A foam titanium-based iodine-iron double monatomic electrode and its preparation and application in preparation of singlet oxygen

Abstract

The present application relates to the field of electrochemistry, in particular to a foam titanium-based iodine-iron double monatomic electrode, preparation thereof and application in preparation of singlet oxygen. The configuration of the foam titanium-based iodine-iron double monatomic electrode provided by the present application has a double monatomic synergistic effect, can utilize iodine monatomic to dissociate water molecules to release atomic hydrogen, and the atomic hydrogen is used for reducing oxygen adsorbed on an activated iron site, so that the active site is fully utilized, the atomic utilization efficiency and the reaction activity are improved, and the occurrence of a competitive side reaction is reduced; the foam titanium-based iodine-iron double monatomic electrode material significantly improves the rate of electrochemical synthesis of singlet oxygen, expands the use scenarios of in-situ utilization of singlet oxygen, and has excellent performance in the fields of degradation of aromatic organic pollutants in water, removal of antibiotic resistance genes, and purification of pollutants such as pathogenic viruses in the air.

Description

Technical Field

[0001] This invention relates to the field of electrochemical technology, and in particular to a foamed titanium-based iodine-iron double single-atom electrode, its preparation, and its application in the preparation of singlet oxygen. Background Technology

[0002] As a newly emerging reactive oxygen species, singlet oxygen is considered a functional species with high redox potential and long lifetime, and is widely applicable to the purification and detoxification of pollutants in gas, liquid, and gas-liquid interfaces. Currently, traditional methods for synthesizing singlet oxygen mainly include photosensitization, enzymatic reactions, and advanced oxidation methods. However, these traditional methods are often limited by complex production facilities, harsh reaction conditions, or expensive oxidant inputs, failing to achieve stable, mild, green, and efficient singlet oxygen synthesis, severely restricting its application in environmental pollution control.

[0003] Electrochemical reduction and activation of oxygen is a mild and controllable singlet oxygen synthesis technology. This technology utilizes the Earth's abundant ground-state oxygen as a raw material, requiring only a continuous supply of electricity and oxygen to continuously generate singlet oxygen, thus facilitating the removal of pollutants from various environmental media. Patent CN117385390A discloses a method for electrochemically synthesizing singlet oxygen using a foamed titanium-based iron single-atom electrode. This electrode enhances the adsorption and activation of oxygen on the electrode surface and the directional conversion of intermediate products, emphasizing that the singlet oxygen yield of this electrode material can reach 6040.2 μmol / L. However, the electrode material requires calcination in a hydrogen atmosphere during preparation, which is not conducive to large-scale industrial production. Therefore, despite significant progress, how to further improve the singlet oxygen yield and achieve its efficient and controllable generation while meeting the requirements of large-scale industrial production remains a goal that those skilled in the art will continue to explore. Summary of the Invention

[0004] To address the aforementioned problems, the present invention aims to provide a foamed titanium-based iodine-iron dual single-atom electrode, its preparation, and its application in the preparation of singlet oxygen. The foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) provided by this invention utilizes the reduction and activation of oxygen by atomic hydrogen (·H) from water dissociation, enhancing the efficient and directional conversion process of oxygen, thereby achieving high-yield singlet oxygen synthesis (the foamed titanium-based iodine-iron dual single-atom electrode exhibits highly efficient electrochemical synthesis of singlet oxygen). The singlet oxygen preparation method provided by this invention offers a strategy for large-scale practical application in environmental purification and detoxification (removal and degradation of pollutants at gas, liquid, and gas-liquid interfaces, as well as disinfection).

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] The first objective of this invention is to provide a method for preparing a foamed titanium-based iodine-iron dual single-atom electrode, comprising the following steps:

[0007] (A1) The iron salt precursor solution was sprayed onto the surface of the foamed titanium carrier, dried by infrared drying, and then subjected to high temperature treatment to obtain a foamed titanium-based iron single-atom electrode.

[0008] (A2) The iodine precursor solution is coated on the surface of the foamed titanium-based iron single-atom electrode prepared in step (A1), dried by infrared drying and then subjected to high temperature treatment to obtain the foamed titanium-based iodine iron double single-atom electrode: I1Fe1-Ti.

