CN113447559A - 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 105
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002135 nanosheet Substances 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001514 detection method Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 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 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 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 61
- 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
- 239000000243 solution Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 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
- 230000004044 response Effects 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 11
- 238000006392 deoxygenation reaction Methods 0.000 claims description 9
- 238000002484 cyclic voltammetry Methods 0.000 claims description 7
- 238000000970 chrono-amperometry Methods 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 229910001431 copper ion Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
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- 239000011540 sensing material Substances 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
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- 230000036541 health Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000011895 specific detection Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000000151 deposition 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
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002452 interceptive effect Effects 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
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal 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
- 238000005171 square wave anodic stripping voltammetry Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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Abstract
The invention provides an ultrathin high-stability black phosphorus nanocomposite material, a preparation method thereof and Cu2+A detection sensor belongs to the technical field of nano material preparation and application. The black phosphorus nanocomposite material is obtained by combining a black phosphorus nanosheet and a high molecular polymer through electrostatic adsorption. The preparation method comprises the following steps: deoxidizing the high molecular polymer aqueous solution by using inert gas; centrifugally washing the dispersion liquid of the black phosphorus nanosheets, adding the washed black phosphorus nanosheets into the obtained high-molecular polymer aqueous solution, deoxidizing by using 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 material is simple, does not depend on large-scale equipment, and is low in cost. Application of black phosphorus composite nano-particles to Cu2+The detection sensor is used for detecting the position of the sensor,has good stability and strong anti-interference performance.
Description
Technical Field
The invention relates to the technical field of preparation and application of nano materials, in particular to an ultrathin high-stability black phosphorus nano composite material and a preparation method thereof, and Cu2+And detecting the sensor.
Background
Because the heavy metal ions have the characteristics of nondegradable property, high toxicity and the like, the pollution of the heavy metal ions is harmful to the human health and seriously damages the ecological environment. Wherein, Cu2+As a common heavy metal ion, it is also a trace element indispensable to normal metabolism of the living body. However, excessive Cu intake by humans2+Can lead to the development of many diseases. Therefore, a rapid, convenient and effective Cu is developed2+The detection method is very necessary for human health and environmental protection. Existing Cu2+Among detection methods, electrochemical methods are widely used and developed because of their advantages such as simple operation, low cost, small amount of samples required, and easy miniaturization. At present, the detection of Cu is concerned2+The electrochemical sensor mainly focuses on the design and development of the sensing material to improve the sensing performance of the sensing material. In recent years, two-dimensional nano materials are widely used for preparing electrode sensing materials to improve Cu due to unique physical and chemical properties2+Sensitivity and selectivity of detection. However, the sensor constructed based on the traditional two-dimensional material such as graphene has the problems of complex detection process, poor selectivity and the like. Therefore, the electrochemical sensor is constructed based on the novel two-dimensional nano material through reasonable design to realize the Cu-Cu interaction2+The high-sensitivity and high-selectivity rapid detection has very important significance.
The traditional electrochemical sensor constructed based on graphene nano composite material as electrode material mostly adopts differential pulse anodic stripping voltammetry to Cu in water2+And other heavy metal ions. In addition, the detection of heavy metal ions in the water body can be realized by square wave anodic stripping voltammetry. However, theseThe electrochemical sensor has to carry out anodic stripping voltammetry on Cu2+Test analysis is performed, which is complicated and requires first Cu to be electrodeposited2+And carrying out reduction enrichment on the electrode. However, Cu is in the process of electrodeposition2+Hydrolysis and co-deposition with other metal ions can occur to affect Cu2+The enrichment on the surface of the electrode finally results in low sensitivity and poor selectivity of the sensor. Therefore, the method has important practical significance for optimizing and designing the novel two-dimensional nano material and further expanding the application of the novel two-dimensional nano material in the fields of biosensing, catalysis, energy sources and the like.
In the prior art, a method for preparing a black phosphorus nano sensor by a person skilled in the art is prepared by connecting black phosphorus and a monomer through a chemical reaction. And the detection metal can achieve the detection purpose by detecting the current change condition in the electrochemical oxidation process.
