Carbon dioxide reduction cathode, photovoltaic device and preparation method and application thereof
By loading an indium single-atom catalyst and a nitrogen-oxygen-doped carbon support onto a carbon-based conductive substrate and combining it with a photovoltaic device, a high-efficiency carbon dioxide reduction photovoltaic device was constructed. This solved the problems of selectivity and low energy conversion efficiency in the carbon dioxide reduction reaction, and achieved a carbon dioxide reduction effect with high selectivity and high energy conversion efficiency.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHANDONG UNIV
- Filing Date
- 2023-11-10
- Publication Date
- 2026-07-07
Smart Images
Figure CN117512650B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of photoelectrocatalytic materials technology, and relates to a carbon dioxide reduction cathode, a photovoltaic device, its preparation method and application. Background Technology
[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.
[0003] Human society's continued reliance on fossil fuels over the past few centuries has led to a rapid rise in atmospheric carbon dioxide concentrations, resulting in a series of environmental problems such as the greenhouse effect and energy shortages. Converting carbon dioxide into high-value products can both reduce carbon dioxide concentrations and emissions, thus simultaneously addressing environmental issues and energy shortages. Utilizing renewable energy sources to electrocatalytically convert carbon dioxide into high-value hydrocarbon fuels is very attractive and has received increasing attention. However, due to losses during power transmission, the efficiency of renewable energy generation, and the low selectivity of the carbon dioxide reduction reaction at the cathode, the efficiency of converting renewable energy into the chemical energy of carbon dioxide reduction products remains relatively low. Summary of the Invention
[0004] To address the shortcomings of existing technologies, the present invention aims to provide a carbon dioxide reduction cathode, a photovoltaic device, its fabrication method, and its applications. The present invention, on the one hand, prepares a highly efficient carbon dioxide reduction electrode using an indium single-atom catalyst as the active component; on the other hand, it couples a highly efficient photovoltaic device with an electrochemical cell, thereby constructing a carbon dioxide reduction photovoltaic device with high cathode product selectivity and high energy conversion efficiency.
[0005] To achieve the above objectives, the present invention is implemented through the following technical solution:
[0006] In a first aspect, the present invention provides a carbon dioxide reduction cathode, comprising a carbon-based conductive substrate and an indium single-atom catalyst supported on the carbon-based conductive substrate, wherein the indium single-atom catalyst comprises a nitrogen-oxygen-doped carbon support and indium single atoms supported on the nitrogen-oxygen-doped carbon support, wherein the indium single atoms are bonded to nitrogen and oxygen through coordination bonds.
[0007] Preferably, the indium single-atom catalyst is loaded at 1-2 mg / cm³ at the cathode. 2 .
[0008] Preferably, the carbon-based conductive substrate includes at least one of hydrophobic carbon paper, carbon cloth, and carbon fiber felt.
[0009] Preferably, the preparation method of the indium single-atom catalyst includes the following steps:
[0010] Dopamine hydrochloride was dissolved in water, and then tris(hydroxymethyl)aminomethane, silicon dioxide, and indium salt were added sequentially. After stirring and reacting, the product was separated by centrifugation. After annealing the product, the silicon dioxide was removed to obtain the indium single-atom catalyst.
[0011] Further preferably, the mass ratio of dopamine hydrochloride to tris(hydroxymethyl)aminomethane is 1:0.9-1; the indium salt includes indium chloride; the annealing temperature is 700-800℃, and the annealing time is 1.5-2.5h.
[0012] In a second aspect, the present invention provides a method for preparing a carbon dioxide reduction cathode as described in the first aspect, comprising the following steps: dispersing an indium single-atom catalyst in an organic solvent containing a perfluorosulfonic acid polymer to prepare an ink, and dripping the ink onto a carbon-based conductive substrate and drying it to obtain the cathode.