[0009] In one embodiment of the present invention, in the foamed titanium-based iodine iron dual single-atom electrode, the mass percentage of single-atom iron is 0.05% to 2.0%, and the mass percentage of single-atom iodine is 0.1% to 4.0%.

[0010] The area of ​​the foamed titanium carrier is 3-25 cm². 2 The thickness is 0.5 to 2 mm.

[0011] In one embodiment of the present invention, in step (A1), the iron salt precursor is selected from one of ferric chloride, ferric nitrate, ferric sulfate, or ferric acetylacetone.

[0012] During the infrared drying process, the temperature is 40℃~150℃ and the time is 5min~30min;

[0013] The high-temperature treatment is carried out in an air atmosphere at a temperature of 200℃ to 500℃ for a time of 0.5h to 2h.

[0014] In one embodiment of the present invention, in step (A2), the iodine precursor is selected from one of iodic acid, hydroiodic acid, elemental iodine, sodium iodide, potassium iodide or iron iodide.

[0015] During the infrared drying process, the temperature is 40℃~150℃ and the time is 5min~30min;

[0016] The high-temperature treatment is carried out in an air atmosphere at a temperature of 200℃ to 500℃ for a time of 0.5h to 2h.

[0017] In one embodiment of the present invention, the solvent for the iron salt precursor solution is selected from one or more of ethanol, acetone, water, ethylene glycol or isobutanol.

[0018] The solvent for the iodine precursor solution is selected from one or more of ethanol, acetone, water, ethylene glycol, or isobutanol.

[0019] The second objective of this invention is to provide a foamed titanium-based iodine-iron dual single-atom electrode, which is prepared by the above method.

[0020] The third objective of this invention is to provide an application of a foamed titanium-based iodine-iron dual single-atom electrode in the preparation of singlet oxygen.

[0021] The fourth objective of this invention is to provide an application of a foamed titanium-based iodine-iron double single-atom electrode in the field of virus and organic pollutant purification, wherein the foamed titanium-based iodine-iron double single-atom electrode achieves in-situ purification of viruses and organic pollutants by synthesizing singlet oxygen.

[0022] The fifth objective of this invention is to provide a method for preparing singlet oxygen, comprising the following steps:

[0023] A working electrode, a reference electrode, and a counter electrode are inserted into a single-chamber electrolytic cell filled with electrolyte to carry out an electrolytic reaction and complete the synthesis of singlet oxygen.

[0024] The working electrode is the aforementioned foamed titanium-based iodine iron double single-atom electrode.

[0025] In one embodiment of the present invention, the reference electrode is selected from one of a mercury-mercury oxide electrode, a silver-silver chloride electrode, a saturated calomel electrode, or a mercury-mercurous sulfate electrode.

[0026] In one embodiment of the present invention, the counter electrode is selected from a platinum sheet electrode, a graphite electrode, or a ruthenium-iridium-titanium electrode.

[0027] In one embodiment of the present invention, the electrolyte is a 0.05 mol / L sodium sulfate solution;

[0028] During electrolysis, the reaction voltage is -1.0V to -0.4V, and the reaction time is 1h to 3h.

