Nitrogen-doped titanium dioxide and titanium carbide composite material as well as preparation method and application thereof
Through the preparation of nitrogen-doped titanium dioxide@titanium carbide composite materials, the core-shell structure and nitrogen doping sites are used to improve the selectivity and activity of H2O2 production, and the high cost and environmental pollution problems of H2O2 production process in the prior art are solved. , realizes efficient low-concentration H2O2 application.
Patent Information
- Application Number
- CN202411219554.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-02
- Publication Date
- 2024-12-10
AI Technical Summary
The existing H2O2 production processes have problems of high cost, environmental pollution and low selectivity, especially in applications with low concentrations of H2O2, and it is necessary to develop ORR electrocatalysts with high selectivity.
The nitrogen-doped titanium dioxide @ titanium carbide composite is prepared by calcining and plasma-enhanced chemical vapor deposition methods to form a core-shell structure and nitrogen-doping site, which improves the activity and selectivity of the two electron oxygen reduction reaction.
A high selectivity and active two-electron oxygen reduction reaction is achieved, which simplifies the preparation process, reduces production costs, and reduces the accumulation of oxygen reduction products inside the electrode, and improves kinetic efficiency.
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Figure CN119101944A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of functional materials, and in particular to a nitrogen-doped titanium dioxide@titanium carbide composite material and a preparation method and application thereof. Background Art
[0002] Hydrogen peroxide (H2O2) is valued in the field of green chemistry for its eco-friendliness and multiple uses. It decomposes into harmless water and oxygen, making it a "green" oxidant and reagent. H2O2 is mainly produced through the anthraquinone process and plays a vital role in the chemical industry, where it is valued for its efficiency and cost-effectiveness. Although the anthraquinone process is highly efficient and can produce H2O2 concentrations as high as 70wt%, the process requires a complex and expensive infrastructure for maintenance and has adverse environmental impacts due to the use of hazardous substances for precise monitoring and periodic catalysts. Moreover, in practice, the concentrations of H2O2 required for use are significantly lower. For example, concentrations as low as 0.4wt% and below 6wt% are sufficient for water treatment and antimicrobial purposes, respectively. Therefore, it is expensive and dangerous to produce high-concentration (27wt%) H2O2 solutions and transport them from centralized plants to end users, store and dilute the H2O2 before use.
[0003] Electrochemical catalysis of the two-electron oxygen reduction reaction (2e - The method of producing H2O2 by ORR (oxidation reaction reaction) uses oxygen (O2) and water (H2O) as raw materials, allowing users to produce H2O2 on a small scale on site, solving most of the problems of anthraquinone process. However, the reaction process involves 4e - The competing pathways greatly reduce the selectivity of the desired product H2O2. Therefore, it is crucial to develop ORR electrocatalysts with strong selectivity. Summary of the invention
[0004] The present invention aims to provide a nitrogen-doped titanium dioxide@titanium carbide composite material and a preparation method and application thereof, wherein the nitrogen-doped titanium dioxide@titanium carbide is used for 2e - ORR generates H2O2, which has good activity and selectivity for the two-electron oxygen reduction reaction.
[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0006] The present invention provides a method for preparing a nitrogen-doped titanium dioxide@titanium carbide composite material, comprising the following steps:
[0007] Calcining titanium carbide in an oxygen-containing atmosphere to obtain titanium dioxide@titanium carbide;
[0008] Under the condition of nitrogen-doped gas, the titanium dioxide@titanium carbide is subjected to plasma enhanced chemical vapor deposition to obtain a nitrogen-doped titanium dioxide@titanium carbide composite material.
[0009] Preferably, the oxygen content of the oxygen-containing atmosphere is 21 to 99.9% by volume.
[0010] Preferably, the calcination temperature is 100-500° C., the time is 60-180 min, and the heating rate to the calcination temperature is 0.1-10° C. / min.
[0011] Preferably, the diameter of the titanium carbide is 30-50 nm, and the thickness of the titanium dioxide layer in the titanium dioxide@titanium carbide is 3-20 nm.
[0012] Preferably, the carrier gas used for plasma enhanced chemical vapor deposition is a protective gas or a reducing gas; the protective gas is argon, nitrogen or helium; the reducing gas is hydrogen, a hydrogen-argon mixture or a hydrogen-nitrogen mixture; the partial pressure of the carrier gas is 20 to 100 Pa.
