Preparation method and application of chiral conductive polymer / sulfide composite material

Abstract

The invention discloses a preparation method and application of a chiral conductive polymer / sulfide composite material, and relates to a preparation method and application of a conductive polymer composite material. The invention aims to solve the problems of high cost and strong scarcity of the existing noble metal-based catalyst, and low catalytic efficiency and lack of electron spin regulation ability of an achiral transition metal catalyst. The method comprises the following steps: 1, preparing an NLLA solution; 2, preparing an An solution; 3, preparing a CSA solution; 4, preparing an APS solution; 5, generating a chiral polyaniline nanofiber membrane on an air-water interface; 6, preparing a Ni (NO3) 2 solution; 7, preparing a diluted hydrochloric acid solution; 8, preparing a Na2S solution; and 9, growing a nickel sulfide catalyst membrane on the chiral polyaniline nanofiber membrane. The catalyst is used for electrocatalytic oxidation of glucose.

Description

Technical Field

[0001] The invention relates to a preparation method of a conductive polymer composite material and application thereof. Background Art

[0002] The key to building a green, low-carbon economy lies in replacing fossil resources with renewable biomass. Glucose, the most abundant naturally occurring monosaccharide, is inexpensive, non-toxic, and renewable. It can be electrocatalytically converted into high-value-added chemicals such as gluconic acid, sorbitol, and 5-hydroxymethylfurfural. Furthermore, replacing the typical slow oxygen evolution reaction (OER) at the anode with the glucose oxidation reaction (GOR) significantly reduces the potential required for hydrogen production from water electrolysis, improves energy efficiency, and enables the coordinated production of hydrogen and chemicals.

[0003] The rational design of catalyst systems is a key challenge in advancing this technology towards large-scale application. Precious metals (such as Pt and Ru) offer excellent activity but are limited by scarcity and cost. Achiral transition metal sulfides (such as Ni, Co, and Fe) offer advantages in cost and availability, but they suffer from low catalytic efficiency and lack the ability to manipulate electron spin. Summary of the Invention

[0004] The present invention aims to solve the problems of high cost and scarcity of existing noble metal-based catalysts, low catalytic efficiency and lack of electron spin regulation ability of achiral transition metal catalysts, and further provide a preparation method and application of chiral conductive polymer / sulfide composite materials.

[0005] A method for preparing a chiral conductive polymer / sulfide composite material is carried out according to the following steps:

[0006] 1. Add N-lauroyl-L-alanine to chloroform solution and stir to dissolve to obtain NLLA solution;

[0007] 2. Add aniline monomer into deionized water and stir to dissolve to obtain An solution;

[0008] 3. Add camphorsulfonic acid to deionized water and stir to dissolve to obtain CSA solution;

[0009] The camphorsulfonic acid is L-camphorsulfonic acid or D-camphorsulfonic acid;

[0010] 4. Add ammonium persulfate to deionized water and stir to dissolve to obtain an APS solution;

[0011] 5. An solution and CSA solution were mixed to obtain an An / CSA system, NLLA solution was added dropwise to the surface of the An / CSA system, and then the system was allowed to stand at room temperature once, and then APS solution was injected into the bottom of the An / CSA system, and then the system was allowed to stand at room temperature a second time to form a chiral polyaniline nanofiber membrane at the air-water interface, thereby obtaining a solution with a chiral polyaniline nanofiber membrane on the surface;

[0012] 6. Add nickel nitrate hexahydrate into deionized water and stir to dissolve to obtain a Ni(NO3)2 solution;

[0013] 7. Add concentrated hydrochloric acid to deionized water and stir to dissolve to obtain a dilute hydrochloric acid solution;

[0014] 8. Add sodium sulfide to deionized water and stir to dissolve to obtain Na2S solution;

[0015] 9. The solution with the surface covered with chiral polyaniline nanofiber membrane is placed in a confined space, and then Ni(NO3)2 solution is injected into the bottom of the solution with the surface covered with chiral polyaniline nanofiber membrane. At the same time, in the confined space, dilute hydrochloric acid solution is added to the Na2S solution to release H2S gas. Finally, the solution is allowed to stand at room temperature to grow a nickel sulfide catalyst film on the chiral polyaniline nanofiber membrane, thereby obtaining a chiral conductive polymer / sulfide composite material.

[0016] The invention discloses an application of a chiral conductive polymer / sulfide composite material. The chiral conductive polymer / sulfide composite material is used as a catalyst for electrocatalytic oxidation of glucose.