As a novel two-dimensional nano material, the black phosphorus nanosheet attracts extensive attention in a plurality of research fields due to the unique structure and physicochemical properties, particularly the characteristics of high energy density, large specific surface area, molecular adsorption energy and the like. Due to Cu2+Is between the conduction band and the valence band of black phosphorus, so that Cu2+Can be captured by black phosphorus and reduced into Cu+Therefore, the black phosphorus nanosheet is expected to be used as an electrode material for constructing and detecting Cu2+The electrochemical sensor of (1). However, the black phosphorus nanosheets are poor in chemical and thermal stability, and water and oxygen are subject to degradation under visible light irradiation. Therefore, the sensor based on the black phosphorus nanosheet has the problem of performance degradation over time. Therefore, the key to improving the performance of the sensor is to improve the stability of the black phosphorus nanosheet and optimize the design of the black phosphorus nanosheet.
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 Cu2+And detecting the sensor.
An ultrathin high-stability black phosphorus nanocomposite is obtained by combining a black phosphorus nanosheet and an organic high molecular polymer through electrostatic adsorption; the organic high molecular polymer comprises branched Polyethyleneimine (PEI) or/and polydiallyldimethylammonium chloride (PDDA); the organic high molecular polymer is coated on the surface of the black phosphorus nanosheet and is embedded between layers of the black phosphorus nanosheet, so that the black phosphorus nanocomposite with a sandwich structure is formed.
A preparation method of an ultrathin high-stability black phosphorus nanosheet comprises the following steps:
(1) deoxidizing the organic high molecular polymer aqueous solution for 3-20min by using inert gas;
(2) centrifuging the dispersion liquid of the black phosphorus nanosheets, washing the dispersion liquid with water for 2-5 times, adding the washed black phosphorus nanosheets into the high-molecular polymer aqueous solution obtained in the step (1), carrying out deoxygenation treatment with inert gas, and continuously stirring and reacting for 24-72h at room temperature;
(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 argon or/and nitrogen and other inert gases.
Further, the concentration of the aqueous solution of the high molecular polymer in the step (1) is 1 to 10 mg/mL.
Further, the mass ratio of the black phosphorus nanosheet to the high molecular polymer in the step (2) is 1: 5-1: 30.
cu2+A detection sensor, wherein the sensor comprises the ultrathin high-stability black phosphorus nanocomposite.
Detect Cu2+The method comprises the following steps: using the Cu2+Sensor for Cu in PBS solution2+And (4) detecting the solution, wherein the concentration of the PBS solution is in the range of 0.01-0.1M.
Further, Cyclic Voltammetry (CV) was used for detection, wherein Cu is2+The test conditions were: potential window range: -0.7 to-0.3V to 0.3 to 0.7V, sweep speed range: 10 to 100 mV/s.
Further, using chronoamperometry (IT)And (3) performing measurement, wherein the specific test conditions are as follows: the applied potential is in the range of-0.25 to-0.15V, and 0.25 to 50 mu MCu is added into the PBS solution every 10 to 100s2+The solution was dissolved and the current response profile recorded.
Cu2+The preparation method of the detection sensor comprises the following steps:
s1, dissolving the black phosphorus nano composite material in water to prepare a black phosphorus nano composite material aqueous solution;
and S2, dropwise adding the black phosphorus nanocomposite solution on a working electrode of a printing electrode, and airing at room temperature to obtain the sensor.
Furthermore, the concentration of the black phosphorus nanocomposite aqueous solution in S1 is 5-15 mg/mL.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the invention synthesizes the black phosphorus high polymer nano composite material with a highly stable sandwich structure based on the novel two-dimensional nano material black phosphorus nano sheet and the high molecular polymer. The composite material is synthesized in one step through strong electrostatic adsorption, wherein high polymer molecules can be adsorbed on the surface of the black phosphorus nanosheet and can be embedded between layers of the black phosphorus nanosheet, so that the black phosphorus nanosheet is stripped to be thinner. The black phosphorus high polymer nano composite material has a unique sandwich structure, and the high polymer is coated on the surface of the black phosphorus nano sheet, so that the stability of black phosphorus can be obviously improved, the degradation of the black phosphorus can be prevented, and Cu can be specifically captured2+Chelate formation and subsequent Cu pairing by direct electrochemical reduction2+The rapid, ultra-trace and specific detection. The ultrathin high-stability black phosphorus nanosheet can be directly applied to various fields, and the catalytic performance of the ultrathin high-stability black phosphorus nanosheet in various fields such as biosensing, catalysis and energy can be improved by loading specific catalysts such as noble metal, oxide and sulfide.
