阅读说明：本技术 一种电催化剂及其制备方法 (Electrocatalyst and preparation method thereof ) 是由 穆杨 王明州 侯南南 于 2021-10-20 设计创作，主要内容包括：本发明提供了一种氢掺杂二氧化钛电催化剂的制备方法,使用钛酸四丁酯作为原料,首先利用溶剂热法使钛酸四丁酯在HF水溶液中合成暴露出高能{001}晶面的TiO-(2)前驱体,再利用酸-金属处理的方法对TiO-(2)前驱体进行氢掺杂,将TiO-(2)和金属Zn同时分散到盐酸溶液中,利用TiO-(2)和金属Zn之间的功函数差,将溶液中的氢掺入到TiO-(2)中,最终得到了目标材料氢掺杂暴露出高能晶面的二氧化钛(H-TiO-(2))。本发明提供的方法制得的H-TiO-(2)具有优良的电化学性能以及高选择性,能够在较低过电位下选择性的将O-(2)两电子还原为H-(2)O-(2),实现了在常温常压的温和条件下电催化合成H-(2)O-(2),具有广阔的实际应用的潜力。本发明还提供了一种氢掺杂二氧化钛电催化剂。(The invention provides a preparation method of a hydrogen-doped titanium dioxide electrocatalyst, which uses tetrabutyl titanate as a raw material, and firstly synthesizes the TiO with exposed high-energy {001} crystal face in HF aqueous solution by using the tetrabutyl titanate through a solvothermal method 2 Precursor, and treating TiO with acid-metal 2 Hydrogen doping the precursor to obtain TiO 2 Dispersing in hydrochloric acid solution together with metal Zn, and using TiO 2 The difference of work function between the metal Zn and the metal Zn, and the hydrogen in the solution is doped into the TiO 2 Finally obtaining the titanium dioxide (H-TiO) of the target material with hydrogen doping and exposed high-energy crystal face 2 ). The H-TiO prepared by the method provided by the invention 2 Has excellent electrochemical performance and high selectivity, and can selectively convert O into O under lower overpotential 2 Reduction of two electrons to H 2 O 2 Realizes the electrocatalytic synthesis of H under the mild conditions of normal temperature and normal pressure 2 O 2 And has wide potential of practical application. The invention also provides a hydrogen-doped titanium dioxide electrocatalyst.)

1. An electrocatalyst which is hydrogen doped titanium dioxide; the electrocatalyst exposes the high energy {001} crystal plane.

2. Electrocatalyst according to claim 1, characterized in that the electrocatalyst is hydrogen doped in TiO₂The high energy 001 crystal plane.

3. A method of preparing the electrocatalyst of claim 1, comprising:

reacting tetrabutyl titanate with HF to obtain a precursor solution;

carrying out hydrothermal reaction on the precursor solution to obtain TiO₂A precursor;

subjecting the TiO to a reaction₂And mixing the precursor, hydrochloric acid and Zn to obtain the electrocatalyst.

4. The method according to claim 3, wherein the HF is an HF solution, and the mass concentration of the HF solution is 20-30%.

5. The method according to claim 3, wherein the volume ratio of tetrabutyl titanate to HF is 4 (2-3).

6. The method according to claim 3, wherein the temperature of the hydrothermal reaction is 170-190 ℃.

7. The method according to claim 3, wherein the hydrothermal reaction is preferably completed by further comprising:

drying the obtained reaction product;

the drying temperature is 40-60 ℃.

8. The method of claim 3, wherein the TiO is₂The using amount ratio of the precursor, the hydrochloric acid and the Zn is (0.02-0.03) g: (20-25) mL: (0.05-1) g.

9. The method according to claim 3, wherein the mass fraction of the hydrochloric acid solution is 35-40%.

10. The method of claim 3, further comprising, after said mixing:

drying the obtained mixture;

the drying temperature is 40-60 ℃.

Technical Field

The invention belongs to the technical field of energy chemical industry, particularly relates to an electrocatalyst and a preparation method thereof, and further relates to a method for preparing H by electrocatalytic oxygen reduction₂O₂The electrocatalyst of (1).

