Preparation method and application of GaOOH (at) Ga-based liquid metal catalytic electrode
By preparing a GaOOH@Ga-based liquid metal catalytic electrode and utilizing the synergistic effect between Ga and GaOOH to form a heterojunction interface structure, the selectivity and stability issues of existing catalysts in the carbon dioxide reduction process were solved, and the reduction of carbon dioxide to carbon monoxide with high current density and high Faraday efficiency was achieved.
Patent Information
- Application Number
- CN202511192336.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-25
- Publication Date
- 2025-10-28
AI Technical Summary
Existing electrochemical catalysts suffer from problems such as low selectivity, poor stability, low current density, severe competitive reactions, and high catalyst cost in the carbon dioxide reduction process.
A GaOOH@Ga-based liquid metal catalytic electrode was used to prepare GaOOH@Ga electrode material by a constant potential electroreduction method, forming a heterojunction interface structure. The synergistic effect between Ga and GaOOH was utilized to provide electron donors, thereby improving the electronic structure of active sites and the activation ability of reaction sites.
It achieves highly efficient electrocatalytic carbon dioxide to carbon monoxide production, with a current density exceeding 70 mA/cm2 and a Faraday efficiency exceeding 95%, maintaining a high efficiency of over 90% even after long-term operation.
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Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing a GaOOH@Ga-based liquid metal catalytic electrode and its application, belonging to the field of electrochemical catalysis technology. Background Technology
[0002] Electrochemical carbon dioxide reduction (eCO2RR), as a core pathway for sustainable carbon cycling, can drive CO2 to be converted into high-value-added chemicals (such as CO, formic acid, methane, ethylene, etc.) through clean electricity, showing significant potential to replace traditional fossil fuel-based syngas production processes.
[0003] Currently, many metal electrocatalysts are widely used in the electrochemical reduction of CO2 to CO. These mainly include metal catalysts, single-atom catalysts, molecular catalysts, and alloy catalysts. Different catalysts exhibit varying characteristics in catalytic activity and selectivity due to differences in electronic structure, surface properties, and reaction mechanisms, and each faces its own technological challenges. Current catalysts mainly suffer from low selectivity, poor stability, low current density, severe competing reactions, and high cost. Therefore, there is an urgent need to develop a catalyst that is inexpensive, highly efficient in conversion, stable, has high current density, and can effectively suppress competing reactions. Summary of the Invention
[0004] To address the problems of low selectivity, poor stability, low current density, severe competition reactions, and high cost of existing electrochemical catalytic carbon dioxide reduction catalysts, this invention proposes a method for preparing and applying a GaOOH@Ga-based liquid metal catalytic electrode. This GaOOH@Ga-based liquid metal catalytic electrode can be used for the electrocatalytic reduction of carbon dioxide to carbon monoxide, achieving a current density exceeding 70 mA / cm² throughout the reduction process. 2 The Faraday efficiency for generating carbon monoxide exceeds 95%, and after 20 hours of operation, the Faraday efficiency for carbon monoxide remains above 90%, demonstrating high catalytic performance.
[0005] A method for preparing a GaOOH@Ga-based liquid metal catalytic electrode, the specific steps of which are as follows: (1) Add liquid Ga metal dropwise to ethanol and disperse it by ultrasonication to obtain Ga dispersion; (2) The Ga dispersion was centrifuged to separate the layers, the supernatant was removed, and the bottom precipitate was dried under vacuum to obtain Ga microparticles; (3) Ga particles, ethanol, PVP, acetylene black and Nifion solution are mixed evenly to obtain a suspension. The suspension is evenly coated onto carbon paper and dried under vacuum to obtain a Ga electrode. (4) Using a Ga electrode as the cathode, a graphite electrode, a platinum electrode or an IrO2·Ta2O5 coated titanium electrode as the anode, an organic solution electrolyte as the cathode electrolyte, and an aqueous sulfuric acid solution as the anode electrolyte, GaOOH@Ga-based liquid metal catalytic electrode is obtained by constant voltage electrolysis in an H-type electrolytic cell at room temperature and pressure.
[0006] Preferably, in step (1), the volume of the Ga dispersion is 2-5% of the volume of the Ga liquid, the ultrasonic dispersion temperature is 30-50℃, and the time is 0.5-2h.
[0007] Preferably, the vacuum drying temperature in step (2) is 20~80℃.