[0013] Preferably, the conditions for the plasma enhanced chemical vapor deposition include: the partial pressure of the nitrogen-containing doping gas is 20-60 Pa; the nitrogen-containing doping gas is nitrogen or ammonia; and the deposition power is 64-100W.
[0014] Preferably, the conditions of the plasma enhanced chemical vapor deposition include: a deposition temperature of 200 to 450° C., a deposition time of 10 to 60 min, and a heating rate of 0.5 to 10° C. / min.
[0015] The present invention provides a nitrogen-doped titanium dioxide@titanium carbide composite material prepared by the preparation method described in the above technical solution.
[0016] Preferably, in the nitrogen-doped titanium dioxide@titanium carbide composite material, the nitrogen doping amount is 1.5-4wt%.
[0017] The present invention provides the use of the nitrogen-doped titanium dioxide@titanium carbide composite material described in the above technical solution in generating hydrogen peroxide by a two-electron oxygen reduction reaction.
[0018] The present invention provides a method for preparing a nitrogen-doped titanium dioxide @ titanium carbide composite material, wherein titanium carbide powder is calcined to obtain titanium dioxide @ titanium carbide, and titanium dioxide @ titanium carbide is subjected to plasma enhanced chemical vapor deposition to obtain a nitrogen-doped titanium dioxide @ titanium carbide composite material. During the calcination process, titanium dioxide is grown on the surface of titanium carbide by in-situ topological chemical oxidation to form a core-shell composite structure, and then plasma enhanced chemical vapor deposition is performed to achieve nitrogen doping to obtain a nitrogen-doped titanium dioxide @ titanium carbide composite material. Among them, the core-shell structure can effectively increase the active area of the reaction, so that more atoms can be doped as active sites for the reaction, and the adsorption energy of titanium dioxide and titanium carbide to hydrogen peroxide is inconsistent, which is conducive to accelerating the discharge of hydrogen peroxide, a product of oxygen reduction, thereby improving the activity of the two-electron oxygen reduction reaction; and nitrogen doping is achieved by vapor deposition, and the electron density and spin density of the original adjacent atoms are changed to a certain extent due to the difference in electronegativity, thereby improving the conductivity and accelerating the electron transfer of the two-electron oxygen reduction reaction. Therefore, the composite material can not only ensure the effective contact between the active material and the electrolyte and reduce the accumulation of the oxygen reduction product hydrogen peroxide inside the electrode, but also help promote electron transfer in the oxygen reduction process and improve the kinetics of the two-electron oxygen reduction reaction.
[0019] Different from the time-consuming traditional wet chemical synthesis method, the present invention uses effective topological chemical oxidation and plasma enhanced chemical vapor deposition to directly synthesize nitrogen-doped titanium dioxide @ titanium carbide. The method is simple and does not require any complicated process and post-treatment, which effectively simplifies the preparation process, shortens the synthesis time, and achieves rapid synthesis.
[0020] The method of the present invention can obtain different types of electrocatalysts by regulating process parameters, including adjusting the crystal form of titanium dioxide, the thickness of titanium dioxide and the content of nitrogen doping, so that the electrocatalyst has good activity and selectivity for two-electron oxygen reduction reaction. For example, the crystal form of titanium dioxide can be effectively controlled by regulating the calcination temperature, the thickness of titanium dioxide can be adjusted by adjusting the oxygen content, and the nitrogen doping content can be adjusted by adjusting the deposition time or the amount of doping gas, which is conducive to accelerating interfacial electron transfer. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Figure 1 The X-ray diffraction patterns of titanium dioxide@titanium carbide sintered at different temperatures in Examples 1 to 3 and the titanium carbide in Comparative Example 1;
[0022] Figure 2 The linear sweep voltammetric curves of titanium dioxide@titanium carbide sintered at different temperatures in Examples 1 to 3 and the titanium carbide in Comparative Example 1;
[0023] Figure 3 is a transmission electron microscope image of titanium dioxide @ titanium carbide in Example 1;
[0024] Figure 4 This is the X-ray photoelectron spectrum of nitrogen-doped titanium dioxide@titanium carbide prepared in Example 1;
[0025] Figure 5 The linear sweep voltammetric curves of titanium carbide and nitrogen-doped titanium carbide in Comparative Examples 1-2;
[0026] Figure 6 The linear sweep voltammetry curves of different materials in Example 1 and Comparative Example 1 are shown;
[0027] Figure 7 The linear sweep voltammetric curves of nitrogen-doped titanium dioxide@titanium carbide in Examples 1 to 3;
[0028] Figure 8 The selectivity of producing hydrogen peroxide by two-electron oxygen reduction reaction of different materials in Examples 1 to 3 and Comparative Example 1. DETAILED DESCRIPTION
[0029] The present invention provides a method for preparing a nitrogen-doped titanium dioxide@titanium carbide composite material, comprising the following steps:
[0030] Calcining titanium carbide in an oxygen-containing atmosphere to obtain titanium dioxide@titanium carbide;
[0031] Under the condition of nitrogen-doped gas, the titanium dioxide@titanium carbide is subjected to plasma enhanced chemical vapor deposition to obtain a nitrogen-doped titanium dioxide@titanium carbide composite material.