Background

Hydrogen peroxide (H)₂O₂) One of the most important chemical products, widely used in chemical synthesis and medicineThe pharmaceutical, environmental and fuel cell technologies have made their demand to increase greatly in recent years. Current Industrial Synthesis of H₂O₂Highly dependent on the anthraquinone process, which involves the ordered oxidation and reduction of anthraquinone molecules, although this process can be used for large scale production, there are still many challenges to be solved, for example from H₂O₂Separating out organic impurities, treating industrial waste and reacting with H₂O₂And potential safety risks associated with storage and transportation. Another synthesis H₂O₂The method is that hydrogen and oxygen are directly synthesized into H by using a catalyst₂O₂However, the mixing process of hydrogen and oxygen has a risk of explosion. Electrochemistry is a safe, green and environment-friendly technology, and becomes a promising solution. The electrochemical process of the two-electron oxygen reduction reaction (2e-ORR) can directly reduce O₂Reduction to H₂O₂The method has the advantages of mild reaction conditions, easy operation, safety, harmlessness and the like. O is₂The reduction is divided into two-electron path and four-electron path, and the two-electron oxygen reduction generates a target product H₂O₂However, four electron oxygen reduction will produce a by-product H₂And O, causing the waste of energy. Therefore, the key to achieving this process scale is the development of efficient, economically feasible, highly selective and highly active electrocatalysts.

Noble metals (such as Pt, Pd, Au) and their alloys can be used for catalytic oxygen reduction reaction at present, because they possess high catalytic performance, but their scarcity and high price limit their application. Thus, the development of high performance, non-noble metal electrocatalysts using inexpensive commercial raw materials for H production from two electron ORRs₂O₂Presents a significant challenge to practical application. The transition metal oxide has advantages of low price, stable structure, etc. compared to the noble metal-based catalyst, but cannot be directly used as an electrocatalyst due to its non-active redox property. How to develop a transition metal oxide electrocatalyst with high redox activity, which can catalyze the two-electron oxidation process to synthesize H₂O₂It is very critical.

TiO₂As an important metal oxide semiconductor, the metal oxide semiconductor has the advantages of low price, stable structure, environmental friendliness and the like. However, TiO is hindered by its lower conductivity and reactivity₂Becomes a high-efficiency electrocatalyst.

Disclosure of Invention

In view of the above, the present invention is to provide an electrocatalyst and a preparation method thereof, which solves the problem of H production by electrocatalysis₂O₂The catalyst has the problems of high overpotential, low selectivity and the like, and realizes large-scale industrial production; the electrocatalyst provided by the invention has the advantages of stable structure, low price and environmental friendliness, is a transition metal oxide electrocatalyst, and is prepared by combining a hydrothermal method with an acid-metal treatment method to obtain H-TiO with remarkable electrocatalytic activity and high selectivity₂An electrocatalyst.

The invention provides an electrocatalyst which is hydrogen doped titanium dioxide; the electrocatalyst exposes the high energy {001} crystal plane.

Preferably, the electrocatalyst is one in which hydrogen is doped into TiO₂The high energy 001 crystal plane.

The invention provides a preparation method of the electrocatalyst according to the technical scheme, which comprises the following steps:

reacting tetrabutyl titanate with HF to obtain a precursor solution;

carrying out hydrothermal reaction on the precursor solution to obtain TiO₂A precursor;

subjecting the TiO to a reaction₂And mixing the precursor, hydrochloric acid and Zn to obtain the electrocatalyst.

Preferably, the HF is an HF solution, and the mass concentration of the HF solution is 20-30%.

Preferably, the volume ratio of the tetrabutyl titanate to the HF is 4 (2-3).

Preferably, the temperature of the hydrothermal reaction is 170-190 ℃.

Preferably, the hydrothermal reaction further comprises, after completion of the hydrothermal reaction:

drying the obtained reaction product;

the drying temperature is 40-60 ℃.

Preferably, the TiO is₂The using amount ratio of the precursor, the hydrochloric acid and the Zn is (0.02-0.03) g: (20-25) mL: (0.05-1) g.

Preferably, the mass fraction of the hydrochloric acid solution is 35-40%.

Preferably, the mixing further comprises:

drying the obtained mixture;

the drying temperature is 40-60 ℃.