[0029] The foamed titanium-based iodine-iron dual single-atom electrode provided by this invention can achieve a singlet oxygen electrosynthesis yield of 62.8 μmol / L·min; the foamed titanium-based iodine-iron dual single-atom electrode can further effectively degrade aromatic organic pollutants in water, achieving removal rates of 99.6%, 99.8%, and 99.2% for phenol, sulfamethoxazole, and p-chlorophenol, respectively, within 2 hours; the foamed titanium-based iodine-iron dual single-atom electrode has a highly efficient removal effect on antibiotic resistance genes, and can remove antibiotic resistance genes within 1 hour. NDM-1 and bla OXA-58The removal rates of resistance genes reached 3.64 and 4.05 log, respectively; the foamed titanium-based iodine-iron dual single-atom electrode can efficiently inactivate pathogenic viruses in indoor air, and can kill more than 99.9% of H1N1 virus in the air in a short time; the foamed titanium-based iodine-iron dual single-atom electrode has a significant purification function for common volatile organic compounds, and can continuously and stably oxidize and remove 99.9% of formaldehyde in the air, while the carbon dioxide conversion rate reaches 98.8%. In summary, the foamed titanium-based iodine-iron dual single-atom electrode provided by this invention has both efficient singlet oxygen electrosynthesis capability and broad application potential, providing a green and low-carbon singlet oxygen electrosynthesis pathway and in-situ utilization technology.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The configuration of the foam titanium-based iodine iron double single-atom electrode provided by the present invention has a double single-atom synergistic effect, which can utilize the iodine single atom to dissociate water molecules to release atomic hydrogen. The atomic hydrogen is used to reduce the oxygen adsorbed on the activated iron site, thereby making full use of the active site, improving the atomic utilization efficiency and reaction activity, and reducing the occurrence of competitive side reactions.

[0032] (2) The foamed titanium-based iodine iron double single-atom electrode material provided by the present invention solves the problems of low singlet oxygen synthesis rate, complex and expensive preparation process and inability to be industrialized and mass-produced in the prior art. It significantly improves the singlet oxygen electrosynthesis rate and expands the application scenarios of in-situ utilization of singlet oxygen. It has excellent performance in the fields of degradation of aromatic organic pollutants in water, removal of antibiotic resistance genes, disinfection and inactivation of pathogenic viruses in the air, and purification of common volatile organic pollutants. Attached Figure Description

[0033] Figure 1 This is an AC-TEM image of the foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) prepared in Example 1 of this invention (black circles represent iron single atoms, and white circles represent iodine single atoms);

[0034] Figure 2 This is an X-ray energy dispersive spectroscopy (EDS) mapping of the foamed titanium-based iodine iron double single-atom electrode (I1Fe1-Ti) prepared in Example 1 of this invention;

[0035] Figure 3 This is the EPR spectrum of singlet oxygen electrosynthesis from the foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) prepared in Example 1 of this invention;

[0036] Figure 4 This is a singlet oxygen yield diagram of the foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) prepared in Example 1 of this invention;

[0037] Figure 5 This is a singlet oxygen yield diagram of the foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) prepared in Examples 1, 4, 5, 6 and 7 of this invention (with different iron loadings);

[0038] Figure 6 This is a singlet oxygen yield diagram of the foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) prepared in Examples 1, 9, 10, 11 and 12 of this invention (with different iodine loadings);

[0039] Figure 7 This is a graph showing the degradation performance of the foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) prepared in Example 1 of this invention on aromatic pollutants in water.

[0040] Figure 8 This is a performance evaluation diagram of the foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) prepared in Example 1 of this invention for the removal of antibiotic resistance genes;

[0041] Figure 9 This is a performance evaluation diagram of the foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) prepared in Example 1 of this invention for disinfection and inactivation of harmful viruses indoors;

[0042] Figure 10 This is a performance evaluation diagram of the foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) prepared in Example 1 of this invention for the continuous purification of indoor volatile organic compounds. Detailed Implementation

[0043] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0044] Unless otherwise specified, all reagents used in the following embodiments are commercially available reagents, and all detection methods and techniques used are conventional detection methods and techniques in the art.

[0045] Example 1

[0046] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0047] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 900 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2After drying with an infrared lamp (50℃, 5min) on a 0.68mm thick plate, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under air atmosphere, it is annealed at 400℃ for 1.5h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 1.0wt%.

[0048] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 800 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (50 °C, 5 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 400 °C for 1.5 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 2.0 wt%.

[0049] The foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) prepared in this embodiment was characterized using AC-TEM and energy-dispersive X-ray spectroscopy (EDS mapping). Figure 1 and Figure 2 As shown), through Figure 1 and Figure 2 It can be observed that I and Fe are anchored on the foamed titanium substrate in the form of single atoms; through Figure 2 It can be observed that iodine and iron single atoms are uniformly distributed on the surface of the foamed titanium, proving that the iodine-iron double single-atom material has been successfully synthesized.

