Transition metal carbon-nitrogen material with hierarchical pore structure as well as preparation method and application of transition metal carbon-nitrogen material

Abstract

The invention discloses a transition metal carbon-nitrogen material with a hierarchical pore structure as well as a preparation method and application of the transition metal carbon-nitrogen material. Ordered macropores, mesopores and micropores exist in the structure of the transition metal carbon-nitrogen material, the specific surface area range is 600-1300m < 2 > / g, the average pore size is 5-50nm, and the pore volume is 1.0-5.0 cm < 3 > / g. According to the preparation method, a porous, especially mesoporous structure can be accurately constructed, the aperture and form of the material can be controlled, and the material has a high specific surface area, so that more catalytic active sites are exposed, the adsorption and selectivity of a reaction substrate are accurately regulated and controlled, and the potential advantage of improving the catalytic efficiency is achieved.

Description

Technical Field

[0001] This application relates to a transition metal carbon-nitrogen material with a hierarchical pore structure, its preparation method and application, belonging to the field of electrocatalytic materials. Background Technology

[0002] With the rapid development of lithium batteries, hydrogen fuel cells, and various electrocatalysts, electrode materials are constantly being updated. Among them, transition metal carbon-nitrogen materials have received widespread research attention due to their high capacity and low cost. However, to optimize the catalytic efficiency of these materials, it is necessary to significantly increase the exposure density of active sites. Therefore, a common method is to increase the specific surface area of ​​the material through pore-forming techniques. Existing technologies, such as CN202310900762.6 and CN202210696293.6, use reagents such as urea and sodium chloride as pore-forming agents to create pores during the preparation of transition metal carbon-nitrogen materials, thereby achieving a high specific surface area. However, these techniques make it difficult to precisely control the pore size and the specific surface area of ​​the material.

[0003] In porous transition metal carbonitriding materials used in electrodes, the pore size distribution (micropores, mesopores, macropores) is crucial to their performance. Micropores can serve as active sites for reactions, while mesopore structures can act as mass transfer channels, accelerating reaction kinetics. Therefore, precise control of mesopore size can improve reaction selectivity. However, current reported techniques still focus on micropore construction, and the precise construction of mesopores in transition metal carbonitriding materials remains a significant challenge. Summary of the Invention

[0004] To address the challenge of precisely constructing mesopores in existing transition metal carbonitride materials, this application proposes a method for preparing transition metal carbonitride materials with a hierarchical pore structure. This method involves sequentially mixing a template material, ligands, and a metal source solution, followed by high-temperature calcination and carbonization of the resulting precursor, and finally etching the template material. This material exhibits a hierarchical pore structure from micropores to mesopores, with mesopore sizes controllable by the template, and possesses a high specific surface area.

[0005] According to one aspect of this application, a transition metal carbonitride material with a hierarchical pore structure is provided, wherein the structure of the transition metal carbonitride material contains ordered macropores, mesopores and micropores.

[0006] The pore size of the macropore is >50nm;

[0007] The pore size of the mesopore is 2–50 nm;

[0008] The pore size of the micropores is 1–2 nm;

[0009] The average pore size of the transition metal carbonitride material is 5–50 nm.

[0010] The specific surface area of ​​the transition metal carbonitriding material is 600–1300 m². 2 / g;

[0011] The transition metal carbonitride material has a pore volume of 1.0–5.0 cm³. 3 / g.

[0012] Contains transition metal elements;

[0013] The transition metal element is selected from at least one of molybdenum, tungsten, and vanadium.

[0014] According to another aspect of this application, a method for preparing the above-mentioned transition metal carbonitride material with hierarchical pore structure is provided, comprising the following steps:

[0015] The raw materials containing template agent, transition metal source, ligand and solvent are mixed, reacted, dried, calcined, etched and dried to obtain the transition metal carbonitride material with hierarchical pore structure.

[0016] The template agent is selected from at least one of silica sol, nano silica, all-silica molecular sieve, aluminosilicate molecular sieve, and titanium-silica molecular sieve;

[0017] The transition metal source is selected from at least one of molybdenum trioxide, sodium molybdate, ammonium molybdate, tungsten trioxide, sodium metatungstate, ammonium metatungstate, vanadium pentoxide, sodium metavanadate, and ammonium metavanadate.

