Preparation method and application of PEDOT coated amorphous NiCoP / CC material

Abstract

The invention provides a preparation method of a PEDOT (poly (3, 4-ethylenedioxythiophene)) coated amorphous NiCoP / CC (NiCoP / CC) material, which is characterized by comprising the following steps: S1, preparing the NiCoP / CC material by adopting an electrochemical deposition method; and S2, placing the NiCoP / CC material in an aqueous solution containing EDOT, lauryl sodium sulfate and lithium perchlorate for electrochemical polymerization of PEDOT to prepare the NiCoP / CC-PEDOT composite material. The NiCoP / CC material prepared by an electrochemical deposition method has a more complex electronic structure, and the catalytic performance of the material is enhanced, so that an amorphous material has higher activity than a crystalline material. The surface of the CC / NiCoP composite electrode material is coated with a layer of PEDOT to block the reaction of the material in a neutral environment so as to play a role in protecting the electrode material. Lauryl sodium sulfate is added into the deposition liquid so as to better disperse the EDOT monomer. Meanwhile, the ClO4 <-> provides anions required by the PEDOT to absorb from a solution in the electropolymerization process, so that the PEDOT is successfully polymerized.

Description

Technical Field

[0001] This invention relates to the field of micro / nanomaterial preparation technology, and in particular to a method for preparing a PEDOT-coated amorphous NiCoP / CC material and its application in dopamine detection. Background Technology

[0002] Dopamine (DA), a crucial neurotransmitter in the mammalian central nervous system, plays a vital role in various physiological processes, including motor control, cognitive function, mood regulation, and reward mechanisms. Studies have shown that abnormal DA levels can lead to numerous mental health disorders, such as depression, attention deficit hyperactivity disorder (ADHD), and Parkinson's disease. Therefore, developing highly sensitive and selective DA detection technologies is of great significance for neuroscience research and clinical diagnosis. Electrochemical biosensors for DA detection have attracted increasing attention due to their simplicity, high sensitivity, rapid response, and ease of miniaturization.

[0003] In recent years, bimetallic phosphides have attracted widespread attention as highly sensitive sensing materials and have been widely used in electrochemical biosensors. When transition metal elements form binary transition metal phosphides, they exhibit multiple oxidation states and produce strong synergistic effects, thereby greatly improving their electrochemical performance. For example, the synergistic effect between transition metal elements in bimetallic phosphides can effectively reduce the reaction barrier, produce good catalytic kinetics, and enhance catalytic performance. In addition, with the development of transition metal elements into bimetallic transition metal phosphides, they are conducive to generating abundant active sites and regulating electronic structure. NiCoP, as a metal-rich phosphide, is gradually being applied in the fields of catalysis and sensors due to its high catalytic activity, metal-like properties, and good chemical stability. However, the synthesis process of NiCoP has obvious drawbacks. This preparation method requires low-temperature phosphating after hydrothermal reaction, with harsh reaction conditions, expensive equipment, and long and complex waiting time. In addition, toxic and flammable phosphine gas is generated during the process. Moreover, electrochemically synthesized NiCoP is unstable when tested in phosphate buffer solution, hindering the detection of DA. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a PEDOT-coated amorphous NiCoP / CC material for dopamine detection and its preparation method. The prepared NiCoP / CC@PEDOT material exhibits a short detection response time, high sensitivity, and excellent electrochemical performance.

[0005] The specific technical solution is as follows: A method for preparing PEDOT-coated amorphous NiCoP / CC material, characterized by including the following steps.

[0006] S1 uses electrochemical deposition to prepare NiCoP / CC materials;

[0007] S2 prepared NiCoP / CC@PEDOT composite material by electrochemically polymerizing PEDOT in an aqueous solution containing EDOT, sodium dodecyl sulfate and lithium perchlorate.