[0013] Thirdly, the present invention provides a carbon dioxide reduction photovoltaic device, comprising a solar cell, an anode, a carbon dioxide reduction cathode as described in the first aspect, and a flow cell, wherein the anode and the carbon dioxide reduction cathode are connected to the solar cell via wires, and the anode and the carbon dioxide reduction cathode are placed in the flow cell.
[0014] Preferably, the anode is a NiFe-LDH-loaded metal electrode, the metal electrode comprising nickel foam, and the anode preparation method includes the following steps: dissolving nickel salt, iron salt, ammonium fluoride and urea in water to prepare a mixed solution, and placing the metal electrode in the mixed solution to carry out a hydrothermal reaction, thereby obtaining the anode.
[0015] Preferably, the flow cell includes a gas diffusion electrolysis cell or a membrane electrode cell, and the electrolyte in the flow cell includes a potassium bicarbonate solution or a potassium hydroxide solution.
[0016] Fourthly, the present invention provides the application of carbon dioxide reduction cathodes as described in the first aspect and / or carbon dioxide reduction photovoltaic devices as described in the third aspect in the electrocatalytic and / or photocatalytic reduction of carbon dioxide to prepare formate.
[0017] The beneficial effects achieved by one or more technical solutions of the present invention are as follows:
[0018] (1) The carbon dioxide reduction cathode prepared in this invention exhibits high current density and high selectivity in the reaction of carbon dioxide reduction to formate, with a current density close to -150 mA / cm². -2 At current densities, its formate selectivity reaches as high as 97.5%, which shows broad prospects for practical applications.
[0019] (2) The carbon dioxide reduction photovoltaic device assembled in this invention has a higher solar energy to formic acid conversion efficiency and formic acid production rate than similar photoelectrocatalytic carbon dioxide reduction devices. The solar energy to formic acid conversion efficiency is 13.22%, and the formic acid production rate is 0.17 mmol / h / cm. 2 . Attached Figure Description
[0020] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.
[0021] Figure 1 X-ray diffraction (XRD) image of the indium single-atom catalyst in Example 1;
[0022] Figure 2 This is the X-ray photoelectron spectrum of the indium single-atom catalyst in Example 1, where A is the full spectrum and B is the In 3d spectrum;
[0023] Figure 3 This is an aberration-corrected high-angle annular dark-field scanning transmission electron microscope image of the indium single-atom catalyst in Example 1.
[0024] Figure 4 The X-ray absorption spectrum of the indium single-atom catalyst in Example 1 is shown, where A is the K-edge XANES spectrum, B is the K-edge FT-EXAFS spectrum, and C is the corresponding EXAFS fitting curve in R space.
[0025] Figure 5 The linear sweep voltammetric curves (A) of the cathode in argon atmosphere and carbon dioxide atmosphere in Example 2, the selectivity diagram (B) of electrocatalytic carbon dioxide reduction to formate at different voltages, and the stability diagram (C) of electrocatalytic carbon dioxide reduction are shown.
[0026] Figure 6 This is a schematic diagram of the carbon dioxide reduction photovoltaic device in Example 3;
[0027] Figure 7 The image shows the performance of the carbon dioxide reduction photovoltaic device in Example 3. Detailed Implementation
[0028] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments and comparative examples.
[0029] Example 1
[0030] Preparation of a highly loaded indium single-atom catalyst: 1.79 g of dopamine hydrochloride was dissolved in 500 mL of water, and then 1.7 g of tris(hydroxymethyl)aminomethane was added with stirring. 1.00 g of silica, dispersed in 100 mL of water, was added to the system. After 10 minutes, 10 mL of a 0.1 mol / L indium-containing catalyst was added. 3+ An aqueous solution was injected into the system, and the reaction continued for 12 hours. The product was separated by centrifugation, dried, and annealed at 750°C for 2 hours under an argon atmosphere. Finally, the silica template was etched away with NaOH solution to obtain a highly loaded indium single-atom catalyst (In-O₂N₂ SACs). Figure 1 As shown, the XRD pattern of the indium single-atom catalyst does not show obvious peaks for indium nanoparticles or indium oxide. Figure 2 As shown, indium single-atom catalysts contain carbon, nitrogen, oxygen, and indium elements, and the valence state of indium in indium single-atom catalysts is between zero and +3. Figure 3 As shown, no indium nanoparticles or metal oxides such as indium oxide were found, proving that indium exists in a single-atom state. Figure 4 As shown, in the indium single-atom catalyst, the indium sites are dispersed in a single-atom state, with each indium atom coordinated to two oxygen atoms and two nitrogen atoms.