[0018] The ligand has the structure shown in Formula I;

[0019]

[0020] Among them, R1, R2, R3, R4, R5, and R6 are independently selected from one of -H, -NO2, -SO3H, -F, -Cl, -Br, -I, -CF3, -CO2R, -OR, -CH2OR, -CH2R, and -C6H4R;

[0021] Wherein, R in -CO2R, -OR, -CH2OR, -CH2R, and -C6H4R is selected from one of H, CH3, C2H5, C3H8, and C6H5;

[0022] The solvent is selected from at least one of methanol, ethanol, tetrahydrofuran, and water.

[0023] The mass ratio of the template agent to the ligand is 1 to 4:1;

[0024] Optionally, the mass ratio of the template agent to the ligand is 1.7 to 3.6:1;

[0025] Optionally, the mass ratio of the template agent to the ligand is any value among 1, 2, 3, and 4, or a range between any two.

[0026] The molar ratio of the transition metal source to the ligand is 1:(1-2);

[0027] Optionally, the molar ratio of the transition metal source to the ligand is any value of 1:1, 1:2, or any range between the two.

[0028] Optionally, the mixing includes the following steps:

[0029] Mix a solvent solution containing a template agent, a solvent solution containing a transition metal source, and a solvent solution containing a ligand;

[0030] In the solvent solution containing the template agent, the ratio of template agent to solvent is 1-10g:100ml;

[0031] Optionally, in the solvent solution containing the template agent, the ratio of the template agent to the solvent is any value or a range between 1g:100ml, 2g:100ml, 3g:100ml, 4g:100ml, 5g:100ml, 6g:100ml, 7g:100ml, 8g:100ml, 9g:100ml, and 10g:100ml.

[0032] The concentration of the solvent solution containing the transition metal source is 0.1–1 M;

[0033] Optionally, the concentration of the solvent solution containing the transition metal source is any value among 0.1M, 0.5M, 1M, 2M, 3M, 4M, 5M, 6M, 7M, 8M, 9M, and 10M, or a range between any two.

[0034] The concentration of the solvent solution containing the ligand is 0.1–1 M.

[0035] Optionally, the concentration of the solvent solution containing the ligand is any value among 0.1M, 0.5M, 1M, 2M, 3M, 4M, 5M, 6M, 7M, 8M, 9M, and 10M, or a range between any two.

[0036] The reaction temperature is 60–100°C;

[0037] Optionally, the temperature of the reaction is any value of 60°C, 70°C, 80°C, 90°C, 100°C, or a range between any two.

[0038] The reaction is continuously stirred until the solvent evaporates to dryness.

[0039] The drying temperature is 100–120°C;

[0040] Optionally, the drying temperature is any value among 100°C, 110°C, and 120°C, or a range between any two.

[0041] The roasting temperature is 500–1200℃;

[0042] Optionally, the roasting temperature is any value or a range between 500℃, 600℃, 700℃, 800℃, 900℃, 1000℃, 1100℃, and 1200℃.

[0043] The roasting time is 0.5 to 10 hours;

[0044] Optionally, any value from 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or a range between any two.

[0045] The heating rate of the roasting is 1-20℃ / min;

[0046] Optionally, the heating rate of the calcination is any value among 1℃ / min, 5℃ / min, 10℃ / min, 15℃ / min, and 20℃ / min, or a range between any two.

[0047] The calcination atmosphere is a non-reactive gas atmosphere;

[0048] The inactive gas for takeoff is selected from at least one of nitrogen, argon, and helium;

[0049] The etching agent used in the etching process is selected from at least one of hydrofluoric acid, sodium hydroxide, and ammonium hydrofluoride.

[0050] The concentration of the etching agent is 0.5–5 M;

[0051] Optionally, the concentration of the etchant is any value among 0.5M, 1M, 2M, 3M, 4M, and 5M, or a range between any two.

[0052] The etching time is 2–24 hours;

[0053] Optionally, the etching time is any value or a range between 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, and 24h.

[0054] The drying temperature is 40–80°C;

[0055] Optionally, the drying temperature is any value among 40°C, 50°C, 60°C, 70°C, and 80°C, or a range between any two.

[0056] The drying time is 8–24 hours;

[0057] Optionally, the drying time is any value among 8h, 16h, and 24h, or a range between any two.

[0058] The drying process is vacuum drying.