[0008] Preferably, based on 100 parts of the suspension in step (3), Ga particles account for 5-10 parts, ethanol accounts for 80-90 parts, PVP accounts for 1-4 parts, acetylene black accounts for 1-4 parts, and Nifion solution accounts for 1-6 parts.
[0009] Preferably, in step (4), the solute of the organic solution electrolyte is one or more of tetrabutylammonium perchlorate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, and tetrabutyltrifluoromethanesulfonic acid; the solvent of the organic solution electrolyte is one or more of acetonitrile, dimethyl sulfoxide, N-methylpyrrolidone, and N,N-dimethylformamide; the concentration of the organic solution electrolyte is 0.1~1.5 mol / L; and the concentration of the sulfuric acid aqueous solution is 0.1~1 mol / L.
[0010] Preferably, the constant voltage in step (4) is -1.5~-2.3V, and the time is 24~72h.
[0011] Application of the GaOOH@Ga-based liquid metal catalytic electrode in the electrocatalytic reduction of carbon dioxide to carbon monoxide: using the GaOOH@Ga-based liquid metal catalytic electrode as the cathode, a graphite electrode, a platinum electrode, or an IrO2·Ta2O5 coated titanium electrode as the anode, an organic solution electrolyte filled with saturated CO2 as the cathode electrolyte, and an aqueous sulfuric acid solution as the anode electrolyte, in an H-type electrolytic cell, at room temperature and pressure, constant voltage electrolytic catalytic reduction of CO2 to CO in situ is carried out and the CO is deposited at the cathode.
[0012] Preferably, the solute of the organic electrolyte is one or more of tetrabutylammonium perchlorate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, and tetrabutyltrifluoromethanesulfonic acid; the solvent of the organic electrolyte is one or more of acetonitrile, dimethyl sulfoxide, N-methylpyrrolidone, and N,N-dimethylformamide; the concentration of the organic electrolyte is 0.1~1.5 mol / L; and the concentration of the sulfuric acid aqueous solution is 0.1~1 mol / L.
[0013] Preferably, the constant voltage is -1.8 to -2.4V.
[0014] The principle of the GaOOH@Ga-based liquid metal catalytic electrode for catalytic reduction of carbon dioxide to carbon monoxide: The GaOOH@Ga electrode material prepared by the potentiostatic electroreduction method forms a unique heterojunction interface structure. In this heterojunction interface, there is a significant synergistic effect between Ga and GaOOH, which can effectively promote the electrochemical reaction process of CO2 reduction to CO. The core Ga acts as an electron donor in the electrochemical reduction process, continuously and stably providing electrons to the reaction system. This electron-donating behavior optimizes the electronic structure of the active sites, thereby enhancing the adsorption and activation capacity of the active sites for reaction intermediates by regulating the electron cloud distribution and electron state density around the active sites. The outer GaOOH layer, with its unique chemical composition and crystal structure, provides abundant and highly active reaction sites for the electrochemical carbon dioxide reduction reaction. These active sites can effectively adsorb CO2 molecules, reduce the activation energy of the reaction, and promote the reaction, thus giving our GaOOH@Ga-based liquid metal catalytic electrode high current density, good stability, and high catalytic efficiency.
[0015] The beneficial effects of this invention are: (1) The present invention uses an electrochemical reduction method to prepare GaOOH@Ga catalytic electrode, which can efficiently obtain non-noble metal catalyst electrode; (2) The GaOOH@Ga-based liquid metal catalytic electrode of this invention can be used for the electrocatalytic reduction of carbon dioxide to carbon monoxide. During the entire reduction process, the current density exceeds 70 mA / cm². 2 The Faraday efficiency for generating carbon monoxide exceeds 95%, and after 20 hours of operation, the Faraday efficiency for carbon monoxide remains above 90%, demonstrating high catalytic performance. Attached Figure Description
[0016] Figure 1 The scanning electron microscope (SEM) image and energy dispersive spectroscopy (EDS) spectrum of the GaOOH@Ga-based liquid metal catalytic electrode in Example 1 are shown. Figure 2 The diagram shows the constant potential current and Faraday efficiency of CO2 electroreduction using the GaOOH@Ga-based liquid metal catalytic electrode in Example 1. Figure 3 The diagram shows the constant potential current and Faraday efficiency of CO2 electroreduction using the GaOOH@Ga-based liquid metal catalytic electrode in Example 2. Figure 4 The diagram shows the constant potential current and Faraday efficiency of the CO2 electroreduction of the GaOOH@Ga-based liquid metal catalytic electrode in Example 3. Detailed Implementation
[0017] The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the content described.