The preparation method of the ultrathin high-stability black phosphorus nanosheet is simple, does not depend on large-scale equipment, and is low in cost; in addition, the electrode pair Cu modified by the black phosphorus nano composite material2+Has good catalytic effect and strong anti-interference capability, and is based on the black phosphorusCompared with the traditional sensor, the sensor constructed by the nano composite material has the advantages of simpler test process, high economic and practical applicability and better industrialization prospect in the aspect of daily water body detection.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a Transmission Electron Micrograph (TEM) of example 1 of the present invention: (A) is a black phosphorus nano-sheet, (B) is a black phosphorus-PEI nano composite material; atomic Force Microscopy (AFM): (C) is black phosphorus nano-sheet, (D) is black phosphorus-PEI nano composite material;
FIG. 2 is a graph of sensor performance results obtained from the preparation of example 1 of the present invention; wherein (A) is sensor to Cu with different concentrations2+CV response of (A), (B) is sensor pair Cu2+Detecting an anti-interference result;
FIG. 3 shows that the Cu prepared from the black phosphorus nanosheet and the black phosphorus-PEI nanocomposite respectively in the embodiment 1 of the present invention2+Stability of the electrochemical sensor. (Black phosphorus-PEI is expressed as BP-PEI);
FIG. 4 shows a sensor pair of 200 μ M Cu constructed from different raw material ratios (B:1:10, C:1:15, D:1:20) of the black phosphorus nanocomposite material of the present invention2+There was a clear reduction peak in CV response.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1 (Black phosphorus nanosheet to PEI mass ratio of 1:15)
1. The preparation method of the ultrathin high-stability black phosphorus nanosheet comprises the following steps:
(1) PEI is prepared into 3mg/mL PEI aqueous solution (5mL), and then the PEI aqueous solution is subjected to oxygen removal treatment for 5min by inert gases such as argon or nitrogen.
(2) And centrifuging the dispersion liquid of the black phosphorus nanosheet at 10000rpm/min for 20min and washing the dispersion liquid with deionized water for 3 times. And adding the centrifuged 1mg of black phosphorus nanosheet into the prepared PEI aqueous solution, and carrying out deoxygenation treatment for 20min by using inert gases such as argon or nitrogen again.
(3) The reaction was stirred at 500rpm/min for 48h at room temperature. And after the reaction is finished, washing the reaction product for 5 times by using deionized water to obtain the ultrathin high-stability black phosphorus-PEI nano composite material.
2, preparing a copper ion sensor:
s1, preparing the black phosphorus-PEI nano composite material into 10mg/mL aqueous solution;
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 nanosheet to PEI mass ratio of 1:10)
1. The preparation method of the ultrathin high-stability black phosphorus nanosheet comprises the following steps:
(1) PEI is prepared into 3mg/mL PEI aqueous solution (3.3mL), and then the PEI aqueous solution is subjected to oxygen removal treatment for 5min by inert gases such as argon or nitrogen.
(2) And centrifuging the dispersion liquid of the black phosphorus nanosheet at 10000rpm/min for 20min and washing the dispersion liquid with deionized water for 3 times. And adding the centrifuged 1mg of black phosphorus nanosheet into the prepared PEI aqueous solution, and carrying out deoxygenation treatment for 20min by using inert gases such as argon or nitrogen again.
(3) The reaction was stirred at 500rpm/min for 48h at room temperature. And after the reaction is finished, washing the reaction product for 5 times by using deionized water to obtain the ultrathin high-stability black phosphorus-PEI nano composite material.
2, preparing a copper ion sensor:
s1, preparing the black phosphorus-PEI nano composite material into 10mg/mL aqueous solution;
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 nanosheet to PEI mass ratio of 1:20)
1. The preparation method of the ultrathin high-stability black phosphorus nanosheet comprises the following steps:
(1) PEI is prepared into a 3mg/mL PEI aqueous solution (6.7mL), and then the PEI aqueous solution is subjected to oxygen removal treatment for 5min by using inert gases such as argon or nitrogen.