[0059] Specifically, it includes the following steps:

[0060] Step 1: Preparation of the precursor. The template material is dispersed in a solvent, preferably in a ratio of 1–10 g of template material to 100 mL of deionized water. The ligand is dissolved in the solvent to prepare a 0.1–1 M solution, which is then slowly added to the template dispersion under continuous stirring. The metal source is dissolved in the solvent to prepare a 0.1–1 M solution, which is then slowly added to the mixture under continuous stirring. The mixture is stirred continuously at 60–100 °C until the solvent evaporates completely. The mixture is then dried in an oven at 100–120 °C to obtain the material precursor.

[0061] Step 2: The obtained precursor is subjected to high-temperature carbonization treatment. 5g of the precursor is placed in a high-temperature furnace, and argon or nitrogen is used as a protective atmosphere. The temperature is raised to 500-1200℃ at a heating rate of 1-20℃ and held for 0.5-10h. The furnace is then cooled to obtain a transition metal carbonitride material loaded on a template.

[0062] Step 3: Immerse the transition metal carbonitride material obtained in Step 2 on the template with an etchant for 2–24 hours, filter, and wash with deionized water until neutral. Dry the filtered solid in a vacuum drying oven at 40–80°C for 8–24 hours to obtain the transition metal carbonitride material.

[0063] According to another aspect of this application, an application of the aforementioned transition metal carbon-nitrogen material with a hierarchical pore structure is provided as a catalyst for Fenton-like oxidation reactions that degrade organic matter.

[0064] According to another aspect of this application, an application is provided for the above-mentioned transition metal carbonitride material with hierarchical pore structure, used as a battery material for lithium batteries and hydrogen fuel cells.

[0065] The beneficial effects that this application can produce include:

[0066] 1) The transition metal carbonitriding material provided in this application has a hierarchical pore structure, containing ordered macropores, mesopores, and micropores, with a specific surface area ranging from 600 to 1300 m². 2 / g, with an average pore size of 5–50 nm and a pore volume of 1.0–5.0 cm³. 3 / g.

[0067] 2) The method for preparing transition metal carbon-nitrogen materials provided in this application can accurately construct their porous, especially mesoporous, structures, control the pore size and morphology of the materials, and have a high specific surface area, thereby exposing more catalytic active sites and precisely controlling the adsorption and selectivity of reaction substrates, thus having the potential advantage of improving catalytic efficiency. Attached Figure Description

[0068] Figure 1 This is a SEM image of the porous molybdenum carbonitride material in Example 1 of this application, with a scale of 1 μm.

[0069] Figure 2 The nitrogen adsorption-desorption curves are shown for the porous molybdenum-nitrogen-carbon material in Example 1 of this application.

[0070] Figure 3 This shows the pore size distribution of the porous molybdenum-nitrogen-carbon material in Example 1 of this application. Detailed Implementation

[0071] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0072] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0073] Example 1

[0074] 4 g of silica sol (average particle size 12 nm) and 100 mL of deionized water were added to a 500 mL beaker and dispersed under continuous stirring. 12 mmol (1.7 g) of 8-hydroxyquinoline was dissolved in 50 mL of ethanol and slowly added to the above dispersion; 6 mmol (1.1 g) of ammonium molybdate was dissolved in 50 mL of deionized water and slowly added to the above dispersion. The dispersion was heated to 80 °C until the solvent evaporated, and then dried overnight in an oven at 110 °C to obtain a precursor of mesoporous molybdenum carbonitride material. The obtained precursor was placed in a high-temperature tube furnace under nitrogen protection and heated to 700 °C at a rate of 5 °C / min, and held for 2 h. After the apparatus cooled to room temperature, the calcined solid was removed and soaked in 10% hydrofluoric acid for 12 h. The mixture was filtered, washed with deionized water until neutral, and dried overnight in a vacuum drying oven at 60 °C.

[0075] A total of 1.1g of porous molybdenum carbonitride material was prepared.

[0076] Figure 1 This is a SEM image of the porous molybdenum carbonitride material in Example 1 of this application, with a scale of 1 μm.

[0077] Figure 2The nitrogen adsorption-desorption curves are shown for the porous molybdenum-nitrogen-carbon material in Example 1 of this application.

[0078] Figure 3 This shows the pore size distribution of the porous molybdenum-nitrogen-carbon material in Example 1 of this application.

