Ion channel and ion pump synergistic energy conversion system and method for enhancing permeation power generation performance by light

Abstract

The application discloses an energy conversion system of ion channel and ion pump cooperation and a method for enhancing permeation power generation performance by light, and belongs to the technical field of general process technology of processing and dosing. The PPy ion pump and the PPy@TiO2 ion channel are integrated, and energy conversion similar to the cooperation of ion channels and ion pumps in biological photosynthetic membranes in nature is realized. Through light-driven artificial ion pumps, ion uphill transport is carried out, light energy is converted into an ion gradient, and then the ion downhill transmission is carried out, so that the conversion between the ion gradient and electric energy is realized. The energy conversion system is constructed by connecting the ion channel and the ion pump in series, and the output power of the conversion from light energy and the ion gradient into electric energy is increased.

Description

Technical Field

[0001] This invention relates to the technical field of general processing and batching techniques, specifically to an energy conversion system that combines ion channels and ion pumps and a method for enhancing the performance of light-enhanced permeation power generation. Background Technology

[0002] In nature, green plants convert light energy into chemical energy through photosynthesis, maintaining their own life processes and providing abundant energy to the environment. The photosynthetic membrane is a crucial site for the light-dependent reactions during photosynthesis. Two functional proteins on the membrane—ion channels and ion pumps—work synergistically to regulate the diffusion of protons down their concentration gradient (ion channels) and their transport against their concentration gradient (ion pumps), thus converting light energy into chemical energy. According to Fick's law, diffusion always proceeds towards lower concentrations; therefore, the reverse concentration gradient transport of ion pumps is called "uphill diffusion," and the diffusion down the concentration gradient of ion channels is called "downhill diffusion." The "uphill" ion transport of ion pumps on the photosynthetic membrane mainly depends on surface charge, ion flux, and the potential difference generated across the photosynthetic membrane by incident light. The light-induced potential difference drives ions to ultimately transport from a high electrochemical potential to a low electrochemical potential, effectively converting absorbed light energy into electrochemical energy. The "downhill" ion transport function of ion channels on the photosynthetic membrane is related to the surface charge, asymmetric structure, and ion flux of the ion channels. The ultrathin photosynthetic membrane ensures high ion flux, thereby enabling the efficient conversion of ion gradients into chemical energy.

[0003] Current research has enabled the conversion of environmental energy into electrochemical energy using artificial ion pumps and the conversion of ion gradient energy into electrical energy using artificial ion channels. However, this energy conversion mode still differs significantly from the natural mechanism within biological photosynthetic membranes, which relies on the synergistic regulation of ion pumps and ion channels to actively transport ions uphill and passively transport them downhill, thereby achieving efficient conversion of light energy into electrochemical energy. This results in generally low energy conversion output power for existing single-component artificial ion channel or ion pump devices. Therefore, integrating artificial ion pumps and ion channels to simulate the synergistic energy conversion mechanism in biological photosynthetic membranes is an important way to improve the electrical output performance of devices. Further in-depth research is needed on the relevant mechanisms and device construction in this direction. Summary of the Invention

[0004] To address the aforementioned limitations of existing technologies, the present invention aims to provide an energy conversion system synergistically incorporating ion channels and ion pumps, and a method for enhancing the performance of light-enhanced permeation power generation. This invention integrates an artificial ion pump and an artificial ion channel in series to construct an energy conversion system. The artificial ion pump captures light energy and converts it into a transmembrane ion concentration gradient; the artificial ion channel utilizes the ion gradient established by the ion pump to further convert chemical potential energy into electrical energy. Through the synergistic coupling effect of the ion pump and ion channel, the output power and energy conversion efficiency of the system from light energy and ion chemical energy to electrical energy can be significantly improved.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides a PPy@TiO2 ion channel, wherein the PPy@TiO2 ion channel is prepared by the following method; (1) Pt nanoparticles are sputtered onto one side of the porous anodic aluminum oxide film, i.e., AAO, to form a conductive layer; (2) Electrochemically deposit the conductive polymer PPy onto the conductive layer to form a PPy / AAO film; (3) TiO2 nanoparticles were spin-coated onto the surface of PPy / AAO membrane and dried to obtain PPy@TiO2 ion channels.