[0017] The beneficial effects of the present invention are:

[0018] This invention uses N-lauroyl-L-alanine to construct a two-dimensional confined reaction space at the gas-liquid interface. This is combined with controlled oxidative polymerization initiated by ammonium persulfate to efficiently synthesize polyaniline. Furthermore, camphorsulfonic acid enantiomers are used to induce a stable chiral structure in the polyaniline backbone, enabling the transfer of molecular chirality to the polymer chain. Furthermore, a gas diffusion strategy is used to in situ generate nickel sulfide at the interface, ultimately creating a chiral polyaniline@nickel sulfide composite membrane material with synergistic effects of chirality, conductivity, and catalytic activity. This chiral interface-induced electron spin polarization and the synergistic mechanism of transition metal-based catalysts are utilized to achieve electrocatalytic oxidation of glucose. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a scanning electron microscope image of M-PANI prepared in step 5 of Example 1;

[0020] Figure 2 This is a scanning electron microscope image of P-PANI prepared in step 5 of Example 2;

[0021] Figure 3Transmission electron microscope images of M-PANI and P-PANI prepared in step 5 of Examples 1 and 2;

[0022] Figure 4 Transmission electron microscope image of PANI prepared in step 5 of comparative experiment 1;

[0023] Figure 5 This is the Raman test spectrum of P-PANI prepared in step 5 of Example 2;

[0024] Figure 6 This is the Fourier transform infrared (FT-IR) spectrum of M-PANI prepared in step 5 of Example 1;

[0025] Figure 7 The UV-visible (UV-vis) spectra of M-PANI and P-PANI prepared in step 5 of Examples 1 and 2;

[0026] Figure 8 Circular dichroism (CD) spectra of M-PANI and P-PANI prepared in step 5 of Examples 1 and 2;

[0027] Figure 9 This is the UV-vis spectrum of L-CSA used in step 3 of Example 1;

[0028] Figure 10 CD spectra of L-CSA and D-CSA used in step 3 of Examples 1 and 2;

[0029] Figure 11 Transmission electron microscope image of P-PANI@NiS prepared in Example 2 and its element distribution;

[0030] Figure 12 This is a high-resolution transmission electron microscopy image of P-PANI@NiS prepared in Example 2;

[0031] Figure 13 The micro-area diffraction images of P-PANI@NiS prepared in Example 2 and NiS prepared in Comparative Experiment 2;

[0032] Figure 14 Comparison of Raman spectra of M-PANI prepared in step 5 of Example 1, M-PANI@NiS prepared in step 9, and NiS prepared in comparative experiment 2;

[0033] Figure 15 FT-IR spectra comparison of M-PANI prepared in step 5 of Example 1, M-PANI@NiS prepared in step 9, and NiS prepared in comparative experiment 2;

[0034] Figure 16UV-vis images of M-PANI@NiS and P-PANI@NiS prepared in Examples 1 and 2;

[0035] Figure 17 CD images of M-PANI@NiS and P-PANI@NiS prepared in Examples 1 and 2;

[0036] Figure 18 LSV polarization curves of the P-PANI electrode, P-PANI@NiS electrode, NiS electrode, and bare ITO electrode prepared in Example 1 and Comparative Experiment 2 measured under the same standard;

[0037] Figure 19 The overpotentials of the P-PANI@NiS electrode and NiS electrode prepared in Example 1 and Comparative Experiment 2 in OER and GOR (at 10 mA / cm 2 as a benchmark);

[0038] Figure 20 Comparison of the Tafel slopes of the P-PANI@NiS electrode and NiS electrode prepared in Example 1 and Comparative Experiment 2 in OER and GOR;

[0039] Figure 21 EIS curves of glucose oxidation using the P-PANI@NiS electrode and NiS electrode prepared in Example 1 and Comparative Experiment 2;

[0040] Figure 22 Polarization curves of glucose oxidation performed on the M-PANI@NiS electrode, P-PANI@NiS electrode, and PANI@NiS electrode prepared in Examples 1 to 2 and Comparative Experiment 1;

[0041] Figure 23 The overpotential (10 mA / cm2) of glucose oxidation on the M-PANI@NiS electrode, P-PANI@NiS electrode and PANI@NiS electrode prepared in Examples 1 to 2 and Comparative Experiment 1 2 Bottom) comparison chart;

[0042] Figure 24 Tafel slopes of glucose oxidation performed on the M-PANI@NiS electrode, P-PANI@NiS electrode, and PANI@NiS electrode prepared in Examples 1 to 2 and Comparative Experiment 1;

[0043] Figure 25 EIS images of glucose oxidation of the M-PANI@NiS electrode, P-PANI@NiS electrode, and PANI@NiS electrode prepared in Examples 1 to 2 and Comparative Experiment 1. DETAILED DESCRIPTION

[0044] Specific embodiment 1: This embodiment is a method for preparing a chiral conductive polymer / sulfide composite material, which is carried out according to the following steps:

[0045] 1. Add N-lauroyl-L-alanine to chloroform solution and stir to dissolve to obtain NLLA solution;

[0046] 2. Add aniline monomer into deionized water and stir to dissolve to obtain An solution;

[0047] 3. Add camphorsulfonic acid to deionized water and stir to dissolve to obtain CSA solution;

[0048] The camphorsulfonic acid is L-camphorsulfonic acid or D-camphorsulfonic acid;

[0049] 4. Add ammonium persulfate to deionized water and stir to dissolve to obtain an APS solution;

[0050] 5. An solution and CSA solution were mixed to obtain an An / CSA system, NLLA solution was added dropwise to the surface of the An / CSA system, and then the system was allowed to stand at room temperature once, and then APS solution was injected into the bottom of the An / CSA system, and then the system was allowed to stand at room temperature a second time to form a chiral polyaniline nanofiber membrane at the air-water interface, thereby obtaining a solution with a chiral polyaniline nanofiber membrane on the surface;