[0008] Preferably, step 1 specifically involves: using a three-electrode system, with carbon cloth as the working electrode, and depositing NiCoP using cyclic voltammetry. The deposition potential is set to -1.5 to -0.1 V, and the scan rate is 10 mV s⁻¹. The growth of NiCoP is controlled by adjusting the number of deposition cycles. After deposition, the carbon cloth is removed, washed, and dried to obtain NiCoP / CC material.

[0009] Preferably, the carbon cloth has a size of 1.5 × 1.5 cm.

[0010] Preferably, the number of deposition cycles in step 1 is 1 to 30.

[0011] Preferably, the electrochemical deposition solution used in cyclic voltammetry deposition is obtained by dissolving NiSO4·7H2O, CoSO4·7H2O, NaH2PO2, and Na3C6H5O7·2H2O in deionized water.

[0012] Preferably, the concentrations of NiSO4·7H2O in the electrochemical deposition solution are 0.047 mol / L, CoSO4·7H2O are 0.025 mol / L, NaH2PO2 is 0.500 mol / L, and Na3C6H5O7·2H2O is 0.100 mol / L.

[0013] Preferably, in step 2, the concentration of EDOT is 0.03 mol / L, the concentration of sodium dodecyl sulfate is 0.07 mol / L, and the concentration of lithium perchlorate is 0.07 mol / L.

[0014] Preferably, the deposition time of electrochemically polymerized PEDOT in step 2 is 900–2400 s, and the potential of electrochemically polymerized PEDOT is 0.8–1.1 V.

[0015] Preferably, the deposition time of electrochemically polymerized PEDOT in step 2 is 1800s, and the potential of electrochemically polymerized PEDOT is 0.9V.

[0016] An application of a method for preparing PEDOT-coated amorphous NiCoP / CC material in dopamine detection of the prepared NiCoP / CC@PEDOT composite material.

[0017] The beneficial effects of this invention are as follows:

[0018] 1. A layer of polymer is coated onto the surface of the CC / NiCoP composite electrode material to prevent reaction in a neutral environment, thus protecting the electrode material. PEDOT synthesis is mostly achieved through the polymerization of 3,4-ethylenedioxythiophene, but EDOT has very low solubility in water. Therefore, sodium dodecyl sulfate is added to the deposition solution to better disperse the EDOT monomer. Meanwhile, ClO... 4- This provides a method for PEDOT to absorb the required anions from the solution during electropolymerization, thereby enabling successful PEDOT polymerization.

[0019] 2. Amorphous NiCoP prepared by electrochemical deposition has a more complex electronic structure. The absence of an ordered lattice structure leads to an increase in the number of active sites, which enhances the catalytic performance of the material and thus exhibits enhanced electrochemical activity. It can effectively participate in electrochemical reactions, making amorphous materials more active than crystalline materials.

[0020] 3. Sodium citrate plays a significant role in NiCoP electrochemical deposition. As a strong complexing agent, it reacts with Ni... 2+ Co 2+ By complexing metal ions, the concentration of free ions is reduced, the ion diffusion rate is changed, and the deposition rate is slowed down. Because it can change the reduction potential of metal ions, it affects the relative deposition amount of different metal ions and can also regulate crystal growth, thus changing the composition and structure of the coating. By regulating the metal ion deposition process and influencing crystal growth, the uniformity and density of the coating are improved, and by changing the composition and structure of the coating, it also affects its electrochemical performance.

[0021] 4. Coating amorphous NiCoP / CC materials with PEDOT improves their adsorption properties and increases electron diffusion paths. First, the PEDOT nanolayer possesses robustness, conductivity, porosity, and continuity, which not only enhances electron transport rates but also increases the number of active sites for ion adsorption and efflux. Second, PEDOT provides a large electrochemical specific surface area, enabling contact with more dopamine molecules. Finally, electrochemically synthesized amorphous NiCoP exhibits instability in phosphate buffer solutions. Secondary electrochemical deposition of PEDOT allows NiCoP / CC@PEDOT materials to be used for dopamine detection in neutral environments, increasing the composite material's stability and demonstrating high sensitivity, low detection limits, and excellent anti-interference properties. The optimized process parameters were 0.9V and 1800s. (The technical disclosure states that the preferred time is 1800s, but specific examples of a deposition time of 1800s are not provided in the embodiments.)