(2) And centrifuging the dispersion liquid of the black phosphorus nanosheet at 10000rpm/min for 20min and washing the dispersion liquid with deionized water for 3 times. And adding the centrifuged 1mg of black phosphorus nanosheet into the prepared PEI aqueous solution, and carrying out deoxygenation treatment for 20min by using inert gases such as argon or nitrogen again.
(3) The reaction was stirred at 500rpm/min for 48h at room temperature. And after the reaction is finished, washing the reaction product for 5 times by using deionized water to obtain the ultrathin high-stability black phosphorus-PEI nano composite material.
2, preparing a copper ion sensor:
s1, preparing the black phosphorus-PEI nano composite material into 10mg/mL aqueous solution;
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 nanosheet comprises the following steps:
(1) PEI is prepared into 10mg/mL PEI aqueous solution (1.5mL), and then the PEI aqueous solution is subjected to oxygen removal treatment for 20min by inert gases such as argon or nitrogen.
(2) And centrifuging the dispersion liquid of the black phosphorus nanosheet for 30min at the rotating speed of 10000rpm/min, and washing the dispersion liquid for 2 times by using deionized water. And adding the centrifuged 1mg of black phosphorus nanosheet into the prepared PEI aqueous solution, and carrying out deoxygenation treatment for 20min by using inert gases such as argon or nitrogen again.
(3) The reaction was stirred at 500rpm/min for 72h at room temperature. And after the reaction is finished, washing the reaction product for 6 times by using deionized water to obtain the ultrathin high-stability black phosphorus-PEI nano composite material.
2, preparing a copper ion sensor:
s1, preparing the black phosphorus-PEI nano composite material into a 15mg/mL aqueous solution;
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 nanosheet comprises the following steps:
(1) PEI is prepared into 1mg/mL PEI aqueous solution (15mL), and then the PEI aqueous solution is subjected to oxygen removal treatment for 20min by inert gases such as argon or nitrogen.
(2) 1mg of the dispersion of the black phosphorus nanosheet was centrifuged at 10000rpm/min for 30min and washed 5 times with deionized water. And adding the centrifuged 1mg of black phosphorus nanosheet into the prepared PEI aqueous solution, and carrying out deoxygenation treatment for 20min by using inert gases such as argon or nitrogen again.
(3) The reaction was stirred at 500rpm/min for 24h at room temperature. And after the reaction is finished, washing the reaction product for 3 times by using deionized water to obtain the ultrathin high-stability black phosphorus-PEI nano composite material.
2, preparing a copper ion sensor:
s1, preparing the black phosphorus-PEI nano composite material into 5mg/mL aqueous solution;
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 nanosheet comprises the following steps:
(1) PDDA was prepared as a 5mg/mL aqueous PDDA solution (3mL), which was then deoxygenated with argon and nitrogen inert gas for 10 min.
(2) And centrifuging the dispersion liquid of the black phosphorus nanosheet at 10000rpm/min for 20min and washing with deionized water for 2 times. And adding the centrifuged 1mg of black phosphorus nanosheet into the prepared PDDA aqueous solution, and carrying out deoxygenation treatment for 20min by using argon and nitrogen inert gas again.
(3) The reaction was stirred at 500rpm/min for 24h at room temperature. And after the reaction is finished, washing the reaction product for 3 times by using deionized water to obtain the ultrathin high-stability black phosphorus-PDDA nano composite material.
2, preparing a copper ion sensor:
s1, preparing the black phosphorus-PDDA nano composite material into 5mg/mL aqueous solution;
and S2, dropwise adding 5 mu L of the prepared black phosphorus-PDDA nano composite material solution onto a working electrode of the printing electrode, and airing at room temperature to obtain the sensor.
Example 7
1. The preparation method of the ultrathin high-stability black phosphorus nanosheet comprises the following steps:
(1) PDDA was prepared as a 10mg/mL aqueous PDDA solution (1.5mL), which was then deoxygenated with an inert gas argon for 20 min.
