ultrathin high-stability black phosphorus nanocomposite and preparation method and application thereof Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002135 nanosheet Substances 0.000 claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011261 inert gas Substances 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 60
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 19
- 239000002086 nanomaterial Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000010949 copper Substances 0.000 description 43
- 239000002064 nanoplatelet Substances 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 230000004044 response Effects 0.000 description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000008055 phosphate buffer solution Substances 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 238000000970 chrono-amperometry Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003968 anodic stripping voltammetry Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000011540 sensing material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000011895 specific detection Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003943 differential pulse anodic stripping voltammetry Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003950 stripping voltammetry Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention provides an ultrathin high-stability black phosphorus nanocomposite, a preparation method thereof and a Cu 2+ detection sensor, and belongs to the technical field of nanomaterial preparation and application. The black phosphorus nano composite material is obtained by combining black phosphorus nano sheets and a high molecular polymer through electrostatic adsorption. The preparation method comprises the following steps: deoxidizing the high molecular polymer water solution with inert gas; adding the black phosphorus nano-sheets into the obtained high polymer aqueous solution, deoxidizing with inert gas, and continuously stirring at room temperature for reaction; and after the reaction is finished, washing the solid-phase product with water to obtain the ultrathin high-stability black phosphorus nanocomposite. The preparation method of the ultrathin high-stability black phosphorus nanocomposite is simple, does not depend on large-scale equipment, and has low cost. The black phosphorus composite nano-meter is used for a Cu 2+ detection sensor, and has good stability and stronger anti-interference performance.
Description
Technical Field
The invention relates to the technical field of nano material preparation and application, in particular to an ultrathin high-stability black phosphorus nano composite material and a preparation method thereof, and a Cu 2+ detection sensor.
Background
Because the heavy metal ions have the characteristics of nondegradability, high toxicity and the like, the pollution of the heavy metal ions is harmful to the health of human bodies and seriously damages the ecological environment. Wherein, cu 2+ is used as a common heavy metal ion and is also an indispensable trace element in normal metabolism of living bodies. However, excessive ingestion of Cu 2+ by the human body can lead to the development of a number of diseases. Therefore, developing a rapid, convenient, and efficient method for detecting Cu 2+ is very necessary for both human health and environmental protection. In the existing Cu 2+ detection method, the electrochemical method has the advantages of simple operation, low cost, small required sample amount, easy miniaturization and the like, and is widely applied and developed. Currently, electrochemical sensors for detecting Cu 2+ are mainly focused on the design and development of sensing materials to improve the sensing performance thereof. In recent years, two-dimensional nanomaterials have been widely used for preparing electrode sensing materials due to their unique physicochemical properties to improve sensitivity and selectivity for Cu 2+ detection. However, the sensor constructed based on the conventional two-dimensional material such as graphene and the like has the problems of complex detection process, poor selectivity and the like. Therefore, the realization of high-sensitivity and high-selectivity rapid detection of Cu 2+ by constructing an electrochemical sensor through reasonable design based on the novel two-dimensional nanomaterial has very important significance.
The traditional electrochemical sensor constructed by taking the graphene nanocomposite as an electrode material mostly adopts a differential pulse anodic stripping voltammetry to detect other heavy metal ions such as Cu 2+ in a water body. In addition, the detection of heavy metal ions in the water body can be realized by a square wave anode stripping voltammetry. However, these electrochemical sensors all have to be tested for Cu 2+ by anodic stripping voltammetry, which is relatively complex and requires a prior reductive enrichment of Cu 2+ on the electrode by electrodeposition. However, cu 2+ can hydrolyze during electrodeposition and co-deposit with other metal ions to affect the enrichment of Cu 2+ at the electrode surface, ultimately resulting in low sensitivity and poor selectivity of the sensor. Therefore, the novel two-dimensional nano material is optimally designed, and the application of the novel two-dimensional nano material in the fields of biosensing, catalysis, energy sources and the like is further expanded, so that the novel two-dimensional nano material has important practical significance.
In the prior art, a method for preparing the black phosphorus nano sensor by a person skilled in the art is prepared by connecting black phosphorus and a monomer through chemical reaction. And the detection of metals mostly achieves the detection purpose by detecting the current change condition in the electrochemical oxidation process.