TiO₂The physicochemical properties and catalytic activity of the catalyst mainly depend on the microscopic morphology of the surface and the mainly exposed crystal planes. The invention firstly treats TiO₂Crystal face regulation is carried out, high-energy {001} crystal face is selectively exposed, and TiO is improved₂And (4) electrochemical activity. However exposing high energy crystalline TiO₂/{001} although possessing an active site for electrocatalytic oxygen reduction, it reduced to synthesize H for two-electron oxygen₂O₂The selectivity of the method is not high, but the method is more prone to four-electron oxygen reduction to synthesize water, and energy is wasted. Heteroatom doping can significantly alter TiO₂Influence its electrocatalytic activity and selectivity. The invention adopts a hydrogen doping method to dope hydrogen into TiO through acid-metal treatment₂In the crystal lattice. The hydrogen incorporation can be further regulated and controlled by {001} -TiO₂The electron structure and spin polarization of the compound improve the electrocatalytic oxygen reduction synthesis of H₂O₂Selectivity of (2). The invention reports for the first time that H-TiO with high-energy {001} crystal face exposed by hydrogen doping₂The electrocatalyst has high-efficiency electrocatalytic activity and high selectivity, and can effectively synthesize H by electrocatalysis₂O₂And has wide application prospect.

The H-TiO with high energy {001} crystal face exposed by hydrogen doping prepared by the invention₂The Ti source reserves needed by the electrocatalyst are rich and environment-friendly, and are common chemical raw materials, and the price is far lower than that of a noble metal catalyst; preparation of H-TiO₂The electrocatalyst has high yield, pure crystal phase, stable structure and uniform distribution of the layered porous nanosheetsUniform, large specific surface area and more catalytic sites; preparation of H-TiO₂The electrocatalyst has excellent electrochemical activity and high selectivity, and can be used for preparing H by high-efficiency electrocatalytic oxygen reduction₂O₂The method has great significance for practical application; preparation of H-TiO₂The electrocatalyst has better stability, can maintain high electrocatalytic activity for a long time, and is beneficial to electrocatalytic synthesis of H₂O₂The practical application of (1).

Drawings

In FIG. 1, a is the TiO prepared in example 1₂The high-angle annular dark field scanning transmission electron microscope image b is H-TiO₂A high angle annular dark field scanning transmission electron microscope image of the electrocatalyst;

FIG. 2 shows the H-TiO compound prepared in example 1₂And non-hydrogen-doped TiO₂XRD diffraction patterns of the materials;

FIG. 3 shows the preparation of H-TiO according to example 1₂And non-hydrogen-doped TiO₂Nuclear magnetic resonance hydrogen spectrum images of the material;

FIG. 4 shows H-TiO prepared in example 1₂And non-hydrogen-doped TiO₂A graph of the results of a ring-and-disk electrode test of Linear Sweep Voltammetry (LSV) with the material as the cathode;

FIG. 5 shows H-TiO prepared in example 1₂And non-hydrogen-doped TiO₂Electrocatalytic oxygen reduction synthesis of H by using material as cathode₂O₂The result of the selectivity test;

FIG. 6 shows H-TiO prepared in example 1₂And non-hydrogen-doped TiO₂The material is used as the electron transfer number change in the cathode electrocatalytic oxygen reduction process;

FIG. 7 shows H-TiO prepared in example 1₂Materials are respectively in O₂Images of cyclic voltammetry tests (CV tests) performed in saturated and Ar saturated electrolytes;

FIG. 8 shows H-TiO prepared in example 1₂Images of ring current and disc current during long-term stability electrocatalysis testing of materials;

FIG. 9 shows H-TiO prepared in example 1₂And non-hydrogen-doped TiO₂The material is actually combined as a cathode in a double-chamber reactorTo form H₂O₂Change in density image.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. In the examples, the methods used were all conventional methods unless otherwise specified.

The invention provides an electrocatalyst which is hydrogen doped titanium dioxide; the electrocatalyst exposes the high energy {001} crystal plane.

In the present invention, hydrogen in the electrocatalyst is preferably doped in TiO₂The high energy 001 crystal plane.

The invention provides a preparation method of the electrocatalyst according to the technical scheme, which comprises the following steps:

reacting tetrabutyl titanate with HF to obtain a precursor solution;

carrying out hydrothermal reaction on the precursor solution to obtain TiO₂A precursor;

subjecting the TiO to a reaction₂And mixing the precursor, hydrochloric acid and Zn to obtain the electrocatalyst.

In the present invention, the HF is preferably an HF solution, more preferably an aqueous HF solution; the mass fraction of the HF solution is preferably 20-30%, more preferably 22-28%, and most preferably 24-26%.

In the present invention, the volume ratio of tetrabutyl titanate to HF is preferably 4 (2 to 3), more preferably 4 (2.3 to 2.7), and most preferably 4: 2.5.