[0079] from Figure 1 It can be seen that the material has a porous structure. From Figure 2 It can be seen that the specific surface area of ​​this material is 916 m². 2 / g, pore volume 2.0cm³ 3 / g, from Figure 3 It can be seen that the average pore size of the material is 10 nm.

[0080] 0.5 g of the material was added to 50 mL of organic wastewater containing 0.02 g / L of potassium persulfate, stirred thoroughly, and then 0.2 g of potassium persulfate was added. The organic matter degradation rate constant in the wastewater was measured to be 0.082 min. -1 .

[0081] Comparative Example 1

[0082] Add 100 mL of deionized water to a 500 mL beaker. Weigh 12 mmol (1.7 g) of 8-hydroxyquinoline and dissolve it in 50 mL of ethanol, then slowly add it to the beaker containing water. Weigh 6 mmol (1.1 g) of ammonium molybdate and dissolve it in 50 mL of deionized water, then slowly add it to the dispersion. Heat the dispersion to 80 °C until the solvent evaporates, then dry it overnight in an oven at 110 °C to obtain a precursor for molybdenum carbonitriding material. Place the obtained precursor in a high-temperature tube furnace under nitrogen protection, and heat it to 700 °C at a rate of 5 °C / min, holding for 2 h. After the apparatus cools to room temperature, remove the calcined solid to obtain 1.3 g of molybdenum carbonitriding material with a specific surface area of ​​5 m². 2 / g, pore volume 0.002cm³ 3 / g, average pore size 2nm.

[0083] 0.5 g of the material was added to 50 mL of organic wastewater containing 0.02 g / L of potassium persulfate, stirred thoroughly, and then 0.2 g of potassium persulfate was added. The organic matter degradation rate constant in the wastewater was measured to be 0.0001 min. -1 .

[0084] Example 2

[0085] 5 g of nano-silica (average particle size 40 nm) and 100 mL of deionized water were added to a 500 mL beaker and dispersed under continuous stirring. 12 mmol (1.7 g) of 8-hydroxyquinoline was dissolved in 50 mL of ethanol and slowly added to the above dispersion; 6 mmol (1.1 g) of ammonium molybdate was dissolved in 50 mL of deionized water and slowly added to the above dispersion. The dispersion was heated to 80 °C until the solvent evaporated, and then dried overnight in an oven at 110 °C to obtain a precursor of mesoporous molybdenum carbonitride material. The obtained precursor was placed in a high-temperature tube furnace under nitrogen protection and heated to 700 °C at a rate of 5 °C / min, and held for 2 h. After the apparatus cooled to room temperature, the calcined solid was removed and soaked in 10% hydrofluoric acid for 12 h. The mixture was filtered, washed with deionized water until neutral, and dried overnight in a vacuum drying oven at 60 °C. A total of 1.5 g of porous molybdenum carbonitride material with a specific surface area of ​​1022 m² was obtained. 2 / g, pore volume 4.1cm³ 3 / g, average pore size 37nm.

[0086] 0.5 g of the material was added to 50 mL of organic wastewater containing 0.02 g / L of potassium persulfate, stirred thoroughly, and then 0.2 g of potassium persulfate was added. The organic matter degradation rate constant in the wastewater was measured to be 0.091 min. -1 .

[0087] Example 3

[0088] 5g of titanium silicate molecular sieve and 100mL of deionized water were added to a 500mL beaker and dispersed under continuous stirring. 12mmol (1.7g) of 8-hydroxyquinoline was dissolved in 50mL of ethanol and slowly added to the dispersion. 6mmol (1.1g) of ammonium molybdate was dissolved in 50mL of deionized water and slowly added to the dispersion. The dispersion was heated to 80℃ until the solvent evaporated, and then dried overnight in an oven at 110℃ to obtain a precursor of mesoporous molybdenum carbonitride material. The obtained precursor was placed in a high-temperature tube furnace under nitrogen protection and heated to 700℃ at a rate of 5℃ / min, and held for 2 hours. After the apparatus cooled to room temperature, the calcined solid was removed and soaked in 10% hydrofluoric acid for 12 hours. It was filtered, washed with deionized water until neutral, and dried overnight in a vacuum drying oven at 60℃. A total of 1.8g of porous molybdenum carbonitride material with a specific surface area of ​​865m² was obtained. 2 / g, pore volume 2.5cm³ 3 / g, average pore size 28nm.