The black phosphorus nano-sheet is used as a novel two-dimensional nano-material, and has the characteristics of high energy density, large specific surface area, molecular adsorption energy and the like due to the unique structure and physical and chemical properties, so that the black phosphorus nano-sheet is widely focused in a plurality of research fields. Since the redox potential of Cu 2+ is located between the conduction and valence bands of black phosphorus, so that Cu 2+ can be captured by black phosphorus and reduced to Cu +, the black phosphorus nanoplatelets are expected to be used as electrode materials to construct electrochemical sensors for detecting Cu 2+. However, black phosphorus nanoplatelets have poor chemical and thermal stability and degrade with water and oxygen under visible light irradiation. Therefore, the sensor based on the black phosphorus nano-sheet has the problem of performance degradation with the passage of time. Therefore, improving the stability of the black phosphorus nano-sheet and optimizing the design of the black phosphorus nano-sheet are key to improving the performance of the sensor.
Disclosure of Invention
In order to solve the technical problems, the invention provides an ultrathin high-stability black phosphorus nanocomposite and a preparation method thereof, and a Cu 2+ detection sensor.
An ultrathin high-stability black phosphorus nanocomposite is obtained by combining black phosphorus nanoplatelets and organic high-molecular polymers through electrostatic adsorption; the organic high molecular polymer comprises branched Polyethylenimine (PEI) or/and polydiallyl dimethyl ammonium chloride (PDDA); the organic high molecular polymer is coated on the surface of the black phosphorus nano sheet, and is embedded between layers of the black phosphorus nano sheet, so that the black phosphorus nano composite material with a sandwich structure is formed.
The preparation method of the ultrathin high-stability black phosphorus nanosheets comprises the following steps:
(1) Deoxidizing the organic high molecular polymer water solution with inert gas for 3-20min;
(2) Centrifuging the dispersion liquid of the black phosphorus nano-sheets, washing the black phosphorus nano-sheets with water for 2 to 5 times, adding the washed black phosphorus nano-sheets into the high polymer aqueous solution obtained in the step (1), deoxidizing the black phosphorus nano-sheets with inert gas, and continuously stirring the black phosphorus nano-sheets at room temperature for reaction for 24 to 72 hours;
(3) And after the reaction is finished, washing the solid-phase product with water for 3-6 times to obtain the ultrathin high-stability black phosphorus nanocomposite.
Further, the inert gas in the step (1) and the step (2) is inert gas such as argon or/and nitrogen.
Further, the concentration of the high polymer aqueous solution in the step (1) is 1-10mg/mL.
Further, in the step (2), the mass ratio of the black phosphorus nano-sheet to the high molecular polymer is 1:5 to 1:30.
A Cu 2+ detection sensor comprises the ultrathin high-stability black phosphorus nanocomposite.
A method of detecting Cu 2+, the method comprising: the Cu 2+ sensor is used for detecting the Cu 2+ solution in PBS (phosphate buffer solution), and the concentration range of the PBS solution is 0.01-0.1M.
Further, cyclic Voltammetry (CV) was used, wherein the Cu 2+ test conditions were: potential window range: -0.7 to-0.3V to 0.3 to 0.7V, and the sweeping speed range is: 10-100 mV/s.
Further, the measurement is performed by adopting a chronoamperometry (IT), and specific test conditions are as follows: the potential was applied in the range of-0.25 to-0.15V by adding 0.25 to 50. Mu. MCu 2+ solution to the PBS solution every 10 to 100s and recording the current response graph.
A preparation method of a Cu 2+ detection sensor comprises the following steps:
S1, dissolving a black phosphorus nanocomposite in water to prepare a black phosphorus nanocomposite aqueous solution;
and S2, dripping the black phosphorus nanocomposite solution on a working electrode of a printing electrode, and airing at room temperature to obtain the sensor.
Further, the concentration of the black phosphorus nanocomposite aqueous solution in the S1 is 5-15mg/mL.