[0050] Example 2

[0051] This embodiment provides a qualitative test for singlet oxygen capture using a foamed titanium-based iodine-iron dual single-atom electrode (prepared in Example 1) (testing singlet oxygen generated by the electrosynthesis reaction using electron paramagnetic resonance (EPR) method), as detailed below:

[0052] Using TEMP as a characteristic trapping agent, its characteristic binding with singlet oxygen can produce a triplet signal using EPR testing.

[0053] Reaction conditions: The foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) prepared in Example 1 was used as the cathode, a ruthenium-iridium titanium electrode as the anode, and silver / silver chloride as the reference electrode; the reaction electrolyte was 0.05 mol / L sodium sulfate solution (pH=6), and the reaction potential was -0.8 V; oxygen was continuously aerated during the reaction at a flow rate of 50 mL / min. After 10 min of reaction, 1 mL of the reaction solution was tested, and a significant singlet oxygen signal was detected; when tert-butanol (TBA) was added at a concentration of 50 mM as the quencher of atomic hydrogen, the singlet oxygen signal disappeared.

[0054] In summary, this demonstrates that the atomic hydrogen generated by the foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) prepared in Example 1 mediates the electrosynthesis of singlet oxygen in I1Fe1-Ti (e.g., Figure 3 (As shown).

[0055] Example 3

[0056] This embodiment provides a singlet oxygen yield test for a foamed titanium-based iodine-iron dual single-atom electrode (prepared in Example 1), as detailed below:

[0057] Reaction conditions: The foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) prepared in Example 1 was used as the cathode, a ruthenium-iridium titanium electrode as the anode, and silver / silver chloride as the reference electrode; the reaction electrolyte was 0.05 mol / L sodium sulfate solution (pH=6), the reaction volume was 35 mL, and the reaction potential was -0.8 V; oxygen was continuously aerated during the reaction at a flow rate of 50 mL / min, and the reaction time was 2 h. Under these conditions, furfuryl alcohol (FFA) was used to quantify the singlet oxygen generated by the electrode (e.g., ...). Figure 4 (As shown). Through Figure 4 It can be found that the yield of singlet oxygen in I1Fe1-Ti is 62.8 μmol / L·min (7536 μmol / L is produced in total), which is 3.97 times that of singlet oxygen in foam titanium electrode.

[0058] In summary, the foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) prepared in Example 1 has the ability to efficiently generate singlet oxygen.

[0059] Example 4

[0060] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0061] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 10 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2 After drying with an infrared lamp (50℃, 5min) on a 0.68mm thick material, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under an air atmosphere, it is annealed at 400℃ for 1.5h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 0.01wt%.

[0062] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 800 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (50 °C, 5 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 400 °C for 1.5 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 2.0 wt%.

[0063] Example 5

[0064] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0065] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 45 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2 After drying with an infrared lamp (50℃, 5min) on a 0.68mm thick material, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under an air atmosphere, it is annealed at 400℃ for 1.5h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 0.05wt%.

[0066] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 800 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (50 °C, 5 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 400 °C for 1.5 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 2.0 wt%.

[0067] Example 6

[0068] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0069] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 1800 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2 After drying with an infrared lamp (50℃, 5min) on a 0.68mm thick plate, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under air atmosphere, it is annealed at 400℃ for 1.5h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 2.0wt%.

[0070] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 800 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (50 °C, 5 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 400 °C for 1.5 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 2.0 wt%.

[0071] Example 7

[0072] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0073] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 3600 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2 After drying with an infrared lamp (50℃, 5min) on a 0.68mm thick plate, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under air atmosphere, it is annealed at 400℃ for 1.5h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 2.0wt%.

[0074] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 800 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (50 °C, 5 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 400 °C for 1.5 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 2.0 wt%.