[0032] In the present invention, unless otherwise specified, the required raw materials or reagents are commercially available products well known to those skilled in the art.
[0033] In the present invention, the oxygen content of the oxygen-containing atmosphere is preferably 21 to 99.9%, more preferably 30 to 75%, by volume fraction.
[0034] In the present invention, the calcination temperature is preferably 100-500°C, more preferably 200-450°C, more preferably 300-350°C, the time is preferably 60-180min, more preferably 90-160min, further preferably 120-150min, and the heating rate to the calcination temperature is preferably 0.1-10°C / min, more preferably 0.5-5°C / min, further preferably 2-3°C / min.
[0035] In the present invention, the diameter of the titanium carbide is preferably 30 to 50 nm, and the thickness of the titanium dioxide layer in the titanium dioxide@titanium carbide is preferably 3 to 20 nm, more preferably 5 to 18 nm, and further preferably 7 to 12 nm.
[0036] The present invention has no special limitation on the equipment used for the plasma enhanced chemical vapor deposition, and any corresponding equipment known in the art can be used.
[0037] In the present invention, the carrier gas used for plasma enhanced chemical vapor deposition is a protective gas or a reducing gas; the protective gas is argon, nitrogen or helium; the reducing gas is hydrogen, a hydrogen-argon mixture or a hydrogen-nitrogen mixture; the partial pressure of the carrier gas is 20 to 100 Pa, more preferably 22.5 to 80 Pa, and further preferably 30 to 50 Pa.
[0038] In the present invention, the conditions for plasma enhanced chemical vapor deposition preferably include: the partial pressure of the nitrogen-containing doping gas is 20 to 60 Pa, more preferably 25 to 55 Pa, and further preferably 30 to 49.5 Pa; the nitrogen-containing doping gas is nitrogen or ammonia; the deposition power is 64 to 100 W, more preferably 70 to 90 W.
[0039] In the present invention, the conditions of plasma enhanced chemical vapor deposition include: a deposition temperature of 200 to 450°C, more preferably 250 to 400°C, a deposition time of 10 to 60 min, more preferably 20 to 50 min, further preferably 25 to 30 min, and a heating rate of 0.5 to 10°C / min, more preferably 2 to 3°C / min.
[0040] The present invention provides a nitrogen-doped titanium dioxide@titanium carbide composite material prepared by the preparation method described in the above technical solution.
[0041] In the present invention, in the nitrogen-doped titanium dioxide@titanium carbide composite material, the nitrogen doping amount is preferably 1.5 to 4 wt %, more preferably 1.58 to 3.8 wt %, and further preferably 2.5 to 3.56 wt %.
[0042] The present invention provides the use of the nitrogen-doped titanium dioxide@titanium carbide composite material in the two-electron oxygen reduction reaction to generate hydrogen peroxide. The present invention has no special limitation on the method of the application, and the application can be carried out according to methods well known in the art.
[0043] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.