[0018] Example 1: A method for preparing a GaOOH@Ga-based liquid metal catalytic electrode, the specific steps of which are as follows: (1) Metallic Ga liquid was added dropwise to ethanol and ultrasonically dispersed at 30°C for 0.5 h to obtain a Ga dispersion; the volume of metallic Ga liquid in the Ga dispersion accounted for 5%; (2) The Ga dispersion was centrifuged to separate the layers, the supernatant was removed, and the bottom precipitate was dried under vacuum at 30°C to obtain Ga microparticles; the particle size of the Ga microparticles was 10~100μm. (3) A suspension was prepared by uniformly mixing Ga microparticles, ethanol, PVP, acetylene black, and Nifion solution. The suspension was uniformly coated onto carbon paper and vacuum dried to obtain a Ga electrode. The mass ratio of Ga microparticles, ethanol, PVP, acetylene black, and Nifion solution was 5:90:3:1:1. The density of Ga microparticles on the Ga electrode was 20 mg / cm³. 2 ; (4) Using Ga electrode as cathode, platinum electrode as anode, 0.1 mol / L organic solution electrolyte as cathode electrolyte (tetrabutylammonium chloride as solute and acetonitrile as solvent), and 0.1 mol / L sulfuric acid aqueous solution as anode electrolyte, GaOOH@Ga-based liquid metal catalytic electrode was obtained by electrolysis at constant voltage (-1.8V) for 48 h in H-type electrolytic cell at room temperature and pressure. The scanning electron microscope (SEM) image and energy dispersive spectroscopy (EDS) spectrum of the GaOOH@Ga-based liquid metal catalytic electrode in this embodiment are shown below. Figure 1 ,from Figure 1 It can be seen that the GaOOH@Ga liquid metal catalytic electrode we prepared is relatively dense, and the GaOOH on the surface grows disorderedly outward, which can provide a very rich number of reactive sites for the electrochemical reduction of CO2 to CO. This embodiment describes the application of the GaOOH@Ga-based liquid metal catalytic electrode in the electrocatalytic reduction of carbon dioxide to carbon monoxide: using a GaOOH@Ga-based liquid metal catalytic electrode as the cathode, a platinum electrode as the anode, an organic solution electrolyte filled with saturated CO2 (concentration of 0.3 mol / L, solute of tetrabutylammonium chloride, solvent of acetonitrile) as the cathode electrolyte, and a sulfuric acid aqueous solution with a concentration of 0.1 mol / L as the anode electrolyte. In an H-type electrolytic cell, under constant voltage (-2.4V) at room temperature and pressure, CO2 is electrolytically reduced in situ to CO and deposited at the cathode. The potentiostatic current and Faraday efficiency diagrams for CO2 electroreduction using the GaOOH@Ga-based liquid metal catalytic electrode in this embodiment are shown below. Figure 2 ,from Figure 2 It can be seen that the current density is as high as 76 mA / cm².2 The faradaic efficiency for generating carbon monoxide is 95%, and after 20 hours of operation, the faradaic efficiency for generating carbon monoxide can still reach over 90%. Therefore, the GaOOH@Ga-based liquid metal catalytic electrode has excellent catalytic performance in long-term catalytic reactions.