[0051] 6. Add nickel nitrate hexahydrate into deionized water and stir to dissolve to obtain a Ni(NO3)2 solution;

[0052] 7. Add concentrated hydrochloric acid to deionized water and stir to dissolve to obtain a dilute hydrochloric acid solution;

[0053] 8. Add sodium sulfide to deionized water and stir to dissolve to obtain Na2S solution;

[0054] 9. The solution with the surface covered with chiral polyaniline nanofiber membrane is placed in a confined space, and then Ni(NO3)2 solution is injected into the bottom of the solution with the surface covered with chiral polyaniline nanofiber membrane. At the same time, in the confined space, dilute hydrochloric acid solution is added to the Na2S solution to release H2S gas. Finally, the solution is allowed to stand at room temperature to grow a nickel sulfide catalyst film on the chiral polyaniline nanofiber membrane, thereby obtaining a chiral conductive polymer / sulfide composite material.

[0055] The present embodiment adopts N-lauroyl-L-alanine as an amphiphilic surfactant, and its molecules interact with the air interface through the hydrophobic end (lauroyl chain) and the hydrophilic end (L-alanine group) and the water phase, and spontaneously form a monolayer at the gas-liquid interface. The monolayer can construct a two-dimensional restricted reaction space, and regulate its orientation by limiting the lateral growth of polyaniline fibers. In the polymerization reaction, ammonium persulfate is used as an oxidation initiator to trigger the gradual oxidative polymerization of aniline monomers. Camphorsulfonic acid enantiomers are used as chiral inducers to induce polyaniline molecular chains to form a helical conformation through steric hindrance, thereby realizing the transfer of chirality from the molecular scale to the polyaniline chain. Subsequently, based on the gas diffusion control strategy, hydrogen sulfide is reacted with the nickel nitrate precursor in the liquid phase, and the growth of nickel sulfide is achieved at the liquid phase interface with the help of chiral polyaniline.

[0056] This embodiment of constructing a "chiral conductive polymer / sulfide" composite system has dual advantages: the conductive polymer can introduce stable chiral centers through molecular design to achieve spin regulation; the transition metal sulfide provides rich and adjustable active sites. The two work together to achieve high conductivity, high activity and low cost.

[0057] The beneficial effects of this embodiment are:

[0058] This method uses N-lauroyl-L-alanine to create a two-dimensional confined reaction space at the gas-liquid interface. This is combined with controlled oxidative polymerization initiated by ammonium persulfate to efficiently synthesize polyaniline. Furthermore, camphorsulfonic acid enantiomers are used to induce a stable chiral structure in the polyaniline backbone, enabling the transfer of molecular chirality to the polymer chain. Furthermore, a gas diffusion strategy is used to in situ generate nickel sulfide at the interface, ultimately creating a chiral polyaniline@nickel sulfide composite film material with synergistic effects of chirality, conductivity, and catalytic activity. The electrocatalytic oxidation of glucose is achieved by utilizing the synergistic mechanism of electron spin polarization induced by the chiral interface and transition metal-based catalysts.

[0059] Specific embodiment 2: This embodiment differs from specific embodiment 1 in that the concentration of N-lauroyl-L-alanine in the NLLA solution in step 1 is 1.8 mmol / L to 2 mmol / L. Other aspects are the same as those of specific embodiment 1.

[0060] Specific embodiment 3: This embodiment differs from specific embodiment 1 or 2 in that the concentration of aniline monomer in the An solution in step 2 is 0.25 mol / L to 0.27 mol / L. Other aspects are the same as specific embodiment 1 or 2.

[0061] Specific embodiment 4: This embodiment differs from specific embodiments 1 to 3 in that the concentration of camphorsulfonic acid in the CSA solution in step 3 is 0.35 mol / L to 0.45 mol / L. Other aspects are the same as specific embodiments 1 to 3.

[0062] Specific embodiment 5: This embodiment differs from specific embodiments 1 to 4 in that the concentration of ammonium persulfate in the APS solution in step 4 is 3.1 mol / L to 3.3 mol / L. Other aspects are the same as specific embodiments 1 to 4.

[0063] Specific embodiment 6: This embodiment differs from Specific embodiments 1 to 5 in that the volume ratio of the An solution to the CSA solution in step 5 is 1:(0.95-1.05); the volume ratio of the An solution to the NLLA solution in step 5 is (500-510):1; and the volume ratio of the An solution to the APS solution in step 5 is (10-11):1. Other aspects are the same as Specific embodiments 1 to 5.

[0064] Specific embodiment 7: This embodiment differs from Specific embodiments 1 to 6 in that, in step 5, the NLLA solution is added dropwise to the surface of the An / CSA system at a dropwise addition rate of 5 μL / s to 10 μL / s, followed by a 5-6 minute stand at room temperature. Subsequently, the APS solution is injected into the bottom of the An / CSA system at an injection rate of 0.05 mL / s to 0.1 mL / s, followed by a 10-20 hour stand at room temperature. Other steps are the same as Specific embodiments 1 to 6.