Compared with the prior art, the technical scheme of the invention has the following advantages:
The invention synthesizes the black phosphorus polymer nanocomposite with a highly stable sandwich structure based on the novel two-dimensional nanomaterial black phosphorus nanosheets and the polymer. The composite material is synthesized in one step through strong electrostatic adsorption, wherein polymer molecules can be adsorbed on the surface of the black phosphorus nano sheet and can be embedded between layers of the black phosphorus nano sheet, so that the black phosphorus nano sheet is peeled off to be thinner. The black phosphorus polymer nano composite material has a unique sandwich structure, and the polymer is coated on the surface of the black phosphorus nano sheet, so that the stability of black phosphorus can be remarkably improved, the black phosphorus is prevented from being degraded, cu 2+ can be specifically captured to form a chelate, and further, the quick, ultra-trace and specific detection of Cu 2+ can be realized through direct electrochemical reduction. The ultrathin high-stability black phosphorus nano sheet can be directly applied to various fields, and can also improve the catalytic performance of the ultrathin high-stability black phosphorus nano sheet in various fields such as biosensing, catalysis, energy sources and the like by loading specific catalysts such as noble metals, oxides, sulfides and the like.
The preparation method of the ultrathin high-stability black phosphorus nanosheets is simple, does not depend on large-scale equipment and is low in cost; in addition, the electrode modified by the black phosphorus nanocomposite has good catalytic effect on Cu 2+ and strong anti-interference capability, and compared with a traditional sensor, the sensor constructed based on the black phosphorus nanocomposite has simpler testing process and strong economical practicability, and has better industrialization prospect in the aspect of daily water body detection.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 is a Transmission Electron Microscope (TEM) of example 1 of the present invention: (A) The nanometer material is black phosphorus nanometer sheet, and the (B) is black phosphorus-PEI nanometer composite material; atomic Force Microscopy (AFM): (C) The nanometer material is black phosphorus nanometer sheet, and (D) is black phosphorus-PEI nanometer composite material;
FIG. 2 is a graph showing the performance results of the sensor prepared in example 1 of the present invention; wherein (A) is CV response of the sensor to Cu 2+ with different concentrations, and (B) is an anti-interference result of the sensor to Cu 2+ detection;
FIG. 3 shows stability of Cu 2+ electrochemical sensor respectively constructed by black phosphorus nanoplatelets and black phosphorus-PEI nanocomposite prepared in example 1 of the present invention. (black phosphorus-PEI is expressed as BP-PEI);
FIG. 4 shows that the CV response of the sensor constructed by different raw material ratios (B: 1:10, C:1:15, D: 1:20) of the black phosphorus nanocomposite material has obvious reduction peaks for 200 mu M Cu 2+.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1 (Black phosphorus nanoplatelets to PEI mass ratio 1:15)
1. The preparation method of the ultrathin high-stability black phosphorus nano-sheet comprises the following steps:
(1) PEI is prepared into a PEI aqueous solution (5 mL) with the concentration of 3mg/mL, and then the PEI aqueous solution is deoxidized for 5min by inert gases such as argon or nitrogen.
(2) The black phosphorus nanoplatelet dispersion was centrifuged at 10000rpm/min for 20min and washed 3 times with deionized water. Adding 1mg of black phosphorus nano-sheet after centrifugation into the prepared PEI aqueous solution, and carrying out deoxidization treatment for 20min by using inert gases such as argon or nitrogen.
(3) The reaction was stirred continuously at 500rpm/min for 48h at room temperature. And after the reaction is finished, washing the reaction product with deionized water for 5 times to obtain the ultrathin high-stability black phosphorus-PEI nanocomposite.
2, Preparation of a copper ion sensor:
s1, preparing a black phosphorus-PEI nano composite material into a 10mg/mL aqueous solution;
And S2, dripping 5 mu L of the prepared black phosphorus-PEI nanocomposite solution on a working electrode of a printing electrode, and airing at room temperature to obtain the sensor.
Example 2 (Black phosphorus nanoplatelets to PEI mass ratio 1:10)
1. The preparation method of the ultrathin high-stability black phosphorus nano-sheet comprises the following steps:
(1) PEI is prepared into a PEI aqueous solution (3.3 mL) with the concentration of 3mg/mL, and then the PEI aqueous solution is deoxidized for 5min by inert gases such as argon or nitrogen.