(2) And centrifuging the dispersion liquid of the black phosphorus nanosheet at 10000rpm/min for 20min and washing the dispersion liquid with deionized water for 5 times. And adding the centrifuged 1mg of black phosphorus nanosheet into the prepared PDDA aqueous solution, and carrying out deoxygenation treatment for 20min by using argon inert gas again.
(3) The reaction was stirred at 500rpm/min for 72h at room temperature. And after the reaction is finished, washing the reaction product for 2 times by using deionized water to obtain the ultrathin high-stability black phosphorus-PDDA nano composite material.
2, preparing a copper ion sensor:
s1, preparing the black phosphorus-PDDA nano composite material into 10mg/mL aqueous solution;
and S2, dropwise adding 5 mu L of the prepared black phosphorus-PDDA nano composite material solution onto a working electrode of the printing electrode, and airing at room temperature to obtain the sensor.
Test example
1, physical and chemical Property test
The black phosphorus-PEI nano composite material sheet modified by the PEI prepared in example 1 is compared with a single black phosphorus nano sheet, the structural characterization is carried out, and the experimental result is shown in figure 1.
FIG. 1 shows TEM and AFM results of the morphology characterization of a black phosphorus-PEI nanocomposite material and an individual black phosphorus nanosheet, wherein it can be seen that the individual black phosphorus nanosheet has a relatively thick sheet layer and is easily oxidized to form holes, as shown in FIG. 1(A), and the PEI-modified black phosphorus-PEI nanocomposite material has a relatively thin sheet layer and is not easily oxidized and degraded, as shown in FIG. 1 (B); AFM results showed that the thickness of the individual black phosphorus nanoplates is 5nm as shown in FIG. 1(C) and the thickness of the black phosphorus-PEI nanocomposite is 1.5nm as shown in FIG. 1 (D).
2, sensor-specific detection
The specific experimental operation steps are as follows: measurement of Cu ion detection sensor pair Cu prepared in example 1 by chronoamperometry2+Specificity of detection. The specific test conditions are as follows: sequentially adding Cu with the same concentration into 0.01M PBS solution at a potential of-0.2V every 20-100s2+And interfering ion K+、Ca2+、Ni2+、Zn2+、Mn2+、Fe3+、Fe2+Etc. and recording the current response graph. (wherein the concentration range of the PBS solution used in the electrochemical detection of the sensor is 0.01-0.1M, and the range of the applied potential by the chronoamperometry is-0.25V-0.15V).
And (4) experimental conclusion: detection of Cu by Cyclic Voltammetry (CV) on electrochemical sensor constructed by black phosphorus-PEI nanocomposite2+The ability of (A) was tested, and it can be seen from FIG. 2(A) that the black phosphorus-PEI nanocomposite can directly react with Cu without anodic stripping voltammetry2+The reduction test is carried out, the detection process is greatly simplified, and the detection performance of the sensor is improved, wherein the sensor is used for detecting 0-200 mu M Cu2+Has obvious current response. The anti-interference capability of the sensor is tested by adopting a timing current method, and the selected interferent is the common Cu in the water sample2+Some ions coexist, such as: k+、Ca2+、Ni2+、Zn2+、Mn2+、Fe3+、Fe2+And the like. As can be seen in FIG. 2(B), the sensor pair Cu2+Showing a clear response with little response to other interferents at the same concentration. This indicates that the sensor is paired with Cu2+Has better selectivity.
In addition, the stability of the individual black phosphorus nanosheets and the prepared black phosphorus-PEI nanocomposite was studied. As can be seen in FIG. 3, the black phosphorus-PEI nanocompositeThe material can still maintain 99.7 percent of the initial current response after 10 days, and the single black phosphorus nanosheet is opposite to Cu2+The current response of (a) decays rapidly and approaches almost zero after 10 days. This indicates that the black phosphorus-PEI nanocomposite has better stability than the black phosphorus nanoplate.