[0065] Specific embodiment 8: This embodiment differs from Specific embodiments 1 to 7 in that the concentration of nickel nitrate hexahydrate in the Ni(NO3)2 solution described in step 6 is 2 mol / L to 2.2 mol / L; the concentration of the dilute hydrochloric acid solution described in step 7 is 1 mol / L to 1.2 mol / L; and the concentration of sodium sulfide in the Na2S solution described in step 8 is 0.2 mol / L to 0.25 mol / L. This embodiment is the same as Specific embodiments 1 to 7.

[0066] Specific embodiment 9: This embodiment differs from any one of specific embodiments 1 to 8 in that: in step 9, the volume ratio of the solution coated with the chiral polyaniline nanofiber membrane to the Ni(NO3)2 solution is (10-11):1; the volume ratio of the dilute hydrochloric acid solution to the Na2S solution in step 9 is (1-1.2):1; the volume of the enclosed space in step 9 is 8L-9L; in step 9, the Ni(NO3)2 solution is injected into the bottom of the solution coated with the chiral polyaniline nanofiber membrane at an injection rate of 0.05mL / s-0.1mL / s; and in step 9, the solution is allowed to stand at room temperature for 10-20 hours. Other aspects are the same as specific embodiments 1 to 8.

[0067] Specific embodiment ten: This embodiment provides an application of a chiral conductive polymer / sulfide composite material. The chiral conductive polymer / sulfide composite material is used as a catalyst for electrocatalytic oxidation of glucose.

[0068] The following examples are used to verify the beneficial effects of the present invention:

[0069] Example 1:

[0070] A method for preparing a chiral conductive polymer / sulfide composite material is carried out according to the following steps:

[0071] 1. Add N-lauroyl-L-alanine to chloroform solution and stir to dissolve to obtain NLLA solution;

[0072] The concentration of N-lauroyl-L-alanine in the NLLA solution is 1.8 mmol / L;

[0073] 2. Add aniline monomer into deionized water and stir to dissolve to obtain An solution;

[0074] The concentration of aniline monomer in the An solution is 0.26 mol / L;

[0075] 3. Add camphorsulfonic acid to deionized water and stir to dissolve to obtain CSA solution;

[0076] The concentration of camphorsulfonic acid in the CSA solution is 0.4 mol / L;

[0077] The camphorsulfonic acid is L-camphorsulfonic acid (L-CSA);

[0078] 4. Add ammonium persulfate to deionized water and stir to dissolve to obtain an APS solution;

[0079] The concentration of ammonium persulfate in the APS solution is 3.2 mol / L;

[0080] 5. Mix 5 mL of An solution and 5 mL of CSA solution and add them to a culture dish with a diameter of 6 cm to obtain an An / CSA system. At a drop rate of 8 μL / s, 10 μL of NLLA solution is added dropwise to the surface of the An / CSA system, and then the system is allowed to stand at room temperature for 5 minutes. Then, at an injection rate of 0.08 mL / s, 0.5 mL of APS solution is injected into the bottom of the An / CSA system, and the system is allowed to stand at room temperature for 15 hours. A chiral polyaniline nanofiber membrane (M-PANI) is generated at the air-water interface, and a solution with a chiral polyaniline nanofiber membrane on the surface is obtained.

[0081] 6. Add nickel nitrate hexahydrate into deionized water and stir to dissolve to obtain a Ni(NO3)2 solution;

[0082] The concentration of nickel nitrate hexahydrate in the Ni(NO3)2 solution is 2 mol / L;

[0083] 7. Add concentrated hydrochloric acid to deionized water and stir to dissolve to obtain a dilute hydrochloric acid solution;

[0084] The concentration of the dilute hydrochloric acid solution is 1 mol / L;

[0085] 8. Add sodium sulfide to deionized water and stir to dissolve to obtain Na2S solution;

[0086] The concentration of sodium sulfide in the Na2S solution is 0.2 mol / L;

[0087] 9. The solution coated with chiral polyaniline nanofiber membrane was placed in a confined space. Then, 1 mL of Ni(NO3)2 solution was injected into the bottom of the solution coated with chiral polyaniline nanofiber membrane at an injection rate of 0.1 mL / s. At the same time, 1 mL of dilute hydrochloric acid solution was added to 1 mL of Na2S solution in the confined space to release H2S gas. Finally, the solution was allowed to stand at room temperature for 15 hours to grow a nickel sulfide catalyst film on the chiral polyaniline nanofiber membrane, thus obtaining a chiral conductive polymer / sulfide composite material (M-PANI@NiS).

[0088] The volume of the enclosed space is 8L.

[0089] Example 2: This example differs from Example 1 in that the camphorsulfonic acid in step 3 is dextrorotatory camphorsulfonic acid (D-CSA); in step 5, a chiral polyaniline nanofiber membrane (P-PANI) is formed at the air-water interface; and in step 9, a chiral conductive polymer / sulfide composite material (P-PANI@NiS) is obtained. Other steps are the same as in Example 1.