[0089] 0.5 g of the material was added to 50 mL of organic wastewater containing 0.02 g / L of potassium persulfate, stirred thoroughly, and then 0.2 g of potassium persulfate was added. The organic matter degradation rate constant in the wastewater was measured to be 0.063 min. -1 .

[0090] Example 4

[0091] 5 g of nano-silica (average particle size 40 nm) and 100 mL of deionized water were added to a 500 mL beaker and dispersed under continuous stirring. 12 mmol (1.7 g) of 8-hydroxyquinoline was dissolved in 50 mL of ethanol and slowly added to the above dispersion; 6 mmol (1.1 g) of ammonium molybdate was dissolved in 50 mL of deionized water and slowly added to the above dispersion. The dispersion was heated to 80 °C until the solvent evaporated, and then dried overnight in an oven at 110 °C to obtain a precursor of mesoporous molybdenum carbonitride material. The obtained precursor was placed in a high-temperature tube furnace under nitrogen protection and heated to 900 °C at a rate of 5 °C / min, and held for 2 h. After the apparatus cooled to room temperature, the calcined solid was removed and soaked in 10% hydrofluoric acid for 12 h. The mixture was filtered, washed with deionized water until neutral, and dried overnight in a vacuum drying oven at 60 °C. A total of 0.9 g of porous molybdenum carbonitride material with a specific surface area of ​​1036 m² was obtained. 2 / g, pore volume 4.5cm³ 3 / g, average pore size 38nm.

[0092] 0.5 g of the material was added to 50 mL of organic wastewater containing 0.02 g / L of potassium persulfate, stirred thoroughly, and then 0.2 g of potassium persulfate was added. The organic matter degradation rate constant in the wastewater was measured to be 0.088 min. -1 .

[0093] Example 5

[0094] 6 g of nano-silica (average particle size 40 nm) and 100 mL of deionized water were added to a 500 mL beaker and dispersed under continuous stirring. 12 mmol (1.7 g) of 8-hydroxyquinoline was dissolved in 50 mL of ethanol and slowly added to the above dispersion; 6 mmol (1.1 g) of ammonium molybdate was dissolved in 50 mL of deionized water and slowly added to the above dispersion. The dispersion was heated to 80 °C until the solvent evaporated, and then dried overnight in an oven at 110 °C to obtain a precursor of mesoporous molybdenum carbonitride material. The obtained precursor was placed in a high-temperature tube furnace under nitrogen protection and heated to 700 °C at a rate of 5 °C / min, and held for 2 h. After the apparatus cooled to room temperature, the calcined solid was removed and soaked in 10% hydrofluoric acid for 12 h. The mixture was filtered, washed with deionized water until neutral, and dried overnight in a vacuum drying oven at 60 °C. A total of 1.0 g of porous molybdenum carbonitride material with a specific surface area of ​​1201 m² was obtained. 2 / g, pore volume 5.8cm³ 3 / g, average pore size 37nm.

[0095] 0.5 g of the material was added to 50 mL of organic wastewater containing 0.02 g / L of potassium persulfate, stirred thoroughly, and then 0.2 g of potassium persulfate was added. The organic matter degradation rate constant in the wastewater was measured to be 0.103 min. -1 .

[0096] Example 6

[0097] 3g of nano-silica (average particle size 40nm) and 100mL of deionized water were added to a 500mL beaker and dispersed under continuous stirring. 12mmol (1.7g) of 8-hydroxyquinoline was dissolved in 50mL of ethanol and slowly added to the above dispersion; 6mmol (1.1g) of ammonium molybdate was dissolved in 50mL of deionized water and slowly added to the above dispersion. The dispersion was heated to 80℃ until the solvent evaporated, and then dried overnight in an oven at 110℃ to obtain a precursor of mesoporous molybdenum carbonitride material. The obtained precursor was placed in a high-temperature tube furnace under nitrogen protection and heated to 700℃ at a rate of 5℃ / min, and held for 2h. After the apparatus cooled to room temperature, the calcined solid was removed and soaked in 10% hydrofluoric acid for 12h. It was filtered, washed with deionized water until neutral, and dried overnight in a vacuum drying oven at 60℃. A total of 1.1g of porous molybdenum carbonitride material with a specific surface area of ​​684m² was obtained. 2 / g, pore volume 1.2cm³ 3 / g, average pore size 38nm.