In addition, Cyclic Voltammetry (CV) was used to test Cu constructed on different materials2+The performance of the sensors was investigated in comparison. As can be seen in FIG. 4, black phosphorus (A) alone versus 200 μ M Cu2+Little response, PEI alone (E) to 200. mu.M Cu2+Shows only weak reduction peaks, and the sensor pair constructed based on the black phosphorus-PEI nanocomposite (corresponding to examples 1-3: respectively, wherein the mass ratios of the black phosphorus to the PEI nanosheet in the graphs (B), (C) and (D) are 1:10, 1:15 and 1:20) is 200 mu M Cu2+There are distinct reduction peaks in the CV response of FIG. 4(F) is a histogram of the peak currents corresponding to the responses of FIGS. 4(A), (B), (C), (D), (E), from which it can be seen that the black phosphorus-PEI (1:15) nanocomposite is paired with 200. mu.M Cu2+The maximum response peak current value shows that the Cu is constructed based on the black phosphorus-PEI (1:15) nano composite material2+The best performance of the sensor.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. An ultrathin high-stability black phosphorus nanocomposite is characterized in that: the black phosphorus nanocomposite is obtained by combining a black phosphorus nanosheet and an organic high molecular polymer through electrostatic adsorption; the organic high molecular polymer comprises branched polyethyleneimine and/or polydiallyldimethylammonium chloride; the organic high molecular polymer is coated on the surface of the black phosphorus nanosheet and is embedded between layers of the black phosphorus nanosheet, so that the black phosphorus nanocomposite with a sandwich structure is formed.
2. A method for preparing the ultra-thin high-stability black phosphorus nanocomposite as claimed in claim 1, wherein: the method comprises the following steps:
(1) deoxidizing the organic high molecular polymer aqueous solution for 3-20min by using inert gas;
(2) centrifuging the dispersion liquid of the black phosphorus nanosheets, washing the dispersion liquid with water for 2-5 times, adding the washed black phosphorus nanosheets into the organic high-molecular polymer aqueous solution obtained in the step (1), carrying out deoxygenation treatment with inert gas, and continuously stirring and reacting for 24-72h at room temperature;
(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.
3. The method for preparing the ultrathin high-stability black phosphorus nanocomposite material as claimed in claim 2, wherein the method comprises the following steps: in the step (1) and the step (2), the inert gas is argon or/and nitrogen; the concentration of the organic high molecular polymer aqueous solution in the step (1) is 1-10 mg/mL.
4. The method for preparing the ultrathin high-stability black phosphorus nanocomposite material as claimed in claim 2, wherein the method comprises the following steps: in the step (2), the mass ratio of the black phosphorus nanosheet to the organic high molecular polymer is 1: 5-1: 30.
5. cu2+A detection sensor, characterized in that the sensor comprises the ultra-thin high stability black phosphorus nanocomposite material as claimed in claim 1.
6. Detect Cu2+The method of (2), characterized by: the method comprises the following steps: use of Cu as claimed in claim 62+Detection sensor for Cu in PBS solution2+And (4) detecting the solution, wherein the concentration of the PBS solution is in the range of 0.01-0.1M.
7. Detection C according to claim 6u2+The method of (2), characterized by: detection is carried out by cyclic voltammetry CV, where Cu2+The test conditions were: potential window range: -0.7 to-0.3V to 0.3 to 0.7V, sweep speed range: 10 to 100 mV/s.
8. Detecting Cu according to claim 62+The method of (2), characterized by: the measurement is carried out by adopting a chronoamperometry IT, and the specific test conditions are as follows: the applied potential is in the range of-0.25 to-0.15V, and 0.25 to 50 mu M of Cu is added into the PBS solution every 10 to 100s2+The solution was dissolved and the current response profile recorded.
9. Cu as claimed in claim 52+The preparation method of the detection sensor is characterized by comprising the following steps: the method comprises the following steps:
s1, dissolving the black phosphorus nano composite material in water to prepare a black phosphorus nano composite material aqueous solution;
and S2, dropwise adding 1-10 mu L of the black phosphorus nanocomposite aqueous solution onto a working electrode of a printed electrode, and airing at room temperature to obtain the sensor.
10. Cu according to claim 92+The preparation method of the detection sensor is characterized by comprising the following steps: the concentration of the black phosphorus nano composite material aqueous solution in S1 is 5-15 mg/mL.
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