[0006] Furthermore, in step (2), during electrochemical deposition, a potential of 0.9V is applied, and the conductive polymer PPy is deposited in a pyrrole solution containing the supporting electrolyte KCl for 3-5 minutes.

[0007] Furthermore, in step (2), the concentration of pyrrole is 0.1-1 mol / L, and the concentration of the supporting electrolyte KCl is 0.1-1 mol / L.

[0008] Furthermore, in step (3), during spin coating, the TiO2 hydrosol containing TiO2 nanoparticles is spin coated for 20-40 s at 3500-4500 rpm.

[0009] Furthermore, in step (3), the concentration of TiO2 hydrosol is 40-60 mg / ml.

[0010] Furthermore, in step (3), the drying process is carried out at room temperature for 10-14 hours.

[0011] In a second aspect, the present invention provides an energy conversion system that integrates ion channels and ion pumps to construct an ion energy conversion system. The ion channel is the PPy@TiO2 ion channel; The ion pump mentioned is a PPy ion pump; The integration method is as follows: Ion pumps and ion channels are embedded in the chamber walls of a multi-chamber electrochemical cell, forming a series structure in which "low-concentration chamber, PPy ion pump, high-concentration chamber, PPy@TiO2 ion channel" repeats; the two end chambers of the multi-chamber electrochemical cell are low-concentration chambers.

[0012] Furthermore, a pair of Ag / AgCl electrodes are provided in the two end chambers of the multi-chamber electrochemical cell.

[0013] Furthermore, the PPy ion pump is a polypyrrole membrane.

[0014] In a third aspect, the present invention provides a method for enhancing the performance of light-induced permeation power generation, wherein the energy conversion system is constructed in a multi-chamber electrochemical cell; in the energy conversion system, an ion pump is excited by light to generate an internal electric field, converting light energy into an ion gradient and outputting electrical energy; an ion channel converts the ion gradient into electrical energy, further realizing the conversion between ion gradient and electrical energy.

[0015] The beneficial effects of this invention are: The energy conversion system of this invention integrates artificial ion channels and ion pumps to achieve energy conversion similar to the synergistic effect of ion channels and ion pumps in biological photosynthetic membranes. A high-performance PPy artificial ion pump is constructed, utilizing the uphill transport of ions to convert light energy into an ion gradient. Through the PPy@TiO2 ion channel formed by polypyrrole and TiO2, the "downhill" transport of ions is utilized to achieve the conversion of ion gradient into electrical energy. The synergistic effect of the ion channels and ion pump enables the conversion of light energy and ion gradient into electrical energy output power. Attached Figure Description

[0016] Figure 1 Scanning electron microscope image of a PPy ion pump.

[0017] Figure 2 This is a diagram of a current testing device without a quartz window.

[0018] Figure 3 Ion current-voltage (Ion current-voltage) of PPy ion pump under different transmembrane voltages I - V )curve.

[0019] Figure 4 This is a diagram of a current testing device with a single-sided quartz window.

[0020] Figure 5 The ion current-time (It) curves of the PPy ion pump under both light and dark conditions are shown.

[0021] Figure 6 This is a scanning electron microscope image of the PPy@TiO2 ion channel.

[0022] Figure 7 This describes the photoexcited electron transfer process in the PPy@TiO2 ion channel.

[0023] Figure 8 Ion current-voltage (Ion current-voltage) of PPy@TiO2 ion channels under different transmembrane voltages I - V )curve.

[0024] Figure 9 This is a schematic diagram of the energy conversion system of ion channels and ion pumps working together under different transmembrane voltages.

[0025] Figure 10 This is a diagram of a current testing device with quartz windows on both sides.

[0026] Figure 11 Ion current-voltage curves for the energy conversion system of ion channel and ion pump synergistically under different transmembrane voltages. Detailed Implementation

[0027] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0028] To enable those skilled in the art to better understand the technical solution of this application, the technical solution of this application will be described in detail below with reference to specific embodiments.