[0031] Preparation of carbon dioxide reduction cathode: 4 mg of indium single-atom catalyst was dispersed in a mixture of 100 μL Nafion-520 and 400 μL ethanol to prepare catalyst ink. 200 μL of this ink was then dropped onto 1 × 1 cm² hydrophobic carbon paper to obtain the desired carbon dioxide reduction cathode.
[0032] Example 2
[0033] Application of the carbon dioxide reduction cathode in electrocatalytic carbon dioxide reduction (Example 1):
[0034] (1) NiFe-LDH was prepared as an anode using the following steps: 0.58 g Ni(NO3)2·6H2O, 0.14 g FeSO4·7H2O, 0.37 g NH4F, and 1.4994 g CO(NH2)2 were dissolved in 40 mL of water, and a 2×3 cm... 2 The nickel foam was placed in a solution and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene. The autoclave was kept at 120°C for 8 hours, then removed, cooled to room temperature, washed with distilled water and ethanol, and dried in air to obtain the NiFe-LDH anode.
[0035] (2) Place the cathode and anode in a gas diffusion electrolysis cell and use 1M potassium hydroxide solution as the electrolyte solution to carry out carbon dioxide reduction experiment.
[0036] like Figure 5As shown, it can maintain >80% formate product selectivity over a wide potential range of -0.6 to -1.3V vs. RHE, up to 97.5% at -0.7V vs. RHE, and can operate stably for 6 hours without significant performance degradation at -0.8V vs. RHE.
[0037] Example 3
[0038] like Figure 6 As shown, a commercially available indium gallium phosphide / gallium arsenide / germanium solar cell was assembled with the carbon dioxide reduction cathode of Example 1 and the NiFe-LDH and gas diffusion electrolyzer of Example 2 to construct a carbon dioxide reduction photovoltaic device for photoelectrochemical carbon dioxide reduction.
[0039] The performance of carbon dioxide reduction photovoltaic devices, such as Figure 7 As shown, at a current density of 10.08 mA / cm² 2 At that time, the selectivity of formate exceeded 90%, and it could operate stably for 10 hours.
[0040] Example 4
[0041] Preparation of a highly loaded indium single-atom catalyst: 1.79 g of dopamine hydrochloride was dissolved in 500 mL of water, and then 1.75 g of tris(hydroxymethyl)aminomethane was added with stirring. 1.00 g of silica, dispersed in 100 mL of water, was added to the system. After 10 minutes, 10 mL of 0.1 mol / L indium-containing catalyst was added. 3+ An aqueous solution was injected into the system, and the reaction continued for 12 hours. The product was separated by centrifugation, dried, and annealed at 800 degrees Celsius for 1.5 hours in an argon atmosphere. Finally, the silica template was etched away with NaOH solution to obtain a highly loaded indium single-atom catalyst.
[0042] Preparation of carbon dioxide reduction cathode: 5 mg of indium single-atom catalyst was dispersed in a mixture of 100 μL Nafion-520 and 400 μL ethanol to prepare catalyst ink. 200 μL of this ink was then dropped onto 1 × 1 cm² hydrophobic carbon paper to obtain the desired carbon dioxide reduction cathode.