[0022] A highly sensitive electrochemical biosensor for dopamine was fabricated. The effective incorporation of amorphous NiCoP into the electrochemical detection of dopamine broadens the potential applications of amorphous transition metal phosphides. This combination not only provides a new and efficient method for dopamine detection but also lays the foundation for future research into the application of amorphous composite materials in the field of electrochemical sensing. Attached Figure Description

[0023] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0024] in:

[0025] Figure 1 The image shows a SEM image of the NiCoP / CC@PEDOT material in Example 1.

[0026] Figure 2 The image shows a SEM image of the NiCoP / CC material in Example 1.

[0027] Figure 3 The image shows the It curve of the electrochemical sensing of dopamine by NiCoP / CC@PEDOT in Example 1.

[0028] Figure 4 The image shows the It curves of the NiCoP / CC@PEDOT composite materials prepared at different polymerization potentials in the examples, representing the electrochemical sensing of dopamine.

[0029] Figure 5 The image shows the It curves of the NiCoP / CC@PEDOT composite materials prepared at different polymerization times in the examples, representing the electrochemical sensing of dopamine.

[0030] (It is recommended to provide multiple sets of examples and comparative images for comparison of effects) Detailed Implementation

[0031] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Many specific details are set forth in the following description to provide a thorough understanding of the present invention; however, the present invention may be implemented in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0032] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0033] Example 1

[0034] Step 1: Weigh 0.3943g NiSO4·7H2O, 0.2108g CoSO4·7H2O, 1.3197g NaH2PO2, and 0.8823g Na3C6H5O7·2H2O and dissolve them in 30mL of deionized water by stirring to form an electrochemical deposition solution;

[0035] Step 2: Using a three-electrode system, carbon cloth was used as the working electrode. NiCoP was deposited using cyclic voltammetry, with the deposition potential set to -1.5 to -0.1 V and the scan rate at 10 mV / s. -1 The deposition cycle was 20 cycles. After the program was completed, the carbon cloth was removed, washed, and vacuum dried to obtain the NiCoP / CC material. Its SEM image is shown below. Figure 2 As shown;

[0036] Step 3: The NiCoP / CC material was electrochemically polymerized with PEDOT in an aqueous solution containing 0.03M EDOT, 0.07M sodium dodecyl sulfate, and 0.1M lithium perchlorate. The deposition potential was 0.9V, and the deposition time was 1800s, thus preparing the NiCoP / CC@PEDOT composite material. Its SEM image is shown below. Figure 1 As shown.

[0037] A highly sensitive electrochemical biosensor for dopamine was fabricated using the NiCoP / CC@PEDOT composite material prepared in step 3. The It curve for its electrochemical sensing of dopamine is shown in the figure below. Figure 3 As shown.

[0038] Example 2

[0039] Step 1: Weigh 0.3943g NiSO4·7H2O, 0.2108g CoSO4·7H2O, 1.3197g NaH2PO2, and 0.8823g Na3C6H5O7·2H2O and dissolve them in 30mL of deionized water by stirring to form an electrochemical deposition solution;

[0040] Step 2: Using a three-electrode system, carbon cloth was used as the working electrode. NiCoP was deposited using cyclic voltammetry, with the deposition potential set to -1.5 to -0.1 V and the scan rate at 10 mV / s. -1The deposition cycle was 20 cycles. After the program was completed, the carbon cloth was removed, washed, and vacuum dried to obtain NiCoP / CC material.

[0041] Step 3: NiCoP / CC material was placed in an aqueous solution containing 0.03M EDOT, 0.07M sodium dodecyl sulfate and 0.1M lithium perchlorate to electrochemically polymerize PEDOT. The deposition potential was 0.8V and the deposition time was 900s, thus preparing NiCoP / CC@PEDOT composite material.

