Preparation method of NaTaO3 / C3N4 material and application of NaTaO3 / C3N4 material in photocatalytic hydrogen production or antibiotic degradation

Abstract

The invention discloses a carbon nitride loaded sodium tantalate (NaTaO3 / C3N4) material, a preparation method thereof and application of the carbon nitride loaded sodium tantalate (NaTaO3 / C3N4) material in photocatalytic hydrogen production or antibiotic degradation. The preparation method of the NaTaO3 / C3N4 material comprises the following steps: mixing 5g of C3H6N6 and 200ml of H2O, putting the mixture into a constant-temperature water bath kettle, adding concentrated HNO3 and 100ml of H2O, reacting for one hour, raising the temperature of the water bath to 95 DEG C, adding Ta2O5 and 0.6 g of NaOH, reacting for one hour, pouring the mixed solution into ice water, cooling, separating out a solid, putting the solid into a suction filter, filtering, precipitating, and drying to obtain the NaTaO3 / C3N4 material. And finally, drying in a drying oven at 60 DEG C to obtain a precursor. And adding the precursor into a tubular furnace, introducing Ar gas, heating to a specified temperature at a speed of 2 DEG C per minute, maintaining the temperature for four hours, and then cooling to room temperature to finally obtain the NaTaO3 / C3N4 material. The NaTaO3 / C3N4 material has the advantages that the preparation method is simple, the raw materials are cheap and environment-friendly, the energy consumption in the preparation process is low, and the NaTaO3 / C3N4 material has excellent performance when being used for producing hydrogen by photocatalytic decomposition of water and degrading antibiotics.

Description

Technical Field

[0001] The present invention relates to the field of photocatalysis technology, and in particular to a method for preparing a carbon nitride-loaded sodium tantalate (NaTaO3 / C3N4) material and its application in photocatalytic hydrogen production or antibiotic degradation. Background Art

[0002] Energy crises and environmental issues have become major challenges that urgently need to be addressed in China. Developing new, green, safe, and renewable energy sources to replace traditional energy sources has become a major goal and direction for both research and industry. Photocatalytic technology, which can utilize abundant solar energy to decompose water into hydrogen and degrade pollutants, holds great promise and has garnered extensive attention and research. Non-metallic graphitic carbon nitride (g-C3N4) possesses a suitable band gap (2.7 eV) and can decompose water to produce hydrogen under visible light. Its structural stability, excellent thermal stability, and ease of preparation have made it a research hotspot in photocatalysis. However, existing carbon nitride materials generally suffer from low solar light utilization, prone to carrier recombination, and low quantum efficiency, resulting in poor performance in photocatalytic water splitting and organic degradation, severely limiting their practical applications. By introducing the rare earth element tantalum and loading it onto the carbon nitride surface to form a Z-junction photocatalyst, photocatalytic performance can be effectively enhanced. By regulating the surface properties of carbon nitride and the particle size and content of sodium tantalate, problems such as few active sites and high recombination rate of photogenerated electrons and holes can be effectively improved, thereby developing efficient photocatalysts with practical application prospects. Summary of the Invention

[0003] The object of the present invention is to provide a preparation method of NaTaO / C3N4 material and its application in photocatalytic hydrogen production or antibiotic degradation.

[0004] The technical solution adopted by the present invention is: A method for preparing a carbon nitride material includes the following steps: mixing a certain amount of C3H6N6 and 200ml of H2O in a constant-temperature water bath, adding HNO3 and 100ml of H2O and reacting for one hour. The water bath temperature is then raised to 95 degrees Celsius, followed by adding a certain amount of Ta2O5 and 0.6g of NaOH and reacting for one hour. The mixed solution is then poured into ice water and cooled to precipitate a solid. The solid is then filtered and precipitated in a vacuum filter. Finally, the precursor is dried in an oven at 60 degrees Celsius to obtain the precursor. The precursor is then placed in a tube furnace, introduced with Ar gas, and heated at 2 degrees Celsius per minute to a desired temperature. The temperature is maintained for four hours, and then cooled to room temperature to obtain the NaTaO / C3N4 material.

[0005] Preferably, the amount of Ta2O5 used is 3 mmol ~5 mmol.

