Method for enhancing electrolytic reaction efficiency by programmable temperature gradient thermomagnetic effect

Abstract

The invention belongs to the technical field of electrochemistry, and particularly relates to a method for strengthening electrolytic reaction efficiency through a programmable temperature gradient thermomagnetic effect. Specifically, a catalytic electrode comprising a plurality of Curie point materials which are arranged in a stacked manner is constructed, and when the catalytic electrode is heated to a corresponding temperature interval, each layer of material can sequentially show different magnetic properties, so that the reaction process is influenced. The Curie point characteristic of the material is utilized, continuously changing temperature fields are generated in different areas, and specific chemical reactions are selectively activated or inhibited in cooperation with magnetic field switching. The preparation method has the technical advantages that the electrolytic active membrane can be constructed on a plurality of micron-sized-thickness membrane electrode materials with different substrates, the catalytic activity of the membrane electrode material can be adjusted along with the temperature, and the membrane electrode material can be widely applied to the technical fields of electro-catalytic water decomposition, electrodialysis, electro-adsorption and the like.

Description

1. Technical Field

[0001] The present invention belongs to the field of electrochemical technology, and in particular, relates to a method for enhancing the efficiency of electrolytic reactions by using programmable temperature gradient thermomagnetic effects. Current electrolytic cell technology has been relatively mature, but there is little research on the electrodes themselves, especially on how to use temperature fields to regulate the catalytic activity of the electrodes themselves, resulting in poor adjustability of the electrochemical system and difficulty in adapting to different reaction environments. The present invention constructs an electrolytically active membrane on thin-film electrode materials of various substrates, and uses the temperature-adjustable properties of various Curie point materials to change their magnetism and catalytic activity, which can be widely used in technical fields such as electrocatalysis, electrodialysis, and electrosorption. 2. Background Technology

[0002] Electrocatalytic technology has shown a wide range of application potentials in the fields of environment, energy and chemical synthesis. In environmental remediation, electrocatalytic technology is used to degrade organic pollutants in water and air. For example, electrocatalytic reactors are used to degrade drug residues and difficult-to-degrade organic pollutants. In the energy field, electrocatalytic carbon dioxide reduction reactors can convert CO2 into fuels such as methane and methanol. In chemical synthesis, electrocatalytic technology is used to efficiently synthesize high-value-added chemicals. In addition, electrocatalytic reactors have also made significant progress in the fields of solar fuel preparation and water decomposition to produce hydrogen.

[0003] Although electrocatalytic technology has been widely used in many fields, the fixedness of its material activity and selectivity limits its further promotion. Once the electrocatalyst, that is, the electrode material, is determined, its activity and selectivity are fixed, and it is difficult to dynamically adjust according to changes in reaction conditions. For example, in the CO2 reduction reaction, the product selectivity of copper-based catalysts is usually fixed on C2+ products (such as ethylene and ethanol), while gold-based catalysts mainly generate CO. This fixity leads to limited optimization of reaction conditions. In addition, the active sites of electrocatalytic materials usually depend on specific surface structures and electronic states. For example, the edge sites of MoS2 are highly active for hydrogen evolution reaction (HER), but its basal surface is almost inactive. This structural dependence further limits the adjustability of the material. At the same time, the stability problem of electrocatalytic materials is also prominent. For example, in acidic media, ruthenium-based oxides are prone to surface reconstruction in the oxygen evolution reaction (OER), resulting in decreased activity. These shortcomings show that existing electrocatalytic technologies have significant defects in material activity and selectivity, and they urgently need to be improved through technological innovation.

[0004] In order to improve the defects of electrocatalytic technology, many scholars have actively explored material design and performance optimization. For example, through first-principles calculations, Lin Haiping's team at Soochow University found that increasing the reaction temperature can significantly improve the energy conversion efficiency of electrocatalytic reactions through the thermodynamic-electrochemical cascade catalytic reaction mechanism, and experimentally verified catalysts with better performance than IrO2. Zhang Yuchao's team at the Institute of Chemistry, Chinese Academy of Sciences, reviewed the activity and selectivity of plasmon-enhanced electrocatalytic CO2 reduction, pointing out that plasmon effects (such as hot carrier effects and photothermal effects) can significantly improve reaction performance. In addition, Wang Bin's team at China University of Petroleum (East China) proposed an external field-assisted electrocatalytic technology. By introducing physical fields such as heat, light, and magnetism, multiple controls and monitoring of electrocatalytic reactions were achieved, significantly improving reaction kinetics and selectivity. These innovations show that the performance of electrocatalytic technology can be significantly improved through external field regulation and material design.