[0019] Example 2: A method for preparing a GaOOH@Ga-based liquid metal catalytic electrode, the specific steps of which are as follows: (1) Add liquid Ga metal dropwise to ethanol and ultrasonically disperse at 40°C for 1 h to obtain Ga dispersion; the volume of liquid Ga metal in the Ga dispersion accounts for 4%; (2) The Ga dispersion was centrifuged to separate the layers, the supernatant was removed, and the bottom precipitate was dried under vacuum at 50°C to obtain Ga microparticles; the particle size of the Ga microparticles was 10~50μm. (3) A suspension was prepared by uniformly mixing Ga microparticles, ethanol, PVP, acetylene black, and Nifion solution. The suspension was uniformly coated onto carbon paper and dried under vacuum to obtain a Ga electrode. The mass ratio of Ga microparticles, ethanol, PVP, acetylene black, and Nifion solution was 5:87:3:3:2. The density of Ga microparticles on the Ga electrode was 20 mg / cm³. 2 ; (4) Using a Ga electrode as the cathode, a platinum electrode as the anode, an organic solution electrolyte with a concentration of 0.8 mol / L as the cathode electrolyte (tetrabutylammonium bromide as the solute and dimethyl sulfoxide as the solvent), and an aqueous sulfuric acid solution with a concentration of 0.5 mol / L as the anode electrolyte, GaOOH@Ga-based liquid metal catalytic electrode was obtained by electrolysis at constant voltage (-2.3V) for 36 h at room temperature and pressure in an H-type electrolytic cell. This embodiment describes the application of the GaOOH@Ga-based liquid metal catalytic electrode in the electrocatalytic reduction of carbon dioxide to carbon monoxide: using a GaOOH@Ga-based liquid metal catalytic electrode as the cathode, a platinum electrode as the anode, an organic solution electrolyte filled with saturated CO2 (concentration of 0.8 mol / L, solute of tetrabutylammonium bromide, solvent of dimethyl sulfoxide) as the cathode electrolyte, and a sulfuric acid aqueous solution with a concentration of 0.5 mol / L as the anode electrolyte. In an H-type electrolytic cell, under constant voltage (-2.0V) at room temperature and pressure, CO2 is electrolytically reduced in situ to CO and deposited at the cathode. The potentiostatic current and Faraday efficiency diagrams for CO2 electroreduction using the GaOOH@Ga-based liquid metal catalytic electrode in this embodiment are shown below. Figure 3 ,from Figure 3 It can be seen that the current density is as high as 70 mA / cm². 2The faradaic efficiency for generating carbon monoxide is about 91.8%, and after working for 20 hours, the faradaic efficiency for generating carbon monoxide can still reach more than 90%. Therefore, the GaOOH@Ga-based liquid metal catalytic electrode has excellent catalytic performance in long-term catalytic reactions.
[0020] Example 3: A method for preparing a GaOOH@Ga-based liquid metal catalytic electrode, the specific steps of which are as follows: (1) Add liquid Ga metal dropwise to ethanol and ultrasonically disperse at 50°C for 1.8 h to obtain Ga dispersion; the volume of liquid Ga metal in the Ga dispersion accounts for 2%; (2) The Ga dispersion was centrifuged to separate the layers, the supernatant was removed, and the bottom precipitate was dried under vacuum at 70°C to obtain Ga microparticles; the particle size of the Ga microparticles was 10-30 μm. (3) A suspension was prepared by uniformly mixing Ga microparticles, ethanol, PVP, acetylene black, and Nifion solution. The suspension was uniformly coated onto carbon paper and dried under vacuum to obtain a Ga electrode. The mass ratio of Ga microparticles, ethanol, PVP, acetylene black, and Nifion solution was 3:90:3:2:2. The density of Ga microparticles on the Ga electrode was 20 mg / cm³. 2 ; (4) Using a Ga electrode as the cathode, a platinum electrode as the anode, an organic solution electrolyte with a concentration of 1.2 mol / L as the cathode electrolyte (the solute is tetrabutyltrifluoromethanesulfonic acid and the solvent is N,N-dimethylformamide), and an aqueous sulfuric acid solution with a concentration of 0.8 mol / L as the anode electrolyte, GaOOH@Ga-based liquid metal catalytic electrode was obtained by electrolysis at a constant voltage (-1.6V) for 70 h at room temperature and pressure in an H-type electrolytic cell. This embodiment describes the application of the GaOOH@Ga-based liquid metal catalytic electrode in the electrocatalytic reduction of carbon dioxide to carbon monoxide: A GaOOH@Ga-based liquid metal catalytic electrode is used as the cathode, a platinum electrode as the anode, and an organic solution electrolyte filled with saturated CO2 (concentration 1.4 mol / L, solute tetrabutyltrifluoromethanesulfonic acid, solvent N,N-dimethylformamide) is used as the cathode electrolyte. A sulfuric acid aqueous solution with a concentration of 0.8 mol / L is used as the anode electrolyte. In an H-type electrolytic cell, CO2 is electrolytically reduced in situ to CO at a constant voltage (-1.8V) under ambient temperature and pressure, and CO is deposited at the cathode. The potentiostatic current and Faraday efficiency diagrams for CO2 electroreduction using the GaOOH@Ga-based liquid metal catalytic electrode in this embodiment are shown below. Figure 4 ,from Figure 4 It can be seen that the current density is as high as 60 mA / cm². 2The faradaic efficiency for generating carbon monoxide is 90%, and even after 20 hours of operation, the faradaic efficiency for generating carbon monoxide can still reach over 90%. Therefore, the GaOOH@Ga-based liquid metal catalytic electrode has excellent catalytic performance in long-term catalytic reactions.