[0006] Preferably, the amount of concentrated HNO3 is 1ml~2ml.

[0007] Preferably, the pyrolysis temperature is 520 o C~550 o C.

[0008] A NaTaO3 / C3N4 material is prepared by the above method.

[0009] A method for photocatalytically decomposing water to produce hydrogen comprises the following steps: adding the above-mentioned NaTaO3 / C3N4 material, a palladium catalyst and formic acid into water, and then reacting them under light conditions.

[0010] Preferably, the platinum catalyst is H2PtCl6.

[0011] Preferably, the reaction is carried out at 5°C to 10°C, and the reaction time is 1 hour to 8 hours.

[0012] A method for simultaneously photocatalytically decomposing water to produce hydrogen and photocatalytically degrading antibiotics comprises the following steps: adding the carbon nitride material, platinum catalyst and antibiotics into water, and then reacting them under light conditions.

[0013] Preferably, the palladium catalyst is PdCl2.

[0014] Preferably, the reaction is carried out at 5°C to 10°C, and the reaction time is 1 hour to 5 hours.

[0015] The beneficial effects of the present invention are: the NaTaO3 / C3N4 material of the present invention has the advantages of multiple surface pore structures, large specific surface area, multiple active sites, strong absorption of sunlight, and high quantum efficiency, and its preparation method is simple, the raw materials are cheap and environmentally friendly, and the energy consumption during the preparation process is low. It has excellent performance in photocatalytic decomposition of water to produce hydrogen and degradation of antibiotics.

[0016] Specifically: The present invention synthesizes carbon nitride-supported sodium tantalate nanoparticles as a photocatalyst by a one-step method, and has the characteristics of high activity, high specific surface area, and multiple active sites. 2) The present invention adds formic acid as a sacrificial agent to consume photogenerated holes to reduce the recombination of electrons and holes, thereby increasing the hydrogen production rate; 3) The NaTaO3 / C3N4 material of the present invention is used for photocatalytic water splitting, and the hydrogen production in 5 hours can reach 40.5 mmol / g, which is more than 30 times higher than that of traditional carbon nitride materials; 4) The NaTaO3 / C3N4 material of the present invention can decompose water to produce hydrogen while photocatalytically degrading antibiotics; 5) The preparation method of the NaTaO3 / C3N4 material of the present invention is simple and easy to operate, requires simple equipment, and has a controllable process and is environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a graph showing the relationship between H2 production and time when the NaTaO3 / C3N4 materials of Examples 1 to 6 are used for the photocatalytic decomposition of water to produce hydrogen.

[0018] Figure 2 TEM image of carbon nitride material.

[0019] Figure 3 This is the TEM image of the NaTaO3 / C3N4 material of Example 1. DETAILED DESCRIPTION

[0020] The present invention will be further explained and illustrated below with reference to specific embodiments. Example 1

[0021] A 5-NaTaO3 / C3N4 material, the preparation method of which comprises the following steps: A method for preparing a carbon nitride material comprises the following steps: mixing a certain amount of 5g C3H6N6 and 200ml H2O in a constant temperature water bath, adding 1ml concentrated HNO3 and 100ml H2O and reacting for one hour, raising the water bath temperature to 95 degrees Celsius, adding 5mmol Ta2O5 and 0.6g NaOH and reacting for 1 hour, then pouring the mixed solution into ice water to cool and precipitate a solid, then placing it in a suction filter to filter the precipitate, and finally drying it in an oven at 60 degrees Celsius to obtain a precursor. The precursor is added to a tube furnace, Ar gas is introduced, and the temperature is raised to 520 at 2 degrees Celsius per minute. o C, and maintained for four hours, and then cooled to room temperature to finally obtain 5-NaTaO / C3N4 material.