In the invention, the reaction is preferably carried out by slowly and dropwise adding tetrabutyl titanate into an HF solution; the reaction is preferably carried out under stirring; the stirring time is preferably 30-40 min, more preferably 33-37 min, and most preferably 35 min.

In the present invention, the precursor solution is preferably light yellow.

In the present invention, after obtaining the precursor solution, the method preferably further comprises: the precursor solution was transferred to a 100mL teflon autoclave.

In the invention, the temperature of the hydrothermal reaction is preferably 170-190 ℃, more preferably 175-185 ℃, and most preferably 180 ℃; the time of the hydrothermal reaction is preferably 20-30 hours, more preferably 22-28 hours, and most preferably 24-26 hours; the hydrothermal reaction is preferably carried out in an oven.

In the present invention, it is preferable that the hydrothermal reaction further comprises:

and cooling the obtained reaction product, and then centrifuging, washing and centrifuging.

In the present invention, the washing is preferably washing with ethanol and water, respectively; the number of times of cleaning is preferably 3-5 times, and more preferably 4 times; the water is preferably deionized water.

In the present invention, it is preferable that the hydrothermal reaction further comprises:

the resulting reaction product was dried.

In the present invention, it is preferable to dry the centrifuged product.

In the invention, the drying is preferably vacuum drying, and the drying temperature is preferably 40-60 ℃, more preferably 45-55 ℃, and most preferably 50 ℃; the drying time is preferably 24 to 48 hours, more preferably 30 to 40 hours, and most preferably 35 hours.

In the present invention, the TiO is₂The precursor is TiO exposed with high-energy {001} crystal face₂And (3) precursor.

In the present invention, the method of mixing preferably comprises:

subjecting the TiO to a reaction₂Dispersing the precursor into water, adding hydrochloric acid into the dispersion, and finally adding Zn powder.

In the present invention, the water is preferably deionized water.

In the present invention, the TiO is₂The preferable dosage ratio of the precursor to the water is (0.02-0.03) g: (15-25) mL, more preferably (0.023-0.027) g: (18-22) mL, most preferably 0.025 g: 20 mL.

In the present invention, the hydrochloric acid is preferably a hydrochloric acid solution, more preferably an aqueous hydrochloric acid solution; the mass powder fraction of the hydrochloric acid solution is preferably 35-40%, more preferably 36-38%, and most preferably 37%.

In the present invention, the TiO is₂The preferable dosage ratio of the precursor, the hydrochloric acid and the Zn is (0.02-0.03) g: (20-25) mL: (0.05-1) g, more preferably (0.023-0.027) g: (21-24) mL: (0.1-0.8) g, most preferably 0.025 g: (22-23) mL: 0.5 g.

In the present invention, after the mixing is completed, the method preferably further comprises:

the resulting mixture was centrifuged (after the Zn powder was completely dissolved, the precipitate was centrifuged), and washed.

In the present invention, the washing is preferably washing with water and ethanol; the number of washing is preferably 2 to 4, and more preferably 3.

In the present invention, it is preferable that the mixture further comprises:

the resulting mixture was dried.

In the present invention, it is preferable to dry the washed substance.

In the present invention, the drying is preferably vacuum drying; the drying temperature is preferably 40-60 ℃, more preferably 45-55 ℃, and most preferably 50 ℃; the drying time is preferably 24 to 48 hours, more preferably 30 to 40 hours, and most preferably 35 hours.

In the invention, the electrocatalyst is H-TiO with hydrogen doped high-energy {001} crystal face exposed₂。

The H-TiO with high energy {001} crystal face exposed by hydrogen doping prepared by the invention₂The Ti source reserves needed by the electrocatalyst are rich and environment-friendly, and are common chemical raw materials, and the price is far lower than that of a noble metal catalyst; preparation of H-TiO₂The electrocatalyst has high yield, pure crystal phase, stable structure, uniform distribution of the layered porous nanosheets and specific surface areaLarge, many catalytic sites; preparation of electric H-TiO₂The catalyst has excellent electrochemical activity and high selectivity, and can be used for preparing H by efficient electrocatalytic oxygen reduction₂O₂The method has great significance for practical application; preparation of electric H-TiO₂The catalyst has good stability, can maintain high electrocatalytic activity for a long time, and is beneficial to electrocatalytic synthesis of H₂O₂The practical