(2) The black phosphorus nanoplatelet dispersion was centrifuged at 10000rpm/min for 20min and washed 3 times with deionized water. Adding 1mg of black phosphorus nano-sheet after centrifugation into the prepared PEI aqueous solution, and carrying out deoxidization treatment for 20min by using inert gases such as argon or nitrogen.
(3) The reaction was stirred continuously at 500rpm/min for 48h at room temperature. And after the reaction is finished, washing the reaction product with deionized water for 5 times to obtain the ultrathin high-stability black phosphorus-PEI nanocomposite.
2, Preparation of a copper ion sensor:
s1, preparing a black phosphorus-PEI nano composite material into a 10mg/mL aqueous solution;
And S2, dripping 5 mu L of the prepared black phosphorus-PEI nanocomposite solution on a working electrode of a printing electrode, and airing at room temperature to obtain the sensor.
Example 3 (Black phosphorus nanoplatelets to PEI mass ratio 1:20)
1. The preparation method of the ultrathin high-stability black phosphorus nano-sheet comprises the following steps:
(1) PEI is prepared into a PEI aqueous solution (6.7 mL) with the concentration of 3mg/mL, and then the PEI aqueous solution is deoxidized for 5min by inert gases such as argon or nitrogen.
(2) The black phosphorus nanoplatelet dispersion was centrifuged at 10000rpm/min for 20min and washed 3 times with deionized water. Adding 1mg of black phosphorus nano-sheet after centrifugation into the prepared PEI aqueous solution, and carrying out deoxidization treatment for 20min by using inert gases such as argon or nitrogen.
(3) The reaction was stirred continuously at 500rpm/min for 48h at room temperature. And after the reaction is finished, washing the reaction product with deionized water for 5 times to obtain the ultrathin high-stability black phosphorus-PEI nanocomposite.
2, Preparation of a copper ion sensor:
s1, preparing a black phosphorus-PEI nano composite material into a 10mg/mL aqueous solution;
And S2, dripping 5 mu L of the prepared black phosphorus-PEI nanocomposite solution on a working electrode of a printing electrode, and airing at room temperature to obtain the sensor.
Example 4
1. The preparation method of the ultrathin high-stability black phosphorus nano-sheet comprises the following steps:
(1) PEI is prepared into a PEI aqueous solution (1.5 mL) with the concentration of 10mg/mL, and then the PEI aqueous solution is deoxidized for 20min by inert gases such as argon or nitrogen.
(2) The black phosphorus nanoplatelet dispersion was centrifuged at 10000rpm/min for 30min and washed with deionized water 2 times. Adding 1mg of black phosphorus nano-sheet after centrifugation into the prepared PEI aqueous solution, and carrying out deoxidization treatment for 20min by using inert gases such as argon or nitrogen.
(3) The reaction was stirred continuously at 500rpm/min for 72h at room temperature. And after the reaction is finished, washing the reaction product with deionized water for 6 times to obtain the ultrathin high-stability black phosphorus-PEI nanocomposite.
2, Preparation of a copper ion sensor:
S1, preparing a black phosphorus-PEI nano composite material into a 15mg/mL aqueous solution;
And S2, dripping 5 mu L of the prepared black phosphorus-PEI nanocomposite solution on a working electrode of a printing electrode, and airing at room temperature to obtain the sensor.
Example 5
1. The preparation method of the ultrathin high-stability black phosphorus nano-sheet comprises the following steps:
(1) PEI is prepared into 1mg/mL PEI aqueous solution (15 mL), and then the PEI aqueous solution is deoxidized for 20min by inert gases such as argon or nitrogen.
(2) 1Mg of the black phosphorus nanoplatelet dispersion was centrifuged at 10000rpm/min for 30min and washed with deionized water for 5 times. Adding 1mg of black phosphorus nano-sheet after centrifugation into the prepared PEI aqueous solution, and carrying out deoxidization treatment for 20min by using inert gases such as argon or nitrogen.
(3) The reaction was stirred continuously at 500rpm/min for 24h at room temperature. And after the reaction is finished, washing the reaction product with deionized water for 3 times to obtain the ultrathin high-stability black phosphorus-PEI nanocomposite.