[0005] However, the above research is usually achieved by introducing third-party interference factors, such as heat, light, magnetism and other physical fields. This process passively acts on the reaction system itself and has little effect on the electrocatalyst itself. Therefore, how to use the changes in these external factors to make precise adjustments to the electrocatalyst to meet the needs of electrocatalytic applications still needs further research. III. Summary of the invention

[0006] The present invention is made in view of the problems existing in the prior art. The present invention adopts magnetic alloy materials with different Curie points, which are respectively suitable for magnetic field regulation in different temperature ranges, and can selectively activate or inhibit specific chemical reactions according to reaction requirements. For example, in the hydrolysis reaction, the high Curie point material area is preferentially activated, and in the electrodialysis and electroadsorption processes, the appropriate temperature and magnetic field combination is selected according to the polarity of the target substance. This design not only expands the temperature response range, but also improves the adaptability to various reaction types. Studies have shown that after using multi-layer magnetic alloy materials, the reaction selectivity and activity have been significantly improved. For example, in polar electrolyte treatment, the ion mobility is increased by 42.5% and the incidence of side reactions is reduced by 12.7%.

[0007] Secondly, in order to construct an efficient and stable multilayer electrocatalyst, the present invention uses ion beam deposition or magnetron sputtering technology to sequentially deposit magnetic alloy materials with different Curie points on a barium titanate ceramic sheet with good conductivity and corrosion resistance. This multilayer structure allows the activity and selectivity of the electrocatalyst to be switched on a large scale, from one product to another, or from one function to another. For non-polar organic matter, appropriately lowering the temperature and weakening the magnetic field can reduce the occurrence of side reactions, while polar electrolytes require higher temperatures and stronger magnetic fields to promote ion migration. Experimental results show that in this way, the intelligent electrolysis system of the present invention can achieve efficient electrolysis reactions under different conditions, greatly improving application flexibility.

[0008] Finally, in order to achieve intelligent control, the present invention introduces machine learning algorithms such as support vector machine (SVM) and random forest (RF) to predict the optimal reaction conditions. All sensor data are transmitted to the central controller, and the working parameters of the heating system and the electromagnetic coil are automatically adjusted after intelligent analysis of big data to form a closed-loop feedback system. With the help of temperature sensors, pH sensors, dissolved oxygen sensors, etc., the environmental parameters in the reaction chamber are collected in real time, and more accurate parameter recommendations are provided through data analysis. By controlling the direction and intensity of the coil current through the program, the magnetic field can be quickly switched to selectively activate or inhibit specific chemical reactions. The experimental results show that the use of an intelligent control system further reduces material consumption by about 33.7%, energy consumption by 16.2%, and reaction efficiency and selectivity by significantly improving.

[0009] In order to achieve the above object, the technical solution of the present invention is a method for enhancing the efficiency of electrolysis reaction by programmable temperature gradient thermomagnetic effect, characterized in that the method specifically comprises the following steps:

[0010] Step 1, selecting magnetic alloy materials with different Curie points, specifically: ferrite (Fe3O4), Curie point is about 858K; nickel cobalt alloy (Ni-Co), Curie point range 600K; manganese zinc ferrite (Mn-Zn ferrite), Curie point 498K; yttrium barium copper oxide (YBCO), Curie point 92K; the above materials are respectively suitable for magnetic field regulation in different temperature ranges; the above magnetic alloy material can also include neodymium iron boron (NdFeB), whose Curie point is about 585K, which is used to expand the temperature response range, especially in high temperature areas to provide a stronger magnetic effect.