[0098] 0.5 g of the material was added to 50 mL of organic wastewater containing 0.02 g / L of potassium persulfate, stirred thoroughly, and then 0.2 g of potassium persulfate was added. The organic matter degradation rate constant in the wastewater was measured to be 0.070 min. -1 .

[0099] Example 7

[0100] 5 g of nano-silica (average particle size 40 nm) and 100 mL of deionized water were added to a 500 mL beaker and dispersed under continuous stirring. 12 mmol (1.7 g) of 8-hydroxyquinalidine (2-methyl-8-hydroxyquinoline) was dissolved in 50 mL of ethanol and slowly added to the dispersion. 6 mmol (1.1 g) of ammonium molybdate was dissolved in 50 mL of deionized water and slowly added to the dispersion. The dispersion was heated to 80 °C until the solvent evaporated, and then dried overnight in an oven at 110 °C to obtain a precursor of mesoporous molybdenum carbonitride material. The obtained precursor was placed in a high-temperature tube furnace under nitrogen protection and heated to 700 °C at a rate of 5 °C / min, and held for 2 h. After the apparatus cooled to room temperature, the calcined solid was removed and soaked in 10% hydrofluoric acid for 12 h. The mixture was filtered, washed with deionized water until neutral, and dried overnight in a vacuum drying oven at 60 °C. A total of 1.3g of porous molybdenum carbonitride material was prepared, with a specific surface area of ​​1102m². 2 / g, pore volume 3.5cm³ 3 / g, average pore size 36nm.

[0101] 0.5 g of the material was added to 50 mL of organic wastewater containing 0.02 g / L of potassium persulfate, stirred thoroughly, and then 0.2 g of potassium persulfate was added. The organic matter degradation rate constant in the wastewater was measured to be 0.081 min. -1 .

[0102] Example 8

[0103] 5 g of nano-silica (average particle size 40 nm) and 100 mL of deionized water were added to a 500 mL beaker and dispersed under continuous stirring. 12 mmol (1.7 g) of 8-hydroxyquinoline was dissolved in 50 mL of ethanol and slowly added to the above dispersion; 6 mmol (1.4 g) of sodium metatungstate was dissolved in 50 mL of deionized water and slowly added to the above dispersion. The dispersion was heated to 80 °C until the solvent evaporated, and then dried overnight in an oven at 110 °C to obtain a precursor of mesoporous tungsten carbonitride material. The obtained precursor was placed in a high-temperature tube furnace under nitrogen protection and heated to 700 °C at a rate of 5 °C / min, and held for 2 h. After the apparatus cooled to room temperature, the calcined solid was removed, soaked in 2 M sodium hydroxide, and refluxed for 12 h. The mixture was filtered, washed with deionized water until neutral, and dried overnight in a vacuum drying oven at 60 °C. A total of 1.4 g of porous tungsten carbonitride material with a specific surface area of ​​986 m² was obtained. 2 / g, pore volume 2.7cm³ 3 / g, average pore size 36nm.

[0104] 0.5 g of the material was added to 50 mL of organic wastewater containing 0.02 g / L of potassium persulfate, stirred thoroughly, and then 0.2 g of potassium persulfate was added. The organic matter degradation rate constant in the wastewater was measured to be 0.069 min. -1 .

[0105] Example 9

[0106] 5g of nano-silica (average particle size 40nm) and 100mL of deionized water were added to a 500mL beaker and dispersed under continuous stirring. 6mmol (0.8g) of 8-hydroxyquinoline was dissolved in 50mL of ethanol and slowly added to the above dispersion; 6mmol (0.7g) of sodium metavanadate was dissolved in 50mL of deionized water and slowly added to the above dispersion. The dispersion was heated to 80℃ until the solvent evaporated, and then dried overnight in an oven at 110℃ to obtain a precursor of mesoporous vanadium carbonitride material. The obtained precursor was placed in a high-temperature tube furnace under nitrogen protection and heated to 700℃ at a rate of 5℃ / min, and held for 2h. After the apparatus cooled to room temperature, the calcined solid was removed, soaked in 2M sodium hydroxide, and refluxed for 12h. It was filtered, washed with deionized water until neutral, and dried overnight in a vacuum drying oven at 60℃. A total of 0.6g of porous vanadium carbonitride material with a specific surface area of ​​889m² was obtained. 2 / g, pore volume 1.8cm³ 3 / g, average pore size 38nm.