[0029] The combined materials selected in this invention are PPy ion pumps and PPy@TiO2 ion channels. PPy is a typical conjugated conductive polymer with broad-spectrum light absorption capabilities, enabling photoresponsive ion transport properties. Regarding the operation of the PPy ion pump: PPy is a p-type semiconductor that, upon photoexcitation, generates electron-hole pairs. The holes migrate into the membrane, leaving uncompensated electrons, which generate an internal electric field on the membrane, driving ion transport against the concentration gradient, thus forming the ion pump effect (Angew. Chem. Int. Ed. 2022, 61, e202201138). Regarding the operation of the PPy@TiO2 ion channel: n-type semiconductor TiO2 nanoparticles and p-type semiconductor PPy films can form the PPy@TiO2 ion channel. After the PPy surface was modified with n-type TiO2 nanoparticles, the pn heterojunction formed at the interface accelerated the transfer of photoelectrons from PPy to TiO2 under visible light induction. The holes left behind increased the surface charge density of the PPy film and significantly enhanced the light-driven ion current (ACS Applied NanoMaterials, 2024, 7, 13481).

[0030] The test materials used in the embodiments of the present invention, unless otherwise specified, are all conventional test materials in the art and can be purchased through commercial channels.

[0031] Example 1: Preparation of PPy ion pump The PPy ion pump was prepared using an electrodeposition method. In a three-electrode system, a porous anodic alumina coated with platinum on one side served as the working electrode, an Ag / AgCl electrode as the reference electrode, and a platinum sheet as the counter electrode. The electrolyte solution was a 0.1 M pyrrole solution, and a 0.1 M KCl solution was used as the supporting electrolyte for electrochemical deposition. A potentiostatic deposition method was employed, using a CHI660D electrochemical workstation (Shanghai Chenhua) with a potential of 0.9 V (vs. Ag / AgCl) to grow a layer of polypyrrole on the anodic alumina film. After cleaning the electrode surface with deionized water, the PPy ion pump was obtained. A scanning electron microscope image of the PPy ion pump is shown below. Figure 1 .

[0032] At room temperature, the PPy ion pump was placed in an electrochemical cell. The structure of the electrochemical cell is shown in [reference needed]. Figure 2 The dimensions are 1×1 cm. 2 The membrane is sandwiched between perforated acrylic plates and installed at the partition of a multi-chamber electrochemical cell.

[0033] The solutions placed on both sides of the dual-chamber electrolytic cell were 1mM KCl electrolyte solutions. The electrodes were a pair of Ag / AgCl reference electrodes. Voltage-current data were obtained by applying different transmembrane voltages, and the results are shown in Figure 3.

[0034] according to Figure 3 As a result, applying different transmembrane voltages yielded linear voltage-current data, indicating that the ion channel exhibits linear ion transport properties.

[0035] To investigate the effect of light on ion transport against the concentration gradient, a quartz window was used. Figure 4 Electrochemical cell, 1×1 cm in size 2 The membrane is sandwiched between perforated acrylic plates and installed at the partition of a multi-chamber electrochemical cell. The electrodes are a pair of Ag / AgCl reference electrodes used to measure the response current. A black tube is used to protect the electrodes from the influence of light. The KCl concentration on the PPy side is kept constant at 1 mM, while the KCl concentration on the other side is changed to 0.9 mM, with a light intensity of 100 mW / cm². 2 Visible light was used as the light source to illuminate one side of PPy. The current-time (It) plot was obtained by measuring the current change before and after the light exposure. The results are shown in [Figure number missing]. Figure 5 .

[0036] according to Figure 5As a result, chloride ions diffuse freely from high concentration to low concentration in the dark, generating a negative current. After illumination, the sign of the ion current changes from negative to positive, indicating that light drives ion transport against the concentration gradient, demonstrating an ion pump effect.