[0011] Step 2: The substrate material is a barium titanate (BaTiO3) ceramic sheet with good conductivity and corrosion resistance, with a thickness of 0.1 to 1 mm; the surface of the substrate needs to be polished, with a roughness Ra < 0.05 μm, to ensure uniform adhesion of subsequent deposited layers;

[0012] Step 3, using ion beam deposition to prepare multilayer Curie point materials, firstly, using ion beam deposition to prepare a first layer of magnetic alloy material on a substrate; setting the ion beam energy to 500 to 1000 eV and the working pressure to 1×10 -5 Pa, the deposition rate is controlled at 0.1 to 1 nm / s, the deposition time is 1 to 5 h, and the first thin film with a thickness of 100 to 500 nm is formed; the deposition process is repeated to construct a multilayer structure; the other three magnetic alloy materials are deposited in sequence according to the above parameters, and the thickness of each layer is also controlled at 100 to 500 nm, and finally a composite film structure with four or more layers is formed; good bonding strength must be maintained between the layers to avoid stratification; the prepared multilayer structure is placed in a vacuum furnace and annealed under inert gas protection; the annealing temperature is set to 100K below the Curie point of the material, and the time lasts for 1 to 3 hours to optimize the crystal structure and improve the magnetic stability; among them, the ion beam deposition method can also use magnetron sputtering technology as an alternative, which is particularly suitable for preparing thicker magnetic alloy layers; during the magnetron sputtering process, the distance between the target material and the substrate is maintained at 5 to 10 cm, the sputtering power is 100 to 500 W, and the working gas pressure is 1×10 -3 Pa to obtain higher deposition rate and better film quality.

[0013] Step 4: Build a precise and controllable heating system, use a resistance wire heater to surround the electrolysis reaction chamber, and maintain a set temperature gradient through a PID controller; the temperature range is from room temperature to 600K, and the gradient change rate is 10 to 50K / cm, ensuring that each layer of material can exhibit the expected magnetic properties within the corresponding temperature range;

[0014] Step 5, configure the electromagnetic coil array, support DC and AC power supply modes, the maximum output current can reach 10A, the voltage range is 0 to 50V; the coil spacing is 10 to 20cm, and the generated magnetic field strength ranges from 0.1 to 1T; the direction and strength of the coil current are controlled by the program to achieve rapid switching of the magnetic field, thereby selectively activating or inhibiting specific chemical reactions; in special cases, the magnetic field switching method can also introduce superconducting magnets, which can generate high-intensity and stable magnetic fields at extremely low temperatures, suitable for special application requirements in low-temperature ranges;

[0015] Step 6, write a control program to adjust the temperature field and magnetic field conditions according to the required reaction type; for hydrolysis reaction, give priority to activating the high Curie point material area; for electrodialysis and electrosorption, select the appropriate temperature and magnetic field combination according to the polarity of the target substance; for polar electrolytes, a stronger magnetic field needs to be applied at a higher temperature to promote ion migration; for non-polar organic matter, appropriately reduce the temperature and weaken the magnetic field to reduce the occurrence of side reactions;

[0016] Step 7: Configure various types of sensors, including temperature sensors, pH sensors, dissolved oxygen sensors, etc., to collect environmental parameters in the reaction chamber in real time; all sensor data are transmitted to the central controller, which automatically adjusts the working parameters of the heating system and electromagnetic coil after big data intelligent analysis to form a closed-loop feedback system to ensure the best reaction conditions. For salt electrolytes, focus on optimizing the ion conduction path to ensure efficient transmission; the above strategy also includes using machine learning algorithms to predict the optimal reaction conditions, and by collecting a large amount of experimental data to train models, especially support vector machines (SVM) and random forests (RF), identify complex time series relationships, provide more accurate parameter recommendations, and further improve the efficiency of electrolysis reactions. For organic matter, selective degradation is emphasized, and unnecessary by-products are suppressed by adjusting temperature and magnetic field parameters.

[0017] The present invention is beneficial in that:

[0018] 1) Multi-temperature range control: Using magnetic materials with different Curie points to achieve precise temperature gradient control, greatly improve reaction selectivity and activity, and adapt to various reaction requirements.

[0019] 2) Intelligent optimization system: SVM and RF algorithms are introduced to adjust heating and magnetic field parameters in real time to form a closed-loop feedback, significantly improve reaction efficiency and product selectivity, and reduce energy consumption.