[0107] 0.5 g of the material was added to 50 mL of organic wastewater containing 0.02 g / L of potassium persulfate, stirred thoroughly, and then 0.2 g of potassium persulfate was added. The organic matter degradation rate constant in the wastewater was measured to be 0.066 min. -1 .

[0108] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A transition metal carbonitride material with a hierarchical pore structure, characterized in that, The structure of the transition metal carbonitridium material contains ordered macropores, mesopores, and micropores. The average pore size of the transition metal carbonitride material is 5–50 nm. The specific surface area of ​​the transition metal carbonitriding material is 600–1300 m². 2 / g; The transition metal carbonitride material has a pore volume of 1.0–5.0 cm³. 3 / g.

2. The transition metal carbonitride material with a hierarchical pore structure according to claim 1, characterized in that, Contains transition metal elements; The transition metal element is selected from at least one of molybdenum, tungsten, and vanadium.

3. A method for preparing a transition metal carbonitriding material with a hierarchical porous structure as described in any one of claims 1 to 2, characterized in that, Includes the following steps: The raw materials containing template agent, transition metal source, ligand and solvent are mixed, reacted, dried, calcined, etched and dried to obtain the transition metal carbonitride material with hierarchical pore structure.

4. The preparation method according to claim 3, characterized in that, The template agent is selected from at least one of silica sol, nano silica, all-silica molecular sieve, aluminosilicate molecular sieve, and titanium-silica molecular sieve; The transition metal source is selected from at least one of molybdenum trioxide, sodium molybdate, ammonium molybdate, tungsten trioxide, sodium metatungstate, ammonium metatungstate, vanadium pentoxide, sodium metavanadate, and ammonium metavanadate. The ligand has the structure shown in Formula I; Among them, R1, R2, R3, R4, R5, and R6 are independently selected from one of -H, -NO2, -SO3H, -F, -Cl, -Br, -I, -CF3, -CO2R, -OR, -CH2OR, -CH2R, and -C6H4R; Wherein, R in -CO2R, -OR, -CH2OR, -CH2R, and -C6H4R is selected from one of H, CH3, C2H5, C3H8, and C6H5; The solvent is selected from at least one of methanol, ethanol, tetrahydrofuran, and water.

5. The preparation method according to claim 3, characterized in that, The mass ratio of the template agent to the ligand is 1 to 4:1; Preferably, the mass ratio of the template agent to the ligand is 1.7 to 3.6:1; The molar ratio of the transition metal source to the ligand is 1:(1-2).

6. The preparation method according to claim 3, characterized in that, The mixing process includes the following steps: Mix a solvent solution containing a template agent, a solvent solution containing a transition metal source, and a solvent solution containing a ligand; In the solvent solution containing the template agent, the ratio of template agent to solvent is 1-10g:100ml; The concentration of the solvent solution containing the transition metal source is 0.1–1 M; The concentration of the solvent solution containing the ligand is 0.1–1 M.

7. The preparation method according to claim 3, characterized in that, The reaction temperature is 60–100°C; The reaction is continuously stirred until the solvent evaporates to dryness. The drying temperature is 100–120°C; The roasting temperature is 500–1200℃; The roasting time is 0.5 to 10 hours; The heating rate of the roasting is 1-20℃ / min; The calcination atmosphere is a non-reactive gas atmosphere; The inactive gas for takeoff is selected from at least one of nitrogen, argon, and helium; The etching agent used in the etching process is selected from at least one of hydrofluoric acid, sodium hydroxide, and ammonium hydrofluoride.

8. The preparation method according to claim 3, characterized in that, The concentration of the etching agent is 0.5–5 M; The etching time is 2–24 hours; The drying temperature is 40–80°C; The drying time is 8–24 hours; The drying process is vacuum drying.

9. The application of a transition metal carbonitriding material with a hierarchical pore structure as described in any one of claims 1 to 2, characterized in that, As a catalyst for Fenton-like oxidation reactions that degrade organic matter. In the Fenton-like oxidation reaction, the oxidant is at least one of potassium persulfate, potassium peroxymonosulfate, sodium persulfate, and sodium peroxymonosulfate.

10. The application of a transition metal carbonitriding material with a hierarchical pore structure as described in any one of claims 1 to 2, characterized in that, Battery materials used in lithium batteries and hydrogen fuel cells.

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