2, Preparation of a copper ion sensor:
S1, preparing a black phosphorus-PEI nano composite material into a 5mg/mL aqueous solution;
And S2, dripping 5 mu L of the prepared black phosphorus-PEI nanocomposite solution on a working electrode of a printing electrode, and airing at room temperature to obtain the sensor.
Example 6
1. The preparation method of the ultrathin high-stability black phosphorus nano-sheet comprises the following steps:
(1) PDDA was prepared as a 5mg/mL aqueous PDDA solution (3 mL) and then deoxygenated with argon and nitrogen inert gas for 10min.
(2) The black phosphorus nanoplatelet dispersion was centrifuged at 10000rpm/min for 20min and washed with deionized water 2 times. Adding 1mg of black phosphorus nano-sheets after centrifugation into the prepared PDDA aqueous solution, and carrying out deoxidization treatment for 20min by using argon and nitrogen inert gases again.
(3) The reaction was stirred continuously at 500rpm/min for 24h at room temperature. And after the reaction is finished, washing the reaction product with deionized water for 3 times to obtain the ultrathin high-stability black phosphorus-PDDA nanocomposite.
2, Preparation of a copper ion sensor:
s1, preparing a black phosphorus-PDDA nano composite material into a 5mg/mL aqueous solution;
and S2, dripping 5 mu L of the prepared black phosphorus-PDDA nanocomposite solution on a working electrode of a printing electrode, and airing at room temperature to obtain the sensor.
Example 7
1. The preparation method of the ultrathin high-stability black phosphorus nano-sheet comprises the following steps:
(1) PDDA was prepared as a 10mg/mL aqueous PDDA solution (1.5 mL) and then deoxygenated with an inert gas of argon for 20min.
(2) The black phosphorus nanoplatelet dispersion was centrifuged at 10000rpm/min for 20min and washed with deionized water 5 times. Adding 1mg of black phosphorus nano-sheets after centrifugation into the prepared PDDA aqueous solution, and carrying out deoxidization treatment for 20min by using argon inert gas again.
(3) The reaction was stirred continuously at 500rpm/min for 72h at room temperature. And after the reaction is finished, washing the reaction product with deionized water for 2 times to obtain the ultrathin high-stability black phosphorus-PDDA nanocomposite.
2, Preparation of a copper ion sensor:
S1, preparing a black phosphorus-PDDA nano composite material into a 10mg/mL aqueous solution;
and S2, dripping 5 mu L of the prepared black phosphorus-PDDA nanocomposite solution on a working electrode of a printing electrode, and airing at room temperature to obtain the sensor.
Test case
1 Physical and chemical Property test
The PEI modified black phosphorus-PEI nano composite material sheet prepared in the embodiment 1 is compared with a single black phosphorus nano sheet, and structural characterization is carried out, and the experimental result is shown in figure 1.
FIG. 1 shows TEM and AFM results of morphology characterization of a black phosphorus-PEI nanocomposite and an independent black phosphorus nano sheet, wherein the appearance of holes in the independent black phosphorus nano sheet is shown in FIG. 1 (A), and the appearance of holes in the independent black phosphorus nano sheet is shown in FIG. 1 (B); AFM results showed that the thickness of the individual black phosphorus nanoplatelets was 5nm as shown in FIG. 1 (C) and the thickness of the black phosphorus-PEI nanocomposite was 1.5nm as shown in FIG. 1 (D).
2, Sensor-specific detection
The specific experimental operation steps are as follows: the specificity of the copper ion detection sensor prepared in example 1 for Cu 2+ detection was measured by a chronoamperometry. Specific test conditions: the current response curve was recorded by adding Cu 2+, interfering ion K +、Ca2+、Ni2+、Zn2+、Mn2+、Fe3+、Fe2+, and the like to a 0.01M PBS solution at equal concentrations every 20-100s in order at a potential of-0.2V. (wherein the concentration of PBS solution used in electrochemical detection of the sensor is in the range of 0.01-0.1M, and the range of potential applied by chronoamperometry is-0.25 to-0.15V).