[0020] 3) Efficient multilayer structure: Multilayer electrocatalysts are prepared by ion beam deposition to ensure good binding force and magnetic stability, enhance electrocatalytic performance, reduce side reactions, and improve application flexibility. IV. Description of the drawings

[0021] In order to more clearly illustrate the specific embodiments of the present invention, the drawings used in the description of the specific embodiments are briefly described below.

[0022] Figure 1 Schematic diagram of the structure of a multilayer Curie point composite material (electrode).

[0023] Figure 2 The schematic diagram of a water electrolysis reactor constructed of a multilayer Curie point composite material (electrode), wherein the reference numerals are explained as follows: electrolyte phase (1), separator (2), current collector (3), valve group (4), oxygen phase (5), hydrogen phase (6).

[0024] Figure 3 Schematic diagram of a water electrolysis reactor (multi-stack) built with multiple layers of Curie point composite materials (electrodes).

[0025] Figure 4 The current-potential change curve during the water electrolysis process of a water electrolysis reactor built with multi-layer Curie point composite materials (electrodes).

[0026] Figure 5 The current-coulomb efficiency change curve during the water electrolysis process of a water electrolysis reactor built with multi-layer Curie point composite materials (electrodes).

[0027] Figure 6 During the water electrolysis process of a water electrolysis reactor built with multi-layer Curie point composite materials (electrodes), the current change curve corresponding to hydrogen and oxygen evolution changes with the number of electrolytic cells. V. Specific implementation methods

[0028] The present invention is described in detail below with reference to the accompanying drawings and embodiments:

[0029] Embodiment 1:

[0030] A method for enhancing electrolytic reaction efficiency by programmable temperature gradient thermomagnetic effect, characterized in that the method specifically comprises the following steps:

[0031] Step 1, selecting magnetic alloy materials with different Curie points, specifically: ferrite (Fe3O4), Curie point is about 858K; nickel cobalt alloy (Ni-Co), Curie point range 600K; manganese zinc ferrite (Mn-Zn ferrite), Curie point 498K; yttrium barium copper oxide (YBCO), Curie point 92K; the above materials are respectively suitable for magnetic field regulation in different temperature ranges; the above magnetic alloy material can also include neodymium iron boron (NdFeB), whose Curie point is about 585K, which is used to expand the temperature response range, especially in high temperature areas to provide a stronger magnetic effect.

[0032] Step 2: The substrate material is a barium titanate (BaTiO3) ceramic sheet with good conductivity and corrosion resistance, with a thickness of 0.1 to 1 mm; the surface of the substrate needs to be polished, with a roughness Ra < 0.05 μm, to ensure uniform adhesion of subsequent deposited layers;

[0033] Step 3, using ion beam deposition to prepare multilayer Curie point materials, firstly, using ion beam deposition to prepare a first layer of magnetic alloy material on a substrate; setting the ion beam energy to 500 to 1000 eV and the working pressure to 1×10 -5Pa, the deposition rate is controlled at 0.1 to 1 nm / s, the deposition time is 1 to 5 h, and the first thin film with a thickness of 100 to 500 nm is formed; the deposition process is repeated to construct a multilayer structure; the other three magnetic alloy materials are deposited in sequence according to the above parameters, and the thickness of each layer is also controlled at 100 to 500 nm, and finally a composite film structure with four or more layers is formed; good bonding strength must be maintained between the layers to avoid stratification; the prepared multilayer structure is placed in a vacuum furnace and annealed under inert gas protection; the annealing temperature is set to 100K below the Curie point of the material, and the time lasts for 1 to 3 hours to optimize the crystal structure and improve the magnetic stability; among them, the ion beam deposition method can also use magnetron sputtering technology as an alternative, which is particularly suitable for preparing thicker magnetic alloy layers; during the magnetron sputtering process, the distance between the target material and the substrate is maintained at 5 to 10 cm, the sputtering power is 100 to 500 W, and the working gas pressure is 1×10 -3 Pa to obtain higher deposition rate and better film quality.