[0022] A method for photocatalytically decomposing water to produce hydrogen comprises the following steps: 20.00 mg of 5-NaTaO3 / C3N4, 10 mL of formic acid and 140 mL of water were added to the photocatalytic reactor, ultrasonicated for 20 minutes, and then 205 μL of PdCl2 solution with a palladium content of 1.5 mg / mL was added. After the photocatalytic reaction device was installed, vacuum was evacuated, a xenon lamp was used as the light source, and an AM1.5 filter was added for illumination. A cooling device was used to keep the reaction liquid at around 5°C. Detected by gas chromatography, the hydrogen production after 5 hours of reaction was 42.3 mmol / g. Example 2

[0023] A carbon nitride material, the preparation method of which comprises the following steps: Melamine was loaded into a porcelain boat and placed directly into a tubular heating furnace without a cover. Argon was filled in at a flow rate of 150 mL / min. The temperature was increased from room temperature to 520°C at a rate of 2°C / min and kept constant for 4 hours. The mixture was naturally cooled to room temperature. The obtained solid was taken out and ground to obtain carbon nitride material (denoted as CN-520°C).

[0024] A method for photocatalytically decomposing water to produce hydrogen comprises the following steps: 20.00 mg of CN-520℃, 20 mL of formic acid and 140 mL of water were added to the photocatalytic reactor, ultrasonicated for 20 minutes, and then 205 μL of PdCl2 solution with a palladium content of 1.5 mg / mL was added. After the photocatalytic reaction device was installed, vacuum was evacuated, a xenon lamp was used as the light source, and an AM1.5 filter was added for illumination. A cooling device was used to keep the reaction liquid at around 5℃. Detected by gas chromatograph, the hydrogen production after 5 hours of reaction was 5.93 mmol / g. Example 3

[0025] A 1-NaTaO3 / C3N4 material, the preparation method of which comprises the following steps: A method for preparing a carbon nitride material includes the following steps: mixing a certain amount of 5g C3H6N6 and 200ml H2O in a constant temperature water bath, adding 1ml concentrated HNO3 and 100ml H2O and reacting for one hour, raising the water bath temperature to 95 degrees Celsius, adding 1mmol Ta2O5 and 0.6g NaOH and reacting for 1 hour, then pouring the mixed solution into ice water to cool and precipitate solids, then placing it in a suction filter to filter the precipitate, and finally drying it in an oven at 60 degrees Celsius to obtain a precursor. The precursor is added to a tube furnace, Ar gas is introduced, and the temperature is raised to 520 at 2 degrees Celsius per minute. o C, and maintained for four hours, and then cooled to room temperature to finally obtain 1-NaTaO3 / C3N4 material.

[0026] A method for photocatalytically decomposing water to produce hydrogen comprises the following steps: 20.00 mg of 1-NaTaO3 / C3N4, 10 mL of formic acid and 140 mL of water were added to the photocatalytic reactor, ultrasonicated for 20 minutes, and then 205 μL of PdCl2 solution with a palladium content of 1.5 mg / mL was added. After the photocatalytic reaction device was installed, vacuum was evacuated, a xenon lamp was used as the light source, and an AM1.5 filter was added for illumination. A cooling device was used to keep the reaction liquid at around 5°C. Detected by gas chromatography, the hydrogen production after 5 hours of reaction was 9.5 mmol / g. Example 4

[0027] A 2-NaTaO3 / C3N4 material, the preparation method of which comprises the following steps: A method for preparing a carbon nitride material includes the following steps: mixing a certain amount of 5g C3H6N6 and 200ml H2O in a constant temperature water bath, adding 1ml concentrated HNO3 and 100ml H2O and reacting for one hour, raising the water bath temperature to 95 degrees Celsius, adding 2mmol Ta2O5 and 0.6g NaOH and reacting for 1 hour, then pouring the mixed solution into ice water to cool and precipitate solids, then placing it in a suction filter to filter the precipitate, and finally drying it in an oven at 60 degrees Celsius to obtain a precursor. The precursor is added to a tube furnace, Ar gas is introduced, and the temperature is raised to 520 at 2 degrees Celsius per minute. o C, and maintained for four hours, and then cooled to room temperature to finally obtain 2-NaTaO / C3N4 material.