[0037] Example 2: Preparation of PPy@TiO2 ion channels A conductive polymeric film of PPy was prepared by electrochemical polymerization using an anodic alumina porous membrane (AAO) containing cylindrical channels as the supporting substrate. First, a layer of Pt nanoparticles was sputtered onto one side of a 12 mm diameter AAO membrane to form a Pt / AAO film. One end of the Pt / AAO film was then bonded to a 2 cm titanium wire using conductive silver paste for electrode connection. Electrochemical polymerization was performed using a three-electrode configuration: the Pt / AAO membrane with Pt sputtered on one side served as the working electrode, a platinum sheet as the counter electrode, and an Ag / AgCl electrode (3.5 M KCl) as the reference electrode. Electrochemical polymerization was carried out for 4 min at a potential of +0.9 V in an electrolyte containing 0.2 M pyrrole and 0.2 M KCl to obtain the oxidized PPy film, referred to as the PPy / AAO film. TiO2 nanoparticles were prepared by spin-coating 50 mg / ml TiO2 hydrosol onto the surface of a PPy / AAO membrane at 4000 rpm for 30 s. After drying at room temperature for 12 hours, PPy@TiO2 ion channels were obtained. The obtained PPy@TiO2 ion channels were observed by scanning electron microscopy, and the results are shown below. Figure 6 The TiO2 layer thickness is 1.07 μm, and the PPy layer thickness is 1.45 μm.

[0038] like Figure 7 As shown, in the PPy@TiO2 ion channel, the energy bands of PPy and TiO2 are co-aligned, and the close contact between the n-type TiO2 and p-type PPy layers forms a pn junction. The built-in electric field formed by the pn junction drives photogenerated holes in the TiO2 valence band to transfer to the highest occupied molecular orbital (HOMO) of PPy. Simultaneously, photogenerated electrons in the lowest unoccupied molecular orbital (LUMO) of PPy transfer to the conduction band of TiO2 and are subsequently captured by oxygen in the electrolyte. The presence of the pn junction promotes charge separation and increases the positive charge density of the PPy layer.

[0039] The prepared PPy@TiO2 ion channel was placed at room temperature. Figure 2 In the same electrochemical cell, the solutions placed on both sides of the two-chamber electrolytic cell are 1mM KCl electrolyte solutions, and the electrodes are a pair of Ag / AgCl reference electrodes. Linear voltage-current curves were obtained by applying different transmembrane voltages, and the results are shown in Figure 8.

[0040] according to Figure 8 As a result, the ion channel exhibits linear ion transport properties.

[0041] Example 3: Energy Conversion System 1. Composition method By integrating PPy ion pumps with PPy@TiO2 ion channels, a synergistic energy conversion system of ion channels and ion pumps is constructed. The integration method involves alternately mounting ion channel and ion pump membranes on an electrolytic cell to form a series of membrane modules, achieving the conversion of electrochemical energy into electrical energy. A schematic diagram is shown below. Figure 9 As shown.

[0042] A membrane-like PPy ion pump and a PPy@TiO2 ion channel were sandwiched between perforated acrylic plates and then sequentially and alternately assembled at the partitions of a multi-chamber electrochemical cell to form a "low-concentration chamber (C)". L )-PPy ion pump-high concentration chamber (C H )-PPy@TiO2 ion channel-low concentration chamber (C L )-PPy ion pump-high concentration chamber (C H The repeating tandem structure of "-PPy@TiO2 ion channel".

[0043] 2. Performance Testing Power tests were conducted on the PPy ion pump, PPy@TiO2 ion channel, and energy conversion system, respectively. The electrolytic cell used in the tests is described below. Figure 10 The size is 1×1 cm 2 The membrane is sandwiched between perforated acrylic plates and installed at the partition of a multi-chamber electrochemical cell. When the test object is a PPy ion pump, Figure 10 The membranes used in A and B were both PPy ion pumps prepared in Example 1; when the test object was a PPy@TiO2 ion channel... Figure 10 The membranes used in A and B are both PPy@TiO2 ion channels prepared in Example 2; when the test object is an energy conversion system... Figure 10 The membrane used in example A is the PPy ion pump prepared in Example 1. Figure 10 The membrane used in example B is the PPy@TiO2 ion channel prepared in Example 2. A concentration cell with a 50-fold concentration gradient was constructed by fixing the KCl electrolyte concentration on the high-concentration side to 0.5 mol / L and the KCl electrolyte concentration on the low-concentration side to 0.01 mol / L. The effective geometric area (S) of the membrane is 0.03 mm². 2 A transmembrane voltage was applied to the membrane using a Geely-Lippier ammeter, with a range of -0.2 V to 0.2 V and a step size of 0.01 V. The output current was monitored using a pair of Ag / AgCl electrodes to measure the membrane output under this salinity gradient. I - VCurve. Throughout the measurement, light intensity of 270 mW / cm² was applied to the membrane through a quartz window. 2 illumination.