[0044] Example 1
[0045] 1 g of commercially available titanium carbide was placed in a crucible and oxygen was injected, and the crucible was heated to 300°C at a calcination rate of 5°C / min and calcined for 120 min in an atmosphere containing 30% oxygen to obtain titanium dioxide @ titanium carbide (referred to as TiC300), wherein the thickness of the titanium dioxide layer was 7 nm;
[0046] The gas atmosphere was switched, and TiC300 was placed in an atmosphere with nitrogen as the carrier gas. Ammonia was introduced as the doping source for plasma enhanced chemical vapor deposition. The specific reaction conditions were: carrier gas partial pressure of 22.5 Pa, deposition power of 64 W, ammonia partial pressure of 49.5 Pa, heating to 400 °C at 2 °C / min for 30 min, and naturally cooled to room temperature to obtain nitrogen-doped titanium dioxide @ titanium carbide electrocatalyst, denoted as N-TiC300, in which the nitrogen doping amount was 3.56 wt%.
[0047] Example 2
[0048] 1 g of commercially available titanium carbide was placed in a crucible and oxygen was injected into it. The crucible was heated to 350°C at a calcination rate of 2°C / min and calcined for 90 min in an atmosphere containing 75% oxygen to obtain a titanium dioxide @ titanium carbide electrocatalyst (referred to as TiC350), wherein the thickness of the titanium dioxide layer was 12 nm.
[0049] The gas atmosphere was switched, and TiC350 was placed in a gas atmosphere with argon as the carrier gas. Ammonia was introduced as a doping source for plasma enhanced chemical vapor deposition. The specific reaction conditions were: carrier gas partial pressure of 30 Pa, deposition power of 100 W, ammonia partial pressure of 55 Pa, heating to 450 ° C at 3 ° C / min for 20 min, and naturally cooled to room temperature to obtain nitrogen-doped titanium dioxide @ titanium carbide electrocatalyst, denoted as N-TiC350, in which the nitrogen doping amount was 2.5wt%.
[0050] Example 3
[0051] 1 g of commercially available titanium carbide was placed in a crucible, and oxygen was injected into the crucible, and the crucible was heated to 450°C at a calcination rate of 0.5°C / min and calcined for 150 min in an atmosphere containing 99.9% oxygen, to obtain a titanium dioxide @ titanium carbide electrocatalyst (referred to as TiC450), wherein the thickness of the titanium dioxide layer was 15 nm;
[0052] The gas atmosphere was switched, and TiC450 was placed in a gas atmosphere with hydrogen as the carrier gas. Nitrogen was introduced as the doping source for plasma enhanced chemical vapor deposition. The specific reaction conditions were: carrier gas partial pressure of 50 Pa, deposition power of 64 W, nitrogen partial pressure of 25 Pa, heating to 250 ° C at 1 ° C / min for 50 min, and naturally cooled to room temperature to obtain nitrogen-doped titanium dioxide @ titanium carbide electrocatalyst, denoted as N-TiC450, in which the nitrogen doping amount was 1.58wt%.
[0053] Comparative Example 1
[0054] A titanium carbide TiC material without any treatment is used as comparative example 1.
[0055] Comparative Example 2
[0056] 1 g of commercially available titanium carbide was placed in a crucible, and ammonia was introduced as a doping source in an atmosphere of nitrogen as a carrier gas to perform plasma enhanced chemical vapor deposition. The specific reaction conditions were: carrier gas partial pressure of 25 Pa, deposition power of 100 W, ammonia partial pressure of 60 Pa, heating to 350 ° C at 2 ° C / min for 40 minutes, and naturally cooled to room temperature to obtain a nitrogen-doped titanium carbide electrocatalyst, denoted as N-TiC, in which the nitrogen doping amount was 2.03wt%.