[0021] The specific embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.
Claims
1. A method for preparing a GaOOH@Ga-based liquid metal catalytic electrode, characterized in that, The specific steps are as follows: (1) Add liquid Ga metal dropwise to ethanol and disperse it by ultrasonication to obtain Ga dispersion; (2) The Ga dispersion was centrifuged to separate the layers, the supernatant was removed, and the bottom precipitate was dried under vacuum to obtain Ga microparticles; (3) Ga particles, ethanol, PVP, acetylene black and Nifion solution are mixed evenly to obtain a suspension. The suspension is evenly coated onto carbon paper and dried under vacuum to obtain a Ga electrode. (4) Using a Ga electrode as the cathode, a graphite electrode, a platinum electrode or an IrO2·Ta2O5 coated titanium electrode as the anode, an organic solution electrolyte as the cathode electrolyte, and an aqueous sulfuric acid solution as the anode electrolyte, GaOOH@Ga-based liquid metal catalytic electrode is obtained by constant voltage electrolysis in an H-type electrolytic cell at room temperature and pressure.
2. The method for preparing the GaOOH@Ga-based liquid metal catalytic electrode according to claim 1, characterized in that: Step (1) The volume of metallic Ga liquid in the Ga dispersion is 2~5%, the ultrasonic dispersion temperature is 30~50℃, and the time is 0.5~2h.
3. The method for preparing the GaOOH@Ga-based liquid metal catalytic electrode according to claim 1, characterized in that: Step (2) Vacuum drying temperature is 20~80℃.
4. The method for preparing the GaOOH@Ga-based liquid metal catalytic electrode according to claim 1, characterized in that: Based on a mass of 100 parts of the suspension in step (3), Ga particles account for 5-10 parts, ethanol accounts for 80-90 parts, PVP accounts for 1-4 parts, acetylene black accounts for 1-4 parts, and Nifion solution accounts for 1-6 parts.
5. The method for preparing the GaOOH@Ga-based liquid metal catalytic electrode according to claim 1, characterized in that: Step (4) The solute of the organic solution electrolyte is one or more of tetrabutylammonium perchlorate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, and tetrabutyltrifluoromethanesulfonic acid; the solvent of the organic solution electrolyte is one or more of acetonitrile, dimethyl sulfoxide, N-methylpyrrolidone, and N,N-dimethylformamide; the concentration of the organic solution electrolyte is 0.1~1.5 mol / L, and the concentration of the sulfuric acid aqueous solution is 0.1~1 mol / L.
6. The method for preparing the GaOOH@Ga-based liquid metal catalytic electrode according to claim 1, characterized in that: Step (4) The constant voltage is -1.5~-2.3V, and the time is 24~72h.
7. The application of the GaOOH@Ga-based liquid metal catalytic electrode prepared by the method of any one of claims 1 to 6 in the electrocatalytic reduction of carbon dioxide to carbon monoxide.
8. The application according to claim 7, characterized in that: Using a GaOOH@Ga-based liquid metal catalytic electrode as the cathode, a graphite electrode, a platinum electrode, or an IrO2·Ta2O5 coated titanium electrode as the anode, an organic solution electrolyte filled with saturated CO2 as the cathode electrolyte, and an aqueous sulfuric acid solution as the anode electrolyte, CO2 is reduced to CO in situ under constant voltage electrolysis at room temperature and pressure in an H-type electrolytic cell and then deposited at the cathode.
9. The application according to claim 8, characterized in that: The solute in the organic electrolyte is one or more of tetrabutylammonium perchlorate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, and tetrabutyltrifluoromethanesulfonic acid; the solvent in the organic electrolyte is one or more of acetonitrile, dimethyl sulfoxide, N-methylpyrrolidone, and N,N-dimethylformamide; the concentration of the organic electrolyte is 0.1~1.5 mol / L, and the concentration of the sulfuric acid aqueous solution is 0.1~1 mol / L.
10. The application according to claim 8, characterized in that: The constant voltage is -1.8 to -2.4V.