[0090] Comparative Experiment 1: This comparative experiment differs from Example 1 in that the camphorsulfonic acid described in Step 3 is racemic camphorsulfonic acid (a mixture of L- and D-camphorsulfonic acids in equal proportions); in Step 5, a polyaniline nanofiber membrane (PANI) is formed at the air-water interface; and in Step 9, a conductive polymer / sulfide composite material (PANI@NiS) is obtained. All other procedures are the same as in Example 1.

[0091] Comparative experiment 2:

[0092] In a confined space, 10 mL of water was added to a 6 cm diameter Petri dish. 10 μL of NLLA solution was added dropwise to the water surface at a drop rate of 8 μL / s. Then, 1 mL of Ni(NO3)2 solution was injected into the bottom of the water at an injection rate of 0.1 mL / s. Simultaneously, 1 mL of dilute hydrochloric acid solution was added to 1 mL of Na2S solution in a confined space to release H2S gas. Finally, the mixture was allowed to stand at room temperature for 15 h to obtain a NiS film (NiS) at the air-water interface.

[0093] The volume of the enclosed space is 8L.

[0094] (1) Chirality test of M-PANI and P-PANI:

[0095] 1. The M-PANI and P-PANI prepared in step 5 of Example 1 and 2 were loaded on a clean silica substrate, dried at room temperature (25°C), and then used for scanning electron microscopy.

[0096] 2. The M-PANI and P-PANI prepared in step 5 of Example 1 and 2 were loaded onto a clean copper mesh, dried at room temperature (25°C), and then used for transmission electron microscopy.

[0097] 3. The M-PANI and P-PANI prepared in step 5 of Example 1 and 2 were loaded on a clean quartz plate, dried at room temperature (25° C.), and then used for circular dichroism spectroscopy measurement.

[0098] 4. The M-PANI@NiS and P-PANI@NiS prepared in Examples 1 and 2 were loaded on a clean quartz plate, dried at room temperature (25°C), and then used for circular dichroism spectroscopy measurement.

[0099] (2) Electrocatalytic oxidation of glucose:

[0100] 1. The P-PANI prepared in step 5 of Example 2, the P-PANI@NiS prepared in step 9, and the NiS prepared in comparative experiment 2 were transferred to the ITO conductive surface by the pull-up method. After drying at 25°C, the P-PANI electrode, P-PANI@NiS electrode, and NiS electrode were obtained, respectively.

[0101] 2. A standard three-electrode system was used, with a catalyst-loaded ITO electrode as the working electrode, a graphite rod electrode as the counter electrode, and a mercury / mercuric oxide electrode as the reference electrode. OER was tested in a 1 mol / L potassium hydroxide electrolyte. To generate polarization curves, linear sweep voltammetry (LSV) was used with a scan rate of 5 mV / s. The relationship between the test potential and mercury / mercuric oxide was converted to the potential and standard hydrogen electrode using the following formula:

[0102] E RHE =0.098V+E Hg / HgO +0.0592V×pH

[0103] Among them, 0.098V is the standard electrode potential of mercury / mercury oxide electrode, E Hg / HgO The electrochemical impedance spectroscopy (EIS) test was performed at 100000 Hz to 0.01 Hz.

[0104] 3. Glucose was added to 1 mol / L potassium hydroxide electrolyte to make the glucose concentration in the electrolyte 0.1 mol / L. GOR was tested. The polarization curve was obtained by LSV, and EIS test was performed at 100,000 Hz to 0.01 Hz. The test method was the same as that of Example (2) 2.

[0105] (3) Verification of chirality-induced spin selectivity effect:

[0106] 1. The M-PANI@NiS, P-PANI@NiS and PANI@NiS prepared in Examples 1 and 2 and Comparative Experiment 1 were transferred to the ITO conductive surface by the pull-up method. After drying at 25°C, M-PANI@NiS electrodes, P-PANI@NiS electrodes and PANI@NiS electrodes were obtained.

[0107] 2. A standard three-electrode system was used, with a catalyst-loaded ITO electrode as the working electrode, a graphite rod electrode as the counter electrode, and a mercury / mercuric oxide electrode as the reference electrode. Glucose was added to a 1 mol / L potassium hydroxide electrolyte so that the concentration of glucose in the electrolyte was 0.1 mol / L. The effect of chirality on GOR was tested. The polarization curve was obtained by LSV, and EIS testing was performed at 100,000 Hz to 0.01 Hz. The testing method was the same as that in Example (2) 2.

[0108] The transfer process of M-PANI, P-PANI, PANI, M-PANI@NiS, P-PANI@NiS, PANI@NiS, and NiS prepared in the Examples and Comparative Experiments is as follows: a culture dish (6 cm in diameter) containing the above-mentioned membrane is placed in a larger culture dish (16 cm in diameter). Water is added to the small culture dish along the edge. Then, water is added to the large culture dish until the water surface submerges the small culture dish. At this time, the membrane floats out of the culture dish as the liquid level rises and floats on the air-water interface. A solid substrate (such as ITO) is placed under the membrane and lifted upward, and the membrane will be transferred to the solid substrate.