[0044] The test results are shown in Figure 11. Figure 11 As a result, the open-circuit voltage can be obtained ( V oc ) and short-circuit current ( I sc ), through formula P = V oc × I sc / 4S, the output power density is obtained. By connecting an external resistor to the device and changing the resistance value of the external circuit, the actual output power can be obtained, as shown in the following results: For PPy ion pumps: V oc =0.1 V, I sc =4.38×10 -7 A, power P =0.37 W / m 2 .

[0045] For PPy@TiO2 ion channels: V oc =0.19 V, I sc =1.89×10 -7 A, power P =0.30 W / m 2 .

[0046] For energy conversion systems that combine ion channels and ion pumps: V oc =0.21 V, I sc =3.25×10 -6 A, power P =5.69 W / m 2 .

[0047] The power of the synergistic energy conversion system of ion channels and ion pumps is 5.69 W / m. 2 The power is higher than that of the PPy ion pump (0.37 W / m). 2 ) or the power of the PPy@TiO2 ion channel (0.30 W / m 2It is evident that integrating artificial ion pumps and ion channels into a single structure, mimicking the energy conversion mechanism of their synergistic operation in biological photosynthetic membranes, can improve the device's power output performance.

[0048] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. An energy conversion system synergistically incorporating ion channels and ion pumps, characterized in that, Integrating ion channels and ion pumps to construct an ion energy conversion system; The ion channel mentioned is a PPy@TiO2 ion channel; The PPy@TiO2 ion channel was prepared by the following method; (1) Pt nanoparticles are sputtered onto one side of the porous anodic aluminum oxide film, i.e., AAO, to form a conductive layer; (2) Electrochemically deposit the conductive polymer PPy onto the conductive layer to form a PPy / AAO film; (3) TiO2 nanoparticles were spin-coated onto the surface of PPy / AAO film and dried to obtain PPy@TiO2 ion channels; The ion pump is a PPy ion pump; the PPy ion pump is a polypyrrole membrane; The integration method is as follows: Ion pumps and ion channels are embedded in the chamber walls of a multi-chamber electrochemical cell, forming a series structure in which "low-concentration chamber, PPy ion pump, high-concentration chamber, PPy@TiO2 ion channel" repeats; the two end chambers of the multi-chamber electrochemical cell are low-concentration chambers. A pair of Ag / AgCl electrodes are installed in the two end chambers of the multi-chamber electrochemical cell.

2. The energy conversion system synergistically combining ion channels and ion pumps according to claim 1, characterized in that, In step (2), during electrochemical deposition, a potential of 0.9V is applied, and the conductive polymer PPy is deposited in a pyrrole solution containing the supporting electrolyte KCl for 3-5 minutes.

3. The energy conversion system synergistically combining ion channels and ion pumps according to claim 2, characterized in that, In step (2), the concentration of pyrrole is 0.1-1 mol / L, and the concentration of the supporting electrolyte KCl is 0.1-1 mol / L.

4. The energy conversion system synergistically combining ion channels and ion pumps according to claim 1, characterized in that, In step (3), during spin coating, the TiO2 hydrosol containing TiO2 nanoparticles is spin coated for 20-40 s at 3500-4500 rpm.

5. The energy conversion system synergistically combining ion channels and ion pumps according to claim 1, characterized in that, In step (3), the concentration of TiO2 hydrosol is 40-60 mg / ml.

6. The energy conversion system synergistically combining ion channels and ion pumps according to claim 1, characterized in that, In step (3), the drying process is carried out at room temperature for 10-14 hours.

7. A method for enhancing the performance of light-induced permeation power generation, characterized in that, Construct the energy conversion system according to any one of claims 1-6 in a multi-chamber electrochemical cell; in the energy conversion system, the ion pump is excited by light to generate an internal electric field, converting light energy into an ion gradient and outputting electrical energy; Ion channels convert ion gradients into electrical energy, further realizing the conversion between ion gradients and electrical energy.

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