[0028] A method for photocatalytically decomposing water to produce hydrogen comprises the following steps: 20.00 mg of 2-NaTaO3 / C3N4, 10 mL of formic acid and 140 mL of water were added to the photocatalytic reactor, ultrasonicated for 20 minutes, and then 205 μL of PdCl2 solution with a palladium content of 1.5 mg / mL was added. After the photocatalytic reaction device was installed, vacuum was evacuated, and a xenon lamp was used as the light source, with an AM1.5 filter for illumination. A cooling device was used to keep the reaction liquid at around 5°C. Detected by gas chromatograph, the hydrogen production after 5 hours of reaction was 11.1 mmol / g. Example 5

[0029] A 3-NaTaO3 / C3N4 material, the preparation method of which comprises the following steps: A method for preparing a carbon nitride material includes the following steps: mixing a certain amount of 5g C3H6N6 and 200ml H2O in a constant temperature water bath, adding 1ml concentrated HNO3 and 100ml H2O and reacting for one hour, raising the water bath temperature to 95 degrees Celsius, adding 3mmol Ta2O5 and 0.6g NaOH and reacting for 1 hour, then pouring the mixed solution into ice water to cool and precipitate solids, then placing it in a suction filter to filter the precipitate, and finally drying it in an oven at 60 degrees Celsius to obtain a precursor. The precursor is added to a tube furnace, Ar gas is introduced, and the temperature is raised to 520 at 2 degrees Celsius per minute. o C, and maintained for four hours, and then cooled to room temperature to finally obtain 3-NaTaO3 / C3N4 material.

[0030] A method for photocatalytically decomposing water to produce hydrogen comprises the following steps: 20.00 mg of 3-NaTaO / C3N4, 10 mL of formic acid and 140 mL of water were added to the photocatalytic reactor and ultrasonicated for 20 minutes. Then, 205 μL of PdCl2 solution with a palladium content of 1.5 mg / mL was added. After the photocatalytic reaction device was installed, vacuum was evacuated and a xenon lamp was used as the light source with an AM1.5 filter for illumination. A cooling device was used to keep the reaction liquid at around 5°C. The hydrogen production after 5 hours of reaction was 23.7 mmol / g as detected by gas chromatography. Example 6

[0031] A 4-NaTaO3 / C3N4 material, the preparation method of which comprises the following steps: A method for preparing a carbon nitride material includes the following steps: mixing a certain amount of 5g C3H6N6 and 200ml H2O in a constant temperature water bath, adding 1ml concentrated HNO3 and 100ml H2O and reacting for one hour, raising the water bath temperature to 95 degrees Celsius, adding 4mmol Ta2O5 and 0.6g NaOH and reacting for 1 hour, then pouring the mixed solution into ice water to cool and precipitate solids, then placing it in a suction filter to filter the precipitate, and finally drying it in an oven at 60 degrees Celsius to obtain a precursor. The precursor is added to a tube furnace, Ar gas is introduced, and the temperature is raised to 520 at 2 degrees Celsius per minute. o C, and maintained for four hours, and then cooled to room temperature to finally obtain 4-NaTaO3 / C3N4 material.

[0032] A method for photocatalytically decomposing water to produce hydrogen comprises the following steps: 20.00 mg of 4-NaTaO / C3N4, 10 mL of formic acid and 140 mL of water were added to the photocatalytic reactor and ultrasonicated for 20 minutes. Then, 205 μL of PdCl2 solution with a palladium content of 1.5 mg / mL was added. After the photocatalytic reaction device was installed, vacuum was evacuated and a xenon lamp was used as the light source with an AM1.5 filter for illumination. A cooling device was used to keep the reaction liquid at around 5°C. The hydrogen production after 5 hours of reaction was 31.7 mmol / g as detected by gas chromatography. Example 7

[0033] A 5-NaTaO3 / C3N4 material, the preparation method of which comprises the following steps: A method for preparing a carbon nitride material comprises the following steps: mixing a certain amount of 5g C3H6N6 and 200ml H2O in a constant temperature water bath, adding 1ml concentrated HNO3 and 100ml H2O and reacting for one hour, raising the water bath temperature to 95 degrees Celsius, adding 5mmol Ta2O5 and 0.6g NaOH and reacting for 1 hour, then pouring the mixed solution into ice water to cool and precipitate a solid, then placing it in a suction filter to filter the precipitate, and finally drying it in an oven at 60 degrees Celsius to obtain a precursor. The precursor is added to a tube furnace, Ar gas is introduced, and the temperature is raised to 520 at 2 degrees Celsius per minute. o C, and maintained for four hours, and then cooled to room temperature to finally obtain 5-NaTaO3 / C3N4 material.