[0057] Test Data and Characterization
[0058] Figure 1 X-ray diffraction patterns (XRD) of titanium dioxide @ titanium carbide obtained by sintering at different temperatures in Examples 1 to 3 and titanium carbide in Comparative Example 1; Figure 1 It can be seen that the characteristic diffraction peaks of the original TiC sample are located at 35.9°, 41.7°, 60.4°, 72.3° and 76.1°, respectively, on the (111), (200), (220), (311) and (222) crystal planes of the TiC standard card JCPDSno.71-0298. The XRD spectrum of TiC300 corresponds to the original TiC sample, wherein the characteristic diffraction peak of TiC300 at 25.3° corresponds to the JCPDS no.78-2486 of the standard card of anatase titanium dioxide, and the peak intensity increases; the XRD spectrum of TiC350 corresponds to the original TiC sample on the one hand, but the overall peak intensity is weakened, on the other hand, the characteristic diffraction peaks at 25.3°, 37.7°, 48.0°, and 53.8° correspond to the JCPDS no.78-2486 of the standard card of anatase titanium dioxide; the XRD spectrum of TiC450 corresponds to the original TiC sample on the one hand, but the overall peak intensity is further weakened compared with TiC350, on the other hand, the characteristic diffraction peaks at 27.4°, 41.2°, 54.3°, and 56.6° correspond to the JCPDS no.78-2486 of the standard card of rutile titanium dioxide no.75-7155; Explanation: First, the oxygen content increases the thickness of the titanium dioxide layer, thereby showing an enhancement in the diffraction peak; second, as the sintering temperature increases, it is confirmed that the crystal phase of TiO2 changes from mostly anatase phase to mostly rutile phase.
[0059] Figure 2 The linear sweep voltammetric curves of titanium dioxide @ titanium carbide sintered at different temperatures in Examples 1 to 3 and titanium carbide in Comparative Example 1 are shown in the figure. Different materials are used as electrodes on a rotating disk electrode at a speed of 1600 rpm and 0.1 M KOH to perform electrochemical performance tests. The results are shown in the figure. Figure 2As shown in the figure, the limiting current density is TiC 300>TiC>TiC350>TiC450, and the starting potential is TiC300>TiC>TiC350>TiC450, both of which indicate that TiC 300 has a higher two-electron oxygen reduction activity. This indicates that the formation of the core-shell structure makes the activity of TiC300 better than that of TiC, proving the role of the core-shell structure. TiC350 and TiC450 have poor conductivity due to the formation of rutile phase titanium dioxide, which affects their activity.
[0060] Figure 3 is a transmission electron microscope image of titanium dioxide @ titanium carbide TiC300 in Example 1; Figure 3 It can be seen that TiC300 grows titanium dioxide on the surface of titanium carbide through in-situ topological chemical oxidation to form a core-shell composite structure, and the thickness of the titanium dioxide layer is about 7nm; the core-shell structure can effectively increase the active area of the reaction, thereby achieving more atomic doping as active sites for the reaction.
[0061] Figure 4 X-ray photoelectron spectrum of nitrogen-doped titanium dioxide@titanium carbide electrocatalyst prepared in Example 1; Figure 4 It can be seen that the full spectrum of nitrogen-doped titanium dioxide @ titanium carbide electrocatalyst shows the presence of C, N, Ti and O elements, indicating that the titanium dioxide @ titanium carbide electrocatalyst was successfully nitrogen-doped by plasma-enhanced chemical vapor deposition to obtain a nitrogen-doped titanium dioxide @ titanium carbide composite material, in which the nitrogen doping content was 3.56wt%. The introduction of nitrogen doping may have changed the original electron density and spin density of adjacent atoms, accelerated the electron transfer of the two-electron oxygen reduction reaction, and was beneficial to the generation and desorption of reaction intermediates.
[0062] Figure 5 The linear sweep voltammetric curves of titanium carbide and nitrogen-doped titanium carbide in comparative examples 1 to 2 are shown in Table 1. Different materials were used as electrodes on a rotating disk electrode at a speed of 1600 rpm and 0.1 M KOH to conduct electrochemical performance tests. The results are shown in Table 1. Figure 5 The results show that the activity of N-TiC simply doped with nitrogen is significantly better than that of TiC, indicating that the introduction of nitrogen doping can improve the activity.
[0063] Figure 6 The linear sweep voltammetry curves of different materials in Example 1 and Comparative Example 1 are shown in Figure 1. Different materials were used as electrodes on a rotating disk electrode at a speed of 1600 rpm and 0.1 M KOH to perform electrochemical performance tests. The results are shown in Figure 1. Figure 6As shown; the starting potential is N-TiC300>TiC300>TiC, indicating that the growth of titanium dioxide on the surface of titanium carbide by in-situ topological chemical oxidation to form a core-shell composite material and the subsequent plasma-enhanced chemical vapor deposition to obtain nitrogen-doped titanium dioxide@titanium carbide electrocatalyst helps to reduce the accumulation of oxygen reduction product hydrogen peroxide inside the electrode; promote electron transfer in the oxygen reduction process, and improve the kinetics of the two-electron oxygen reduction reaction. Figure 6 It shows that the activity of nitrogen-doped TiO2@TiC is better than that of TiO2@TiC, which further proves the effect of nitrogen doping and core-shell structure. Figure 5 This shows that the synergistic effect of core-shell structure and nitrogen doping is better than the electrocatalytic activity of the material in a single state.