[0075] Example 8

[0076] This embodiment provides a singlet oxygen yield test for foamed titanium-based iodine-iron double single-atom electrodes (prepared in Examples 1 and 4-7, respectively) with different iron loadings, as detailed below:

[0077] Reaction conditions: The foamed titanium-based iodine-iron dual single-atom electrodes prepared in Examples 1 and 4-7 were used as cathodes, ruthenium-iridium titanium electrodes as anodes, and silver / silver chloride as reference electrodes; the reaction electrolyte was 0.05 mol / L sodium sulfate solution (pH = 6), the reaction volume was 35 mL, and the reaction potential was -0.8 V; oxygen was continuously aerated during the reaction at a flow rate of 50 mL / min, and the reaction time was 2 h. Under these conditions, furfuryl alcohol (FFA) was used to quantify the singlet oxygen generated by each electrode (e.g., ...). Figure 5(As shown). Through Figure 5 It can be seen that when the iron content is between 0.05% and 2.0%, the foamed titanium-based iodine-iron dual single-atom electrode exhibits a relatively good singlet oxygen yield (39.4–62.5 μmol / L·min). When the iron content is 0.01% and 4.0%, its singlet oxygen yield is only 36.6% and 45.9% of that of I1Fe1-Ti, respectively.

[0078] This may be because iron acts as an adsorption activation site for oxygen. When the iron content is too low, the number of iron single atoms decreases, leading to a decline in the ability to activate oxygen. When the iron content is too high, iron single atoms undergo clustering, altering the oxygen adsorption structure and causing a decrease in the selectivity of the reaction that activates oxygen to produce singlet oxygen.

[0079] Example 9

[0080] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0081] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 900 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2 After drying with an infrared lamp (50℃, 5min) on a 0.68mm thick plate, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under air atmosphere, it is annealed at 400℃ for 1.5h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 1.0wt%.

[0082] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 10 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (50 °C, 5 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 400 °C for 1.5 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 0.02 wt%.

[0083] Example 10

[0084] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0085] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 900 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2After drying with an infrared lamp (50℃, 5min) on a 0.68mm thick plate, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under air atmosphere, it is annealed at 400℃ for 1.5h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 1.0wt%.

[0086] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 40 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (50 °C, 5 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 400 °C for 1.5 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 0.1 wt%.

[0087] Example 11

[0088] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0089] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 900 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2 After drying with an infrared lamp (50℃, 5min) on a 0.68mm thick plate, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under air atmosphere, it is annealed at 400℃ for 1.5h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 1.0wt%.

[0090] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 1600 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (50 °C, 5 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 400 °C for 1.5 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 4.0 wt%.

[0091] Example 12

[0092] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0093] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 900 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2After drying with an infrared lamp (50℃, 5min) on a 0.68mm thick plate, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under air atmosphere, it is annealed at 400℃ for 1.5h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 1.0wt%.

[0094] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 2400 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (50 °C, 5 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 400 °C for 1.5 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 6.0 wt%.

[0095] Example 13

[0096] This embodiment provides a singlet oxygen yield test for foamed titanium-based iodine-iron dual single-atom electrodes (prepared in Examples 1 and 9-12, respectively) with different iodine loadings, as detailed below:

[0097] Reaction conditions: The foamed titanium-based iodine-iron dual single-atom electrodes prepared in Examples 1 and 9-12 were used as cathodes, ruthenium-iridium-titanium electrodes as anodes, and silver / silver chloride as reference electrodes; the reaction electrolyte was 0.05 mol / L sodium sulfate solution (pH = 6), the reaction volume was 35 mL, and the reaction potential was -0.8 V; oxygen was continuously aerated during the reaction at a flow rate of 50 mL / min, and the reaction time was 2 h. Under these conditions, furfuryl alcohol (FFA) was used to quantify the singlet oxygen generated by each electrode (e.g., ...). Figure 6 (As shown). Through Figure 6 It can be seen that when the iodine content is between 0.1% and 4.0%, the foamed titanium-based iodine-iron dual single-atom electrode exhibits a relatively good singlet oxygen yield (37.9–62.5 μmol / L·min). When the iodine content is 0.02% and 6.0%, its singlet oxygen yield is only 29.3% and 42.4% of that of I1Fe1-Ti, respectively.