[0109] Figure 1 This is a scanning electron microscope image of M-PANI prepared in step 5 of Example 1. As can be seen from the figure, at a large scale, the membrane is continuously distributed, while at a small scale or in a local position, it presents a nanofiber structure with a diameter of 20nm to 60nm.

[0110] Figure 2 This is a scanning electron microscope image of P-PANI prepared in step 5 of Example 2. As can be seen from the figure, at a large scale, the membrane is continuously distributed, while at a small scale or in a local position, it presents a nanofiber structure with a diameter of 20nm to 100nm.

[0111] Figure 3Transmission electron microscope images of M-PANI and P-PANI prepared in step 5 of Examples 1 and 2 are shown. As can be seen from the figure, the nanofibers have a coiled spiral morphology and a diameter of 15nm to 35nm.

[0112] Figure 4 This is the transmission electron microscope image of PANI prepared in step five of comparative experiment 1; as can be seen from the figure, the nanofibers do not show a spiral morphology and have a diameter of 18nm to 25nm.

[0113] Figure 5 This is the Raman test spectrum of P-PANI prepared in step 5 of Example 2. As can be seen from the figure, the Raman spectrum shows characteristic peaks of CC deformation, CN stretching vibration, CH bending vibration, and benzene ring bending deformation, which confirm the presence of polyaniline.

[0114] Figure 6 This is the Fourier transform infrared (FT-IR) spectrum of M-PANI prepared in step 5 of Example 1. As can be seen from the figure, 1569 cm -1 Corresponding to the C=C stretching vibration of the quinone ring, 1492 cm -1 Corresponding to the C=C stretching vibration of the benzene ring, 1302 cm -1 Corresponding to CN stretching vibration, 1141 cm -1 Corresponding to the in-plane bending vibration of the CH on the aromatic ring, 799cm -1 The corresponding CH in-plane bending vibration further explains the process of aniline being oxidized to polyaniline.

[0115] Figure 7 The UV-visible (UV-vis) spectra of M-PANI and P-PANI prepared in step 5 of Examples 1 and 2 are shown. As can be seen from the figure, strong UV absorption peaks are exhibited near 300nm and 400nm.

[0116] Figure 8 Circular dichroism (CD) spectra of M-PANI and P-PANI prepared in step 5 of Examples 1 and 2. As can be seen from the figure, M-PANI and P-PANI exhibit CD signals with opposite optical activities.

[0117] Figure 9 This is the UV-vis spectrum of L-CSA used in step 3 of Example 1. As can be seen from the figure, L-CSA only has an absorption peak near 300 nm, indicating that the absorption peak in M-PANI does not only come from L-CSA.

[0118] Figure 10The CD spectra of L-CSA and D-CSA used in step 3 of Examples 1 and 2 are shown in FIG. 1 . As can be seen from the figure, L-CSA and D-CSA exhibit CD spectra with opposite signals near 300 nm, while Figure 8 New CD signals appeared in M-PANI and P-PANI near 400nm, 450nm and in the range of 500nm to 650nm, indicating that the chiral doping acid (camphorsulfonic acid) successfully induced the chirality of the polyaniline chain, prompting polyaniline to exhibit new chiral signals.

[0119] Figure 11 This is the transmission electron microscope image of P-PANI@NiS prepared in Example 2 and its element distribution; it can be seen from the figure that Ni, S, C, N, and O elements are evenly distributed, indicating that NiS is evenly distributed on P-PANI.

[0120] Figure 12 This is a high-resolution transmission electron microscope image of P-PANI@NiS prepared in Example 2. As can be seen from the image, NiS lattice fringes exist in P-PANI@NiS.

[0121] Figure 13 These are the micro-area diffraction images of P-PANI@NiS prepared in Example 2 and NiS prepared in Comparative Experiment 2. It can be seen from the figure that NiS exists in P-PANI@NiS, which is consistent with the results of high-resolution transmission electron microscopy images.

[0122] Figure 14 This is a comparison of the Raman spectra of M-PANI prepared in step 5 of Example 1, M-PANI@NiS prepared in step 9, and NiS prepared in comparative experiment 2. As can be seen from the figure, there are very obvious M-PANI characteristic peaks in M-PANI@NiS, as well as Raman characteristic peaks of NiS, indicating that M-PANI@NiS contains both M-PANI and NiS.

[0123] Figure 15 This is a comparison of the FT-IR spectra of M-PANI prepared in step 5 of Example 1, M-PANI@NiS prepared in step 9, and NiS prepared in comparative experiment 2. As can be seen from the figure, there are very obvious M-PANI infrared characteristic peaks in M-PANI@NiS, and there are also two obvious NiS infrared characteristic peaks, further illustrating the composition of M-PANI@NiS.

[0124] Figure 16 The UV-vis images of M-PANI@NiS and P-PANI@NiS prepared in Examples 1 and 2 are shown. As can be seen from the figure, after the growth of NiS, the characteristic UV absorption peak of chiral polyaniline still exists stably.