[0042] Example 3

[0043] Step 1: Weigh 0.3943g NiSO4·7H2O, 0.2108g CoSO4·7H2O, 1.3197g NaH2PO2, and 0.8823g Na3C6H5O7·2H2O and dissolve them in 30mL of deionized water by stirring to form an electrochemical deposition solution;

[0044] Step 2: Using a three-electrode system, carbon cloth was used as the working electrode. NiCoP was deposited using cyclic voltammetry, with the deposition potential set to -1.5 to -0.1 V and the scan rate at 10 mV / s. -1 The deposition cycle was 20 cycles. After the program was completed, the carbon cloth was removed, washed, and vacuum dried to obtain NiCoP / CC material.

[0045] Step 3: NiCoP / CC material was placed in an aqueous solution containing 0.03M EDOT, 0.07M sodium dodecyl sulfate and 0.1M lithium perchlorate to electrochemically polymerize PEDOT. The deposition potential was 0.9V and the deposition time was 900s, thus preparing NiCoP / CC@PEDOT composite material.

[0046] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A preparation method of PEDOT-coated amorphous NiCoP / CC material, characterized in that, The method comprises the following steps: S1, preparing a NiCoP / CC material by electrochemical deposition; S2, electrochemically polymerizing PEDOT in an aqueous solution containing EDOT, sodium dodecyl sulfate and lithium perchlorate to obtain a NiCoP / CC@PEDOT composite material.

2. The preparation method of PEDOT-coated amorphous NiCoP / CC material according to claim 1, characterized in that, In step 1, a three-electrode system is used, carbon cloth is used as a working electrode, and NiCoP is deposited by cyclic voltammetry, the deposition potential is set to-1.5 to-0.1 V, the scanning rate is 10 mV s-1, the growth of NiCoP is controlled by adjusting the deposition cycles, and after the deposition is completed, the carbon cloth is taken out, washed and dried to obtain the NiCoP / CC material.

3. The preparation method of PEDOT-coated amorphous NiCoP / CC material according to claim 2, characterized in that, The size of the carbon cloth is 1.5*1.5 cm.

4. The preparation method of PEDOT-coated amorphous NiCoP / CC material according to claim 2, characterized in that, In step 1, the deposition cycles are 1 to 30 cycles.

5. The preparation method of PEDOT-coated amorphous NiCoP / CC material according to claim 2, characterized in that, The electrochemical deposition solution used in the cyclic voltammetry deposition is obtained by dissolving NiSO4·7H2O, CoSO4·7H2O, NaH2PO2 and Na3C6H5O7·2H2O in deionized water.

6. The preparation method of PEDOT-coated amorphous NiCoP / CC material according to claim 5, characterized in that, In the electrochemical deposition solution, the concentration of NiSO4·7H2O is 0.047 mol / L, the concentration of CoSO4·7H2O is 0.025 mol / L, the concentration of NaH2PO2 is 0.500 mol / L, and the concentration of Na3C6H5O7·2H2O is 0.100 mol / L.

7. The method for preparing a PEDOT-coated amorphous NiCoP / CC material according to claim 1, characterized in that, In step 2, the concentration of EDOT is 0.03 mol / L, the concentration of sodium dodecyl sulfate is 0.07 mol / L, and the concentration of lithium perchlorate is 0.07 mol / L.

8. The method for preparing a PEDOT-coated amorphous NiCoP / CC material according to claim 1, characterized in that, In step 2, the deposition time of electrochemically polymerizing PEDOT is 900 to 2400 s, and the potential of electrochemically polymerizing PEDOT is 0.8 to 1.1 V.

9. The method for preparing a PEDOT-coated amorphous NiCoP / CC material according to claim 1, characterized in that, In step 2, the deposition time of electrochemically polymerizing PEDOT is 1800 s, and the potential of electrochemically polymerizing PEDOT is 0.9 V.

10. The application of the NiCoP / CC@PEDOT composite material prepared by the preparation method of PEDOT-coated amorphous NiCoP / CC material according to any one of claims 1-9 in dopamine detection.

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