[0034] A method for simultaneously photocatalytically decomposing water to produce hydrogen and photocatalytically degrading antibiotics comprises the following steps: 20.00 mg of 5-NaTaO / C3N4, 10 mL of 110 mg / L ofloxacin and 100 mL of water were added to the photocatalytic reactor and ultrasonicated for 20 minutes. 205 μL of PdCl2 solution with a palladium content of 1.5 mg / mL was installed on the photocatalytic reaction device and vacuumed. A xenon lamp was used as the light source, and an AM1.5 filter was added for illumination. A cooling device was used to keep the reaction liquid at around 5°C. Detection by gas chromatography showed that the hydrogen production after 5 hours of reaction was 20.5 mmol / g, and the degradation rate of ofloxacin was 52.8%. Example 8

[0035] A 5-NaTaO3 / C3N4 material, the preparation method of which comprises the following steps: A method for preparing a carbon nitride material includes the following steps: mixing a certain amount of 5g C3H6N6 and 200ml H2O in a constant temperature water bath, adding 1ml concentrated HNO3 and 100ml H2O and reacting for one hour, raising the water bath temperature to 95 degrees Celsius, adding 5mmol Ta2O5 and 0.6g NaOH and reacting for 1 hour, then pouring the mixed solution into ice water to cool and precipitate solids, then placing it in a suction filter to filter the precipitate, and finally drying it in an oven at 60 degrees Celsius to obtain a precursor. The precursor is added to a tube furnace, Ar gas is introduced, and the temperature is raised to 480 at 2 degrees Celsius per minute. o C, and maintained for four hours, and then cooled to room temperature to finally obtain 5-NaTaO3 / C3N4 material.

[0036] A method for simultaneously photocatalytically decomposing water to produce hydrogen and photocatalytically degrading antibiotics comprises the following steps: 20.00 mg of 5-NaTaO / C3N4, 10 mL of 110 mg / L ofloxacin and 100 mL of water were added to the photocatalytic reactor and ultrasonicated for 20 min. 205 μL of PdCl2 solution with a palladium content of 1.5 mg / mL was installed in the photocatalytic reaction device and vacuum was applied. A xenon lamp was used as the light source, and an AM1.5 filter was added for illumination. A cooling device was used to maintain the reaction solution at around 5°C. Detection by gas chromatography showed that the hydrogen production after 5 h of reaction was 14.5 mmol / g, and the degradation rate of ofloxacin was 22.9%. Example 9

[0037] A 5-NaTaO3 / C3N4 material, the preparation method of which comprises the following steps: A method for preparing a carbon nitride material includes the following steps: mixing a certain amount of 5g C3H6N6 and 200ml H2O in a constant temperature water bath, adding 1ml concentrated HNO3 and 100ml H2O and reacting for one hour, raising the water bath temperature to 95 degrees Celsius, adding 3mmol Ta2O5 and 0.6g NaOH and reacting for 1 hour, then pouring the mixed solution into ice water to cool and precipitate solids, then placing it in a suction filter to filter the precipitate, and finally drying it in an oven at 60 degrees Celsius to obtain a precursor. The precursor is added to a tube furnace, Ar gas is introduced, and the temperature is raised to 480 at 2 degrees Celsius per minute. o C, and maintained for four hours, and then cooled to room temperature to finally obtain 3-NaTaO3 / C3N4 material.