[0034] Step 4: Build a precise and controllable heating system, use a resistance wire heater to surround the electrolysis reaction chamber, and maintain a set temperature gradient through a PID controller; the temperature range is from room temperature to 600K, and the gradient change rate is 10 to 50K / cm, ensuring that each layer of material can exhibit the expected magnetic properties within the corresponding temperature range;

[0035] Step 5, configure the electromagnetic coil array, support DC and AC power supply modes, the maximum output current can reach 10A, the voltage range is 0 to 50V; the coil spacing is 10 to 20cm, and the generated magnetic field strength ranges from 0.1 to 1T; the direction and strength of the coil current are controlled by the program to achieve rapid switching of the magnetic field, thereby selectively activating or inhibiting specific chemical reactions; in special cases, the magnetic field switching method can also introduce superconducting magnets, which can generate high-intensity and stable magnetic fields at extremely low temperatures, suitable for special application requirements in low-temperature ranges;

[0036] Step 6, write a control program to adjust the temperature field and magnetic field conditions according to the required reaction type; for hydrolysis reaction, give priority to activating the high Curie point material area; for electrodialysis and electrosorption, select the appropriate temperature and magnetic field combination according to the polarity of the target substance; for polar electrolytes, a stronger magnetic field needs to be applied at a higher temperature to promote ion migration; for non-polar organic matter, appropriately reduce the temperature and weaken the magnetic field to reduce the occurrence of side reactions;

[0037] Step 7: Configure various types of sensors, including temperature sensors, pH sensors, dissolved oxygen sensors, etc., to collect environmental parameters in the reaction chamber in real time; all sensor data are transmitted to the central controller, which automatically adjusts the working parameters of the heating system and electromagnetic coil after big data intelligent analysis to form a closed-loop feedback system to ensure the best reaction conditions. For salt electrolytes, focus on optimizing the ion conduction path to ensure efficient transmission; the above strategy also includes using machine learning algorithms to predict the optimal reaction conditions, and by collecting a large amount of experimental data to train models, especially support vector machines (SVM) and random forests (RF), identify complex time series relationships, provide more accurate parameter recommendations, and further improve the efficiency of electrolysis reactions. For organic matter, selective degradation is emphasized, and unnecessary by-products are suppressed by adjusting temperature and magnetic field parameters.

[0038] In this embodiment, the schematic diagram of the structure of the multilayer Curie point composite material (electrode) prepared in steps 1 to 3 is shown in the attached figure. Figure 1 shown.

[0039] Embodiment 2:

[0040] The corresponding alkaline tank electrolysis water system is built with the multilayer Curie point composite material prepared in Example 1, and the specific process is as follows: First, a multilayer Curie point composite material is used as an electrode to ensure a significant magnetocaloric effect near the Curie point. The electrolytic cell adopts a zero gap design, and the gap between the electrode and the diaphragm is controlled within 0.5 mm to reduce the ohmic resistance. The diaphragm is made of polyphenylene sulfide composite material with high ion conductivity and chemical stability. The bipolar plate is made of titanium alloy material, and the surface is coated with a corrosion-resistant coating to ensure long-term operation stability. When assembling the electrolytic cell, the cathode, diaphragm, anode and porous transmission layer are installed in sequence, and bolts are used to tighten to ensure sealing. The alkali liquid circulation system includes an alkali liquid buffer, a gas-liquid separator and a circulation pump. The alkali liquid concentration is 6M KOH, and the flow rate and temperature are accurately adjusted through the PLC control system. The power supply system adopts an IGBT rectifier cabinet to support a wide range of current regulation to adapt to the fluctuating input of renewable energy.

[0041] When the system is started, nitrogen is first introduced to purge the electrolytic cell to ensure that there is no residual hydrogen inside. Then the alkali solution circulation pump is turned on, the alkali solution temperature is raised to 70°C, and the current density is adjusted to 200mA / cm through the PLC. 2 , gradually increased to 400mA / cm 2 During operation, the electrode surface temperature is monitored in real time by a temperature sensor, and the Curie point effect is used to dynamically adjust the electrode activity to optimize the efficiency of hydrogen and oxygen evolution reactions. The performance test includes polarization curve measurement and impedance spectrum analysis, and the current density is recorded at 10mA / cm 2 Overpotential and 100h durability test data.