[0098] This may be because iodine serves as a donor site for atomic hydrogen. When the iodine content is too low, the ability to supply atomic hydrogen decreases, slowing down the rate of oxygen activation intermediate formation. When the iodine content is too high, atomic hydrogen tends to accumulate on the electrode surface, generating hydrogen gas (·H+·H→H2), which reduces the reaction selectivity of singlet oxygen synthesis.

[0099] Example 14

[0100] This embodiment provides a performance test of the foamed titanium-based iodine-iron dual single-atom electrode (prepared in Example 1) on the degradation of aromatic pollutants in water (phenol, sulfamethoxazole, and p-chlorophenol were selected as model pollutants), as detailed below:

[0101] Reaction conditions: The foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) prepared in Example 1 was used as the cathode, the ruthenium-iridium-titanium electrode as the anode, and silver / silver chloride as the reference electrode; the reaction electrolyte was 0.05 mol / L sodium sulfate solution (pH=6), the reaction potential was -0.8 V; the reaction volume was 35 mL, and the reaction time was 2 h; oxygen was continuously aerated during the reaction at a flow rate of 50 mL / min; the initial concentration of pollutants was 20 mg / L (e.g., ...). Figure 7 (As shown). Through Figure 7 It can be found that I1Fe1-Ti has a strong removal efficiency for all three pollutants. During the 2-hour period, the removal rates of phenol, sulfamethoxazole and chlorophenol can reach 99.6%, 99.8% and 99.2% respectively.

[0102] In summary, this demonstrates that the foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) prepared in Example 1 has excellent degradation performance for common aromatic organic pollutants in water.

[0103] Example 15

[0104] This embodiment provides a performance evaluation of the foamed titanium-based iodine-iron dual single-atom electrode (prepared in Example 1) for the removal of antibiotic resistance genes in water, as detailed below:

[0105] Reaction conditions: The drug-resistant bacterium Acinetobacter sp. CS-2 (CCTCC AB 2017269) was selected as the blanching agent. NDM-1 and bla OXA-58 Resistance genes were used as the target for detecting disinfection and inactivation performance. A foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) was used as the cathode, a ruthenium-iridium-titanium electrode as the anode, and silver / silver chloride as the reference electrode. The reaction electrolyte was 0.05 mol / L sodium sulfate solution (pH = 6), the reaction potential was -0.8 V, the reaction time was 1 h, the reaction solution volume was 35 mL, and oxygen was continuously aerated during the reaction at a flow rate of 50 mL / min. After the reaction, the collected samples were tested using real-time quantitative PCR to detect bla. NDM-1 and bla OXA-58 The content of resistance genes (such as) Figure 8 (As shown). Through Figure 8 It can be observed that I1Fe1-Ti has an effect on bla at the end of the reaction. NDM-1 and bla OXA-58The removal efficiencies can reach 3.64 and 4.05 log, respectively.

[0106] In summary, this demonstrates that the foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) prepared in Example 1 exhibits excellent antibiotic resistance gene removal performance.

[0107] Example 16

[0108] This embodiment provides a performance evaluation of the removal of pathogenic viruses from indoor air using a foamed titanium-based iodine-iron dual single-atom electrode (prepared in Example 1), as detailed below:

[0109] Reaction conditions: H1N1 virus (BEI Resources, NR-29034) was selected as the disinfection test object; a foam titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) was used as the cathode, a ruthenium-iridium titanium electrode as the anode, and silver / silver chloride as the reference electrode; the reaction electrolyte was 0.05 mol / L sodium sulfate solution (pH=6), and the reaction potential was -0.8V; the reaction was carried out in a cubic reaction chamber (0.5m×0.5m×0.5m) for 1 hour, with the humidity of the chamber kept constant at 60%.

[0110] Before the reaction begins, the solution containing the H1N1 virus is distributed in the reaction chamber in the form of an aerosol. The air in the chamber is first filtered by an air pump to remove large particles and then disinfected and inactivated. The flow rate is 30 L / min. During the reaction, the gas in the chamber is sampled at regular intervals at a flow rate of 15 L / min and inoculated into the culture medium.