[0043] Example 5
[0044] Preparation of a highly loaded indium single-atom catalyst: 1.79 g of dopamine hydrochloride was dissolved in 500 mL of water, and then 1.8 g of tris(hydroxymethyl)aminomethane was added with stirring. 1.00 g of silica, dispersed in 100 mL of water, was added to the system. After 10 minutes, 10 mL of a catalyst containing In was added... 3+An aqueous solution was injected into the system, and the reaction continued for 12 hours. The product was separated by centrifugation, dried, and annealed at 700°C for 2.5 hours in an argon atmosphere. Finally, the silica template was etched away with NaOH solution to obtain a highly loaded indium single-atom catalyst.
[0045] Preparation of carbon dioxide reduction cathode: 2.5 mg of indium single-atom catalyst was dispersed in a mixture of 100 μL Nafion-520 and 400 μL ethanol to prepare catalyst ink. 200 μL of this ink was then dropped onto 1 × 1 cm² hydrophobic carbon paper to obtain the desired carbon dioxide reduction cathode.
[0046] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A carbon dioxide reduction cathode, characterized in that, The invention includes a carbon-based conductive substrate and an indium single-atom catalyst supported on the carbon-based conductive substrate. The indium single-atom catalyst includes a nitrogen-oxygen-doped carbon support and indium single atoms supported on the nitrogen-oxygen-doped carbon support. The indium single atoms are bonded to nitrogen and oxygen through coordination bonds. The preparation method of the indium single-atom catalyst includes the following steps: Dopamine hydrochloride was dissolved in water, and then tris(hydroxymethyl)aminomethane, silicon dioxide, and indium salt were added sequentially. After stirring and reacting, the product was separated by centrifugation. After annealing, the silicon dioxide was removed to obtain the indium single-atom catalyst. The indium single-atom catalyst was In-O2N2SACs. The mass ratio of dopamine hydrochloride to tris(hydroxymethyl)aminomethane is 1:0.9-1; the indium salt includes indium chloride; the annealing temperature is 700-800 ℃, and the annealing time is 1.5-2.5 h.
2. The carbon dioxide reduction cathode as described in claim 1, characterized in that, The indium single-atom catalyst is loaded at a cathode at a concentration of 1-2 mg / cm³. 2 .
3. The carbon dioxide reduction cathode as described in claim 1, characterized in that, The carbon-based conductive substrate includes at least one of hydrophobic carbon paper, carbon cloth, and carbon fiber felt.
4. A method for preparing a carbon dioxide reduction cathode as described in any one of claims 1-3, characterized in that, The process includes the following steps: dispersing an indium single-atom catalyst in an organic solvent containing a perfluorosulfonic acid polymer to prepare an ink, and then dropping the ink onto a carbon-based conductive substrate and drying it to obtain the cathode.
5. A carbon dioxide reduction photovoltaic device, characterized in that, The device includes a solar cell, an anode, a carbon dioxide reduction cathode as described in any one of claims 1-3, and a flow cell, wherein the anode and the carbon dioxide reduction cathode are connected to the solar cell via wires, and the anode and the carbon dioxide reduction cathode are placed in the flow cell; The anode is a NiFe-LDH loaded metal electrode, which includes nickel foam. The anode is prepared by dissolving nickel salt, iron salt, ammonium fluoride and urea in water to prepare a mixed solution, and placing the metal electrode in the mixed solution to carry out a hydrothermal reaction to obtain the anode.
6. The carbon dioxide reduction photovoltaic device as described in claim 5, characterized in that, The flow cell includes a gas diffusion electrolysis cell or a membrane electrode cell, and the electrolyte in the flow cell includes a potassium bicarbonate solution or a potassium hydroxide solution.
7. The application of the carbon dioxide reduction cathode as described in any one of claims 1-3 and / or the carbon dioxide reduction photovoltaic device as described in any one of claims 5-6 in the electrocatalytic and / or photocatalytic reduction of carbon dioxide to prepare formate.