[0038] A method for simultaneously photocatalytically decomposing water to produce hydrogen and photocatalytically degrading antibiotics comprises the following steps: 20.00 mg of 3-NaTaO / C3N4, 10 mL of 110 mg / L ofloxacin and 100 mL of water were added to the photocatalytic reactor and ultrasonicated for 20 min. 205 μL of PdCl2 solution with a palladium content of 1.5 mg / mL was installed in the photocatalytic reaction device and vacuumed. A xenon lamp was used as the light source, and an AM1.5 filter was added for illumination. A cooling device was used to keep the reaction solution at around 5°C. Detected by gas chromatography, the hydrogen production after 5 h of reaction was 8.6 mmol / g, and the degradation rate of ofloxacin was 18.6%. Example 10

[0039] A 1-NaTaO3 / C3N4 material, the preparation method of which comprises the following steps: A method for preparing a carbon nitride material includes the following steps: mixing a certain amount of 5g C3H6N6 and 200ml H2O in a constant temperature water bath, adding 1ml concentrated HNO3 and 100ml H2O and reacting for one hour, raising the water bath temperature to 95 degrees Celsius, adding 1mmol Ta2O5 and 0.6g NaOH and reacting for 1 hour, then pouring the mixed solution into ice water to cool and precipitate solids, then placing it in a suction filter to filter the precipitate, and finally drying it in an oven at 60 degrees Celsius to obtain a precursor. The precursor is added to a tube furnace, Ar gas is introduced, and the temperature is raised to 530 at 2 degrees Celsius per minute. o C, and maintained for four hours, and then cooled to room temperature to finally obtain 1-NaTaO3 / C3N4 material.

[0040] A method for simultaneously photocatalytically decomposing water to produce hydrogen and photocatalytically degrading antibiotics comprises the following steps: 20.00 mg of 1-NaTaO / C3N4, 10 mL of 110 mg / L ofloxacin and 100 mL of water were added to the photocatalytic reactor and ultrasonicated for 20 minutes. 205 μL of PdCl2 solution with a palladium content of 1.5 mg / mL was installed on the photocatalytic reaction device and vacuumed. A xenon lamp was used as the light source, and an AM1.5 filter was added for illumination. A cooling device was used to keep the reaction liquid at around 5°C. Detection by gas chromatography showed that the hydrogen production after 5 hours of reaction was 10.8 mmol / g, and the degradation rate of ofloxacin was 19.6%.

[0041] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A method for preparing carbon nitride-supported sodium tantalate (NaTaO3 / C3N4), characterized in that: The following steps are involved: 5g of C3H6N6 and 200ml of H2O were mixed in a constant-temperature water bath. Concentrated HNO3 and 100ml of H2O were added and allowed to react for one hour. The water bath temperature was raised to 95°C, and Ta2O5 and 0.6g of NaOH were added and allowed to react for one hour. The mixed solution was then poured into ice water and cooled to precipitate a solid. The solid was then filtered through a vacuum filter and finally dried in an oven at 60°C to obtain the precursor. The precursor was then placed in a tube furnace, introduced with Ar gas, and heated at 2°C per minute to the desired temperature. The temperature was maintained for four hours before being cooled to room temperature to obtain the NaTaO / C3N4 material.

2. The method for preparing the NaTaO3 / C3N4 material according to claim 1, wherein: The amount of Ta2O5 used is 0.1mmol~5mmol.

3. The method for preparing the NaTaO3 / C3N4 material according to claim 1, wherein: The amount of HNO3 used is 0.1ml~3ml.

4. The method for preparing the NaTaO3 / C3N4 material according to any one of claims 1 to 3, characterized in that: The pyrolysis temperature is 480 o C~550 o C.

5. A NaTaO / C3N4 material, characterized in that The invention is prepared by the method according to any one of claims 1 to 4.

6. Use of the NaTaO3 / C3N4 material according to claim 5 as a catalyst for photocatalytic reactions.

7. The use according to claim 5, characterized in that: The photocatalytic reaction is a photocatalytic decomposition of water to produce hydrogen reaction or a photocatalytic degradation of antibiotics reaction.

8. A method for producing hydrogen by photocatalytic decomposition of water, characterized in that: The method comprises the following steps: adding the NaTaO3 / C3N4 material according to claim 7, a palladium catalyst and formic acid into water, and then reacting under light conditions.

9. A method for simultaneously performing photocatalytic decomposition of water to produce hydrogen and photocatalytic degradation of antibiotics, characterized in that: The method comprises the following steps: adding the NaTaO3 / C3N4 material according to claim 8, a palladium catalyst and antibiotics into water, and then reacting under light conditions.

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