[0125] Figure 17 CD images of M-PANI@NiS and P-PANI@NiS prepared in Examples 1 and 2. As can be seen from the figure, after the growth of NiS, the CD spectrum of chiral polyaniline still shows opposite signals, which is consistent with the CD spectra of M-PANI and P-PANI before the growth of NiS, indicating that the chiral signal exists stably.

[0126] Figure 18 LSV polarization curves of the P-PANI electrode, P-PANI@NiS electrode, NiS electrode, and bare ITO electrode prepared in Example 1 and Comparative Experiment 2, measured under the same standard. To achieve a stable state for subsequent measurements, all modified electrodes were pretreated with multi-cycle cyclic voltammetry before testing to eliminate the surface passivation layer and activate the electrochemically active surface. The results show that the LSV curves of the bare ITO electrode before and after the addition of glucose almost completely overlap, indicating that the bare ITO electrode has almost no catalytic oxidation activity relative to glucose; although the P-PANI modified electrode has conductive properties, the material itself does not have catalytic activity, and the catalytic oxidation activity is not improved. This is mainly because although polyaniline is conductive, the material itself does not have oxygen evolution properties, so no current increase is seen in the LSV curve; in contrast, the NiS electrode has a significant current change in 1 mol / L potassium hydroxide electrolyte, and the current density is higher after adding glucose, which proves its catalytic ability in the glucose oxidation reaction; it is worth noting that the P-PANI@NiS electrode can obtain a larger current than NiS at the same potential, which is attributed to the interfacial synergistic effect produced by the electron transport channel constructed by the polyaniline conductive network and the oxygen evolution properties of the nickel sulfide active sites, proving that the catalyst has catalytic potential based on GOR and OER processes.

[0127] Figure 19 The overpotentials of the P-PANI@NiS electrode and NiS electrode prepared in Example 1 and Comparative Experiment 2 in OER and GOR (at 10 mA / cm 2 As shown in the figure, in 1 mol / L potassium hydroxide electrolyte, the OER potential of the P-PANI@NiS electrode is 415 mV. When 0.1 mol / L glucose is added to the electrolyte for GOR, its overpotential is significantly reduced to 214 mV, a decrease of 41.9%, proving that the GOR process has a lower thermodynamic energy barrier. Comparative experiments show that the NiS electrode requires an overpotential of 322 mV to achieve the same current density under GOR conditions, indicating that M-PANI@NiS is more effective than NiS for GOR and has a higher catalyst efficiency.

[0128] Figure 20Comparison of the Tafel slopes of the P-PANI@NiS electrode and NiS electrode prepared in Example 1 and Comparative Experiment 2 in OER and GOR; it can be seen from the figure that the Tafel slopes of the P-PANI@NiS and NiS electrodes used for glucose oxidation are 64 mV / dec and 137 mV / dec, respectively, which are significantly lower than the OER Tafel slopes using the P-PANI@NiS (150 mV / dec) and NiS electrodes (234 mV / dec). Since the Tafel slope is closely related to the electron transfer rate, a lower Tafel slope indicates a faster electron transfer rate. The oxidation of glucose shows a lower Tafel slope, indicating faster reaction kinetics. The synergistic effect of the two can improve the reaction rate.

[0129] Figure 21 Figure 3 is the EIS curve of the P-PANI@NiS electrode and NiS electrode prepared in Example 1 and Comparative Experiment 2 for glucose oxidation. As can be seen from the figure, the P-PANI@NiS electrode shows a smaller semicircle or charge transfer resistance in glucose oxidation, which is beneficial to charge transfer.

[0130] Figure 22 Polarization curves for glucose oxidation at the M-PANI@NiS electrode, P-PANI@NiS electrode, and PANI@NiS electrode prepared in Examples 1 and 2 and Comparative Experiment 1. As can be seen from the figure, at the same voltage, the current density obtained by the chiral material significantly exceeds that of the achiral material, emphasizing the role of chirality-induced spin selectivity in improving catalytic activity.

[0131] Figure 23 The overpotential (10 mA / cm2) of glucose oxidation on the M-PANI@NiS electrode, P-PANI@NiS electrode and PANI@NiS electrode prepared in Examples 1 to 2 and Comparative Experiment 1 2 As shown in the figure, the chiral electrocatalyst exhibits a lower overpotential, indicating that compared with the achiral catalyst, the chiral catalyst can achieve a 10mA / cm 2 This indicates that the chiral electrocatalyst is more effective for GOR, reflecting the role of spin-induced selectivity.

[0132] Figure 24 The Tafel slopes of glucose oxidation on the M-PANI@NiS electrode, P-PANI@NiS electrode and PANI@NiS electrode prepared in Examples 1 to 2 and Comparative Experiment 1 are shown in the figure. Compared with the achiral catalyst (139 mV dec -1 ), the chiral electrocatalyst has a lower Tafel slope of 60 mV dec -1 and 64mVdec -1 , the reaction kinetics are higher than those of achiral electrocatalysts.

[0133] Figure 25 EIS images of glucose oxidation performed on the M-PANI@NiS electrode, P-PANI@NiS electrode, and PANI@NiS electrode prepared in Examples 1 to 2 and Comparative Experiment 1. As can be seen from the figure, the M-PANI@NiS and P-PANI@NiS electrodes show smaller semicircle or charge transfer resistance in glucose oxidation, which is more conducive to charge transport, indicating that spin polarization has higher GOR catalytic activity.