[0111] The results are as follows Figure 9 As shown, through Figure 9 It was found that after 1 hour of continuous operation, more than 99.9% of the H1N1 virus in indoor air could be inactivated. As a control, the natural elimination rate of H1N1 without an electrochemical sterilization system was less than 30%.

[0112] In summary, this demonstrates that the foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) prepared in Example 1 has good application prospects for indoor virus inactivation.

[0113] Example 17

[0114] This embodiment provides a performance evaluation of the removal of volatile organic compounds (VOCs) from indoor air using a foamed titanium-based iodine-iron dual single-atom electrode (prepared in Example 1), as detailed below:

[0115] Reaction conditions: Formaldehyde was selected as the VOCs detection target; a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) was used as the cathode, a ruthenium-iridium-titanium electrode as the anode, and silver / silver chloride as the reference electrode; the reaction electrolyte was 0.05 mol / L sodium sulfate solution (pH=6), and the reaction potential was -0.8 V; the reaction was carried out in a 0.2 m × 0.2 m × 0.1 m reaction chamber, and the reaction gases consisted of clean air and formaldehyde standard gas (100 ppm). v The reactor consists of an air mass (N2) and a carrier gas, continuously fed into it at a flow rate of 0.1 L / min, with a formaldehyde standard gas flow rate of 0.02 L / min. During the reaction, the formaldehyde content in the exhaust gas is quantitatively analyzed every 30 minutes, and the carbon dioxide content is calculated. The total reaction time is 10 hours (e.g., ...). Figure 10 (As shown). Through Figure 10 It can be observed that after 90 minutes of reaction, the formaldehyde in the tail gas of the I1Fe1-Ti electrode is only 0.1%, and the formaldehyde conversion rate is stable at 99.9% at the end of the reaction, while the selectivity of carbon dioxide can reach 98.9%.

[0116] In summary, this demonstrates that the foamed titanium-based iodine-iron dual single-atom electrode (I1Fe1-Ti) prepared in Example 1 has a strong effect on removing common indoor VOCs.

[0117] Example 18

[0118] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0119] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 900 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2 After drying with an infrared lamp (40℃, 30min) on a 0.68mm thick plate, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under air atmosphere, it is annealed at 200℃ for 2h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 1.0wt%.

[0120] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 800 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (150 °C, 5 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 500 °C for 0.5 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 2.0 wt%.

[0121] Example 19

[0122] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0123] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 900 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2 After drying with an infrared lamp (50℃, 10min) on a 0.68mm thick plate, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under air atmosphere, it is annealed at 400℃ for 1.5h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 1.0wt%.

[0124] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 800 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (40 °C, 30 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 500 °C for 1 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 2.0 wt%.

[0125] Example 20

[0126] This embodiment provides a method for preparing a foamed titanium-based iodine-iron double single-atom electrode, including the following steps:

[0127] (A1) Dissolve 40 mg of ferric chloride in 4 mL of ethanol to obtain a ferric chloride ethanol solution; then take 900 μL of the ferric chloride ethanol solution and spray it evenly onto a foamed titanium substrate (area 9 cm²). 2 After drying with an infrared lamp (150℃, 5min) on a 0.68mm thick plate, it is placed in a corundum ceramic boat and then placed in a muffle furnace. Under air atmosphere, it is annealed at 500℃ for 0.5h to obtain a foamed titanium-based iron single-atom electrode (Fe1-Ti) with an iron content of 1.0wt%.

[0128] (A2) Dissolve 100 mg of iodic acid in 10 mL of water to obtain an iodic acid solution; then take 800 μL of the iodic acid solution and spray it evenly onto the foamed titanium-based iron single-atom electrode prepared in step (A1). After drying with an infrared lamp (40 °C, 15 min), place it in a corundum ceramic boat and place it in a muffle furnace. Under an air atmosphere, anneal at 400 °C for 1.5 h to obtain a foamed titanium-based iodine-iron double single-atom electrode (I1Fe1-Ti) with an iodine content of 2.0 wt%.