[0042] The test results show that the system has a current density of 400mA / cm at room temperature. 2 When the energy consumption of hydrogen production is 4.17kWh / Nm 3 When the ambient temperature of the electrolytic cell rises to 45°C, the energy consumption of hydrogen production reaches the optimal value of 2.45kWh / Nm 3 It is generally believed that within 80°C, the hydrogen production efficiency of the alkaline cell should increase with the increase of temperature. However, for the temperature gradient thermomagnetic effect reactor of the present invention, when the ambient temperature of the electrolytic cell is increased to 70°C, the hydrogen production energy consumption increases again, reaching 3.72 kWh / Nm 3 The above experimental results prove that the temperature gradient thermomagnetic effect plays a regulatory role in the electrocatalytic performance during hydrogen production.

[0043] In this embodiment, a schematic diagram of a water electrolysis reactor constructed from a multilayer Curie point composite material (electrode) is shown in the attached Figure 2 shown.

[0044] In this embodiment, a schematic diagram of a water electrolysis reactor (multiple reactors) constructed from multiple layers of Curie point composite materials (electrodes) is shown in the attached Figure 3 shown.

[0045] Under the working conditions of the water electrolysis reactor, the current-potential change curve (see Appendix Figure 4 ), current-coulomb efficiency change curve (attached Figure 5 ), the number of electrolytic cells changes, and the current change curve corresponding to hydrogen and oxygen evolution (see Appendix Figure 6 ).

[0046] Embodiment 3:

[0047] Referring to the multilayer Curie point composite material in Example 2, a corresponding alkaline tank water electrolysis system is constructed, and a salt water electrolysis chlorine precipitation system is constructed. Except for the newly introduced electromagnetic coil array, it is basically the same as Example 1, and the specific process is not repeated here.

[0048] The initial experimental conditions were: water flow rate 0.5 L / min, residence time 120 min, electrocatalytic current 2 A, voltage 3 V, temperature room temperature (about 25 ° C). Under the initial conditions, the unit yield of active chlorine was 0.07 g / L·min, the Faraday efficiency was 60%, and the unit energy consumption was 0.8 kWh / kg Cl2.

[0049] After starting the heating system, the temperature gradient was set from room temperature to 400K, with a gradient change rate of 20K / cm. As the temperature gradually increased, the magnetic materials showed different magnetic properties below their respective Curie points, which affected the activity of the catalyst. When the temperature reached 350K, the unit yield of active chlorine increased to 0.115g / L·min, the Faraday efficiency increased to 77.5%, and the unit energy consumption decreased to 0.65kWh / kg Cl2; the temperature continued to rise to 400K, and the yield decreased to 0.105g / L·min due to the increase in side reactions caused by excessively high temperatures, and the Faraday efficiency also dropped back to 72.7%. This shows that there is an optimal temperature range, within which the highest reaction efficiency and the lowest energy consumption can be achieved.

[0050] After starting the electromagnetic coil array, the change test of magnetic field strength is carried out in the optimal temperature range (around 350K):

[0051] When the magnetic field strength is 0.5T, the unit yield of active chlorine increases to 0.14g / L·min, the Faraday efficiency stabilizes at 82.5%, and the unit energy consumption decreases to 0.60kWh / kg Cl2; when the magnetic field strength increases to 0.8T, the unit yield of active chlorine further increases to 0.16g / L·min, the Faraday efficiency reaches 85.7%, and the unit energy consumption decreases to 0.54kWh / kg Cl2; when the magnetic field strength is further increased to 1.7T, the excessively strong magnetic field causes some side reactions to occur, the unit yield of active chlorine decreases slightly to 0.15g / L·min, the Faraday efficiency remains at 83%, and the unit energy consumption increases slightly to 0.57kWh / kg Cl2.

[0052] A large amount of experimental data was collected to train the model, and support vector machine (SVM) and random forest (RF) algorithms were introduced for training. After combining the dual optimization of temperature and magnetic field, the system's unit yield of active chlorine, Faraday efficiency and unit energy consumption were significantly improved. Compared with simple temperature optimization, after introducing magnetic field optimization, the unit yield of active chlorine increased by 25%, the Faraday efficiency increased by 10%, and the unit energy consumption decreased by 15%. Compared with simple magnetic field optimization, combined with temperature optimization, the unit yield of active chlorine increased by 12.5%, the Faraday efficiency increased by 2%, and the unit energy consumption decreased by 2%.