[0064] Figure 7 The linear sweep voltammetric curves of nitrogen-doped titanium dioxide @ titanium carbide in Examples 1 to 3 are shown in Figure 1. Different materials were used as electrodes on a rotating disk electrode at a speed of 1600 rpm and 0.1 M KOH to perform electrochemical performance tests. The results are shown in Figure 1. Figure 7 The activity of Example 1 is significantly better than that of Example 2 and Example 3, indicating that Example 1 has faster reaction kinetics. Figure 2 By comparison, the nitrogen-doped titanium dioxide @ titanium carbide produced by plasma enhanced chemical vapor deposition in Examples 1 to 3 has further improved activity compared to titanium dioxide @ titanium carbide, which indicates that the electrode material doped with nitrogen by plasma enhanced chemical vapor deposition has a faster electron-proton transfer rate, which is beneficial to reducing the adsorption energy of the intermediate on the electrode surface and accelerating the discharge of the oxygen reduction product hydrogen peroxide, thereby improving the activity of the two-electron oxygen reduction reaction.
[0065] Figure 8 The selectivity of producing hydrogen peroxide by two-electron oxygen reduction reaction of different materials in Examples 1 to 3 and Comparative Example 1. Figure 8 As shown, the Faradaic efficiency is Example 1 (94%)>Comparative Example 1 (81%)>Example 2 (70%)>Example 3 (65%), indicating that Example 1 has a higher selectivity for the two-electron oxygen reduction reaction.
[0066] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A method for preparing a nitrogen-doped titanium dioxide@titanium carbide composite material, characterized in that: The following steps are involved: Calcining titanium carbide in an oxygen-containing atmosphere to obtain titanium dioxide@titanium carbide; Under the condition of nitrogen-doped gas, the titanium dioxide@titanium carbide is subjected to plasma enhanced chemical vapor deposition to obtain a nitrogen-doped titanium dioxide@titanium carbide composite material.
2. The preparation method according to claim 1, characterized in that: The oxygen content of the oxygen-containing atmosphere is 21 to 99.9% by volume.
3. The preparation method according to claim 1 or 2, characterized in that: The calcination temperature is 100-500° C., the time is 60-180 min, and the heating rate to the calcination temperature is 0.1-10° C. / min.
4. The preparation method according to claim 3, characterized in that: The diameter of the titanium carbide is 30-50 nm, and the thickness of the titanium dioxide layer in the titanium dioxide@titanium carbide is 3-20 nm.
5. The preparation method according to claim 1, characterized in that: The carrier gas used for plasma enhanced chemical vapor deposition is a protective gas or a reducing gas; the protective gas is argon, nitrogen or helium; the reducing gas is hydrogen, a hydrogen-argon mixed gas or a hydrogen-nitrogen mixed gas; the partial pressure of the carrier gas is 20-100Pa.
6. The preparation method according to claim 1 or 5, characterized in that: The conditions of the plasma enhanced chemical vapor deposition include: the partial pressure of the nitrogen-containing doping gas is 20-60 Pa; the nitrogen-containing doping gas is nitrogen or ammonia; and the deposition power is 64-100W.
7. The preparation method according to claim 6, characterized in that: The conditions of the plasma enhanced chemical vapor deposition include: a deposition temperature of 200 to 450° C., a deposition time of 10 to 60 minutes, and a heating rate of 0.5 to 10° C. / min.
8. The nitrogen-doped titanium dioxide@titanium carbide composite material prepared by the preparation method according to any one of claims 1 to 7.
9. The nitrogen-doped titanium dioxide@titanium carbide composite material according to claim 8, characterized in that: In the nitrogen-doped titanium dioxide@titanium carbide composite material, the nitrogen doping amount is 1.5-4 wt %.
10. Use of the nitrogen-doped titanium dioxide@titanium carbide composite material according to claim 8 or 9 in generating hydrogen peroxide by a two-electron oxygen reduction reaction.