Conclusion of experiment: the ability of an electrochemical sensor constructed from a black phosphorus-PEI nanocomposite to detect Cu 2+ was tested using Cyclic Voltammetry (CV), and as can be seen from FIG. 2 (A), the black phosphorus-PEI nanocomposite can be directly subjected to a reduction test on Cu 2+ without the need of an anodic stripping voltammetry, greatly simplifying the detection process and improving the detection performance of the sensor, which has an obvious current response to Cu 2+ of 0-200. Mu.M. The anti-interference capability of the sensor is tested by adopting a chronoamperometry, and the selected interferents are some ions which are commonly coexistent with Cu 2+ in a water sample, such as: k +、Ca2+、Ni2+、Zn2+、Mn2+、Fe3+、Fe2+, etc. As can be seen from fig. 2 (B), the sensor showed a clear response to Cu 2+, while it showed little response to other interferents of the same concentration. This shows that the sensor has better selectivity to Cu 2+.
In addition, stability of the black phosphorus nanoplatelets alone and the black phosphorus-PEI nanocomposite prepared was investigated. As can be seen from fig. 3, the black phosphorus-PEI nanocomposite still maintained 99.7% of the initial current response after 10 days, while the current response of the black phosphorus nanoplatelets alone to Cu 2+ decayed rapidly and was nearly zero after 10 days. This shows that the black phosphorus-PEI nanocomposite has better stability than the black phosphorus nanoplatelets.
Furthermore, a comparison study of the performance of Cu 2+ sensors constructed based on different materials was performed using Cyclic Voltammetry (CV). As can be seen from fig. 4, the black phosphorus (a) alone showed little response to 200 μΜ Cu 2+, the PEI (E) alone showed only a weak reduction peak for the CV response to 200 μΜ Cu 2+, whereas the sensors constructed based on the black phosphorus-PEI nanocomposite (examples 1-3: where the mass ratio of black phosphorus to PEI nanoplatelets is 1:10,1:15,1:20, respectively) showed a significant reduction peak for the CV response to 200 μΜ Cu 2+, and fig. 4 (F) is a response peak current bar graph corresponding to fig. 4 (a), (B), (C), (D), and E), from which it can be seen that the black phosphorus-PEI (1:15) nanocomposite had the largest peak current response to 200 μΜ Cu 2+, indicating the best performance of the Cu 2+ sensor constructed based on the black phosphorus-PEI (1:15) nanocomposite.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (4)
1. A preparation method of an ultrathin high-stability black phosphorus nanocomposite is characterized by comprising the following steps of: the method comprises the following steps:
(1) Deoxidizing the organic high molecular polymer water solution with inert gas for 3-20min;
(2) Centrifuging the dispersion liquid of the black phosphorus nano-sheets, washing the black phosphorus nano-sheets with water for 2 to 5 times, adding the washed black phosphorus nano-sheets into the organic high polymer aqueous solution obtained in the step (1), deoxidizing the black phosphorus nano-sheets with inert gas, and continuously stirring the black phosphorus nano-sheets at room temperature for reaction for 24 to 72 hours;
(3) After the reaction is finished, washing the solid-phase product with water for 3-6 times to obtain the ultrathin high-stability black phosphorus nanocomposite;
the organic high molecular polymer comprises branched polyethylenimine and/or polydiallyl dimethyl ammonium chloride.
2. The method for preparing the ultrathin high-stability black phosphorus nanocomposite according to claim 1, which is characterized in that: the inert gas in the step (1) and the step (2) is argon or/and nitrogen; the concentration of the organic high molecular polymer aqueous solution in the step (1) is 1-10 mg/mL.
3. The method for preparing the ultrathin high-stability black phosphorus nanocomposite according to claim 1, which is characterized in that: in the step (2), the mass ratio of the black phosphorus nano-sheet to the organic high molecular polymer is 1: 5-1: 30.
4. The method for preparing the ultrathin high-stability black phosphorus nanocomposite according to claim 1, which is characterized in that: the black phosphorus nano composite material is obtained by combining black phosphorus nano sheets and organic high molecular polymers through electrostatic adsorption; the organic high molecular polymer is coated on the surface of the black phosphorus nano sheet, and is embedded between layers of the black phosphorus nano sheet, so that the black phosphorus nano composite material with a sandwich structure is formed.
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