[0053] Example 4

[0054] Referring to the electrolytic salt water chlorine precipitation system constructed with multi-layer Curie point composite materials in Example 3, it is applied to the process of electrocatalytic reduction of CO2 to generate CO, and the specific details are not repeated here.

[0055] The initial experimental conditions were: the inlet gas flow rate was set at 0.6 L / min, the residence time was 150 min, the electrocatalytic current was 3.0 A, the voltage was 2.5 V, and the temperature was maintained at room temperature (about 25 ° C). Under these conditions, the CO unit yield was 0.08 g / L·min, the Faraday efficiency reached 58.00%, and the unit energy consumption was 0.90 kWh / kg CO.

[0056] After starting the heating system, the temperature gradient was set from room temperature to 450K, with a gradient change rate of 25K / cm. As the temperature gradually increased, different magnetic materials exhibited different magnetic properties below their Curie points, which affected the activity of the catalyst. When the temperature rose to 400K, the unit yield of CO increased to 0.13g / L·min, the Faraday efficiency increased to 74%, and the unit energy consumption dropped to 0.75kWh / kg CO; when the temperature continued to rise to 450K, the excessively high temperature led to an increase in side reactions, the yield dropped back to 0.12g / L·min, and the Faraday efficiency also dropped to about 70%. This shows that there is an optimal temperature range within which the highest efficiency and lowest energy consumption can be achieved.

[0057] After starting the electromagnetic coil array, the change of magnetic field intensity was tested in the optimal temperature range (around 400K): when the magnetic field intensity was 0.6T, the unit yield of CO increased to 0.15g / L·min, the Faraday efficiency stabilized at 80.00%, and the unit energy consumption dropped to 0.70kWh / kg CO; when the magnetic field intensity increased to 0.9T, the unit yield of CO further increased to 0.17g / L·min, the Faraday efficiency reached 84%, and the unit energy consumption decreased to 0.65kWh / kg CO; when the magnetic field intensity was further increased to 1.2T, the excessively strong magnetic field triggered some side reactions, the unit yield of CO slightly dropped to 0.16g / L·min, the Faraday efficiency was maintained at 82.00%, and the unit energy consumption slightly increased to 0.67kWh / kg CO.

[0058] By combining the dual optimization of temperature and magnetic field, the system's CO unit yield, Faraday efficiency and unit energy consumption are significantly improved. Compared with simple temperature optimization, the introduction of magnetic field optimization increased the CO unit yield by 22.2%, the Faraday efficiency by 8.93%, and the unit energy consumption by 15%. Compared with simple magnetic field optimization, combined with temperature optimization, the CO unit yield increased by 11.7%, the Faraday efficiency by 4.2%, and the unit energy consumption by 5.3%. These data prove that the combination of multi-field coupling technology and intelligent control can significantly improve the efficiency and economy of electrocatalytic reduction of CO2 to produce CO.

[0059] The specific implementation methods described above are only used to specifically illustrate the spirit of the present invention, and the protection scope of the present invention is not limited thereto. For those skilled in the art, other implementation methods can certainly be easily made by changing, replacing or modifying the technical contents disclosed in this specification, and these other implementation methods should all be included in the protection scope of the present invention.