Claims

1. A method for preparing a chiral conductive polymer / sulfide composite material, characterized in that It is carried out in the following steps:

1. Add N-lauroyl-L-alanine to chloroform solution and stir to dissolve to obtain NLLA solution; 2. Add aniline monomer into deionized water and stir to dissolve to obtain An solution; 3. Add camphorsulfonic acid to deionized water and stir to dissolve to obtain CSA solution; The camphorsulfonic acid is L-camphorsulfonic acid or D-camphorsulfonic acid; 4. Add ammonium persulfate to deionized water and stir to dissolve to obtain an APS solution; 5. An solution and CSA solution were mixed to obtain an An / CSA system, NLLA solution was added dropwise to the surface of the An / CSA system, and then the system was allowed to stand at room temperature once, and then APS solution was injected into the bottom of the An / CSA system, and then the system was allowed to stand at room temperature a second time to form a chiral polyaniline nanofiber membrane at the air-water interface, thereby obtaining a solution with a chiral polyaniline nanofiber membrane on the surface; 6. Add nickel nitrate hexahydrate into deionized water and stir to dissolve to obtain a Ni(NO3)2 solution; 7. Add concentrated hydrochloric acid to deionized water and stir to dissolve to obtain a dilute hydrochloric acid solution; 8. Add sodium sulfide to deionized water and stir to dissolve to obtain Na2S solution; 9. The solution with the surface covered with chiral polyaniline nanofiber membrane is placed in a confined space, and then Ni(NO3)2 solution is injected into the bottom of the solution with the surface covered with chiral polyaniline nanofiber membrane. At the same time, in the confined space, dilute hydrochloric acid solution is added to the Na2S solution to release H2S gas. Finally, the solution is allowed to stand at room temperature to grow a nickel sulfide catalyst film on the chiral polyaniline nanofiber membrane, thereby obtaining a chiral conductive polymer / sulfide composite material.

2. The method for preparing a chiral conductive polymer / sulfide composite material according to claim 1, characterized in that The concentration of N-lauroyl-L-alanine in the NLLA solution described in step 1 is 1.8 mmol / L to 2 mmol / L.

3. The method for preparing a chiral conductive polymer / sulfide composite material according to claim 1, characterized in that The concentration of the aniline monomer in the An solution described in step 2 is 0.25 mol / L to 0.27 mol / L.

4. The method for preparing a chiral conductive polymer / sulfide composite material according to claim 1, characterized in that The concentration of camphorsulfonic acid in the CSA solution in step 3 is 0.35 mol / L to 0.45 mol / L.

5. The method for preparing a chiral conductive polymer / sulfide composite material according to claim 1, characterized in that The concentration of ammonium persulfate in the APS solution in step 4 is 3.1 mol / L to 3.3 mol / L.

6. The method for preparing a chiral conductive polymer / sulfide composite material according to claim 1, characterized in that The volume ratio of the An solution described in step five to the CSA solution is 1:(0.95-1.05); the volume ratio of the An solution described in step five to the NLLA solution is (500-510):1; the volume ratio of the An solution described in step five to the APS solution is (10-11):

1.

7. The method for preparing a chiral conductive polymer / sulfide composite material according to claim 1, characterized in that In step 5, the NLLA solution was added to the surface of the An / CSA system at a drop rate of 5 μL / s to 10 μL / s, and then allowed to stand at room temperature for 5 to 6 minutes. Then, the APS solution was injected into the bottom of the An / CSA system at an injection rate of 0.05 mL / s to 0.1 mL / s, and then allowed to stand at room temperature for 10 to 20 hours.

8. The method for preparing a chiral conductive polymer / sulfide composite material according to claim 1, characterized in that The concentration of nickel nitrate hexahydrate in the Ni(NO3)2 solution described in step six is 2 mol / L to 2.2 mol / L; the concentration of the dilute hydrochloric acid solution described in step seven is 1 mol / L to 1.2 mol / L; the concentration of sodium sulfide in the Na2S solution described in step eight is 0.2 mol / L to 0.25 mol / L.

9. The method for preparing a chiral conductive polymer / sulfide composite material according to claim 1, characterized in that The volume ratio of the solution with the chiral polyaniline nanofiber membrane on the surface and the Ni(NO3)2 solution in step nine is (10-11):1; the volume ratio of the dilute hydrochloric acid solution and the Na2S solution in step nine is (1-1.2):1; the volume of the confined space in step nine is 8L-9L; in step nine, Ni(NO3)2 solution is injected into the bottom of the solution with the chiral polyaniline nanofiber membrane on the surface at an injection rate of 0.05mL / s-0.1mL / s; in step nine, the solution is allowed to stand at room temperature for 10h-20h.

10. Use of a chiral conductive polymer / sulfide composite material prepared as claimed in claim 1, characterized in that Chiral conducting polymer / sulfide composites as catalysts for electrocatalytic oxidation of glucose.

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