[0129] The foamed titanium-based iodine-iron double single-atom electrodes (I1Fe1-Ti) prepared in Examples 18 to 20 were tested for singlet oxygen yield, degradation performance of aromatic pollutants in water (phenol, sulfamethoxazole, and p-chlorophenol were selected as model pollutants), removal performance of antibiotic resistance genes in water, and removal performance of pathogenic viruses in indoor air. It was found that the performance of the foamed titanium-based iodine-iron double single-atom electrodes (I1Fe1-Ti) prepared in Examples 18 to 20 was roughly the same as that of the foamed titanium-based iodine-iron double single-atom electrodes (I1Fe1-Ti) prepared in Example 1.

[0130] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the interpretation of the present invention, without departing from the scope of the invention, should be within the protection scope of the present invention.

Claims

1. A method for preparing a foamed titanium-based iodine-iron dual single-atom electrode, characterized in that, Includes the following steps: (A1) The iron salt precursor solution was sprayed onto the surface of the foamed titanium carrier, dried by infrared drying, and then subjected to high temperature treatment to obtain a foamed titanium-based iron single-atom electrode. (A2) The iodine precursor solution is coated on the surface of the foamed titanium-based iron single-atom electrode prepared in step (A1), dried by infrared drying and then subjected to high temperature treatment to obtain the foamed titanium-based iodine iron double single-atom electrode: I1Fe1-Ti.

2. The method for preparing a foamed titanium-based iodine-iron dual single-atom electrode according to claim 1, characterized in that, In the foamed titanium-based iodine-iron dual single-atom electrode, the mass percentage of single-atom iron is 0.05% to 2.0%, and the mass percentage of single-atom iodine is 0.1% to 4.0%.

3. The method for preparing a foamed titanium-based iodine-iron dual single-atom electrode according to claim 2, characterized in that, In step (A1), the iron salt precursor is selected from one of ferric chloride, ferric nitrate, ferric sulfate, or ferric acetylacetone; During the infrared drying process, the temperature is 40℃~150℃ and the time is 5min~30min; The high-temperature treatment is carried out in an air atmosphere at a temperature of 200℃ to 500℃ for a time of 0.5h to 2h.

4. The method for preparing a foamed titanium-based iodine-iron dual single-atom electrode according to claim 2, characterized in that, In step (A2), the iodine precursor is selected from one of iodic acid, hydroiodic acid, elemental iodine, sodium iodide, potassium iodide or ferric iodide; During the infrared drying process, the temperature is 40℃~100℃ and the time is 5min~30min; The high-temperature treatment is carried out in an air atmosphere at a temperature of 200℃ to 500℃ for a time of 0.5h to 2h.

5. A foamed titanium-based iodine-iron dual single-atom electrode, characterized in that, It is prepared by any one of the methods described in claims 1 to 3.

6. The application of the foamed titanium-based iodine iron double single-atom electrode as described in claim 5 in the preparation of singlet oxygen.

7. The application of the foamed titanium-based iodine-iron dual single-atom electrode as described in claim 5 in the field of virus and organic pollutant purification, characterized in that, The foamed titanium-based iodine-iron dual single-atom electrode achieves in-situ purification of viruses and organic pollutants by synthesizing singlet oxygen.

8. A method for preparing singlet oxygen, characterized in that, Includes the following steps: A working electrode, a reference electrode, and a counter electrode are inserted into a single-chamber electrolytic cell filled with electrolyte to carry out an electrolytic reaction and complete the synthesis of singlet oxygen. The working electrode is the foamed titanium-based iodine iron double single-atom electrode as described in claim 5.

9. The method for preparing singlet oxygen according to claim 8, characterized in that, The reference electrode is selected from one of the following: mercury-mercury oxide electrode, silver-silver chloride electrode, saturated calomel electrode, or mercury-mercurous sulfate electrode. The counter electrode is selected from one of a platinum sheet electrode, a graphite electrode, or a ruthenium-iridium-titanium electrode.

10. A method for preparing singlet oxygen according to claim 8, characterized in that, The electrolyte is a sodium sulfate solution; During electrolysis, the reaction voltage is -1.0V to -0.4V, and the reaction time is 1h to 3h.

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