Claims

1. A method for enhancing the efficiency of electrolytic reaction by programmable temperature gradient thermomagnetic effect, characterized in that The method specifically comprises the following steps: Step 1, selecting magnetic alloy materials with different Curie points, specifically: ferrite (Fe3O4), Curie point is about 858K; nickel cobalt alloy (Ni-Co), Curie point range 600K; manganese zinc ferrite (Mn-Zn ferrite), Curie point 498K; yttrium barium copper oxide (YBCO), Curie point 92K; the above materials are respectively suitable for magnetic field regulation in different temperature ranges; Step 2: The substrate material is a barium titanate (BaTiO3) ceramic sheet with good conductivity and corrosion resistance, with a thickness of 0.1 to 1 mm; the surface of the substrate needs to be polished, with a roughness Ra < 0.05 μm, to ensure uniform adhesion of subsequent deposited layers; Step 3, using ion beam deposition to prepare multilayer Curie point materials, firstly, using ion beam deposition to prepare a first layer of magnetic alloy material on a substrate; setting the ion beam energy to 500 to 1000 eV and the working pressure to 1×10 -5 Pa, the deposition rate is controlled at 0.1 to 1 nm / s, the deposition time is 1 to 5 hours, and the first thin film with a thickness of 100 to 500 nm is formed; the deposition process is repeated to construct a multilayer structure; the other three magnetic alloy materials are deposited in sequence according to the above parameters, and the thickness of each layer is also controlled at 100 to 500 nm, and finally a composite film structure with four or more layers is formed; good bonding strength must be maintained between the layers to avoid stratification; the prepared multilayer structure is placed in a vacuum furnace and annealed under inert gas protection; the annealing temperature is set to 100K below the Curie point of the material, and the time lasts for 1 to 3 hours to optimize the crystal structure and improve the magnetic stability; Step 4: Build a precise and controllable heating system, use a resistance wire heater to surround the electrolysis reaction chamber, and maintain a set temperature gradient through a PID controller; the temperature range is from room temperature to 600K, and the gradient change rate is 10 to 50K / cm, ensuring that each layer of material can exhibit the expected magnetic properties within the corresponding temperature range; Step 5, configure the electromagnetic coil array, support DC and AC power supply modes, the maximum output current can reach 10A, the voltage range is 0 to 50V; the coil spacing is 10 to 20cm, and the generated magnetic field strength ranges from 0.1 to 1T; the direction and strength of the coil current are controlled by the program to achieve rapid switching of the magnetic field, thereby selectively activating or inhibiting specific chemical reactions; Step 6, write a control program to adjust the temperature field and magnetic field conditions according to the required reaction type; for hydrolysis reaction, give priority to activating the high Curie point material area; for electrodialysis and electrosorption, select the appropriate temperature and magnetic field combination according to the polarity of the target substance; for polar electrolytes, a stronger magnetic field needs to be applied at a higher temperature to promote ion migration; for non-polar organic matter, appropriately reduce the temperature and weaken the magnetic field to reduce the occurrence of side reactions; Step 7, configure various types of sensors, including temperature sensors, pH sensors, dissolved oxygen sensors, etc., to collect real-time environmental parameters in the reaction chamber; all sensor data are transmitted to the central controller, which automatically adjusts the working parameters of the heating system and the electromagnetic coil after intelligent analysis of big data to form a closed-loop feedback system to ensure optimal reaction conditions. For salt electrolytes, focus on optimizing the ion conduction path to ensure efficient transmission; for organic matter, emphasize selective degradation, and suppress the generation of unnecessary by-products by adjusting temperature and magnetic field parameters.

2. A method for enhancing electrolytic reaction efficiency by programmable temperature gradient thermomagnetic effect according to claim 1, characterized in that: The magnetic alloy material described in step 1 also includes neodymium iron boron (NdFeB), whose Curie point is about 585K, which is used to expand the temperature response range, especially to provide a stronger magnetic effect in the high temperature area.

3. A method for enhancing electrolytic reaction efficiency by programmable temperature gradient thermomagnetic effect according to claim 1, characterized in that: The ion beam deposition method described in step 3 can also use magnetron sputtering technology as an alternative, which is particularly suitable for preparing thicker magnetic alloy layers. During the magnetron sputtering process, the distance between the target and the substrate is maintained at 5 to 10 cm, the sputtering power is 100 to 500 W, and the working gas pressure is 1×10 -3 Pa to obtain higher deposition rate and better film quality.

4. A method for enhancing electrolytic reaction efficiency by programmable temperature gradient thermomagnetic effect according to claim 1, characterized in that: The magnetic field switching method described in step 5 also involves the introduction of a superconducting magnet, which can generate a high-intensity and stable magnetic field at extremely low temperatures and is suitable for special application requirements in the low-temperature range.

5. A method for enhancing electrolytic reaction efficiency by programmable temperature gradient thermomagnetic effect according to claim 1, characterized in that: The electrocatalytic strategies for different electrolytes described in step 7 also include using machine learning algorithms to predict the optimal reaction conditions, and by collecting a large amount of experimental data to train models, especially support vector machines (SVM) and random forests (RF), to identify complex time series relationships, provide more accurate parameter recommendations, and further improve the efficiency of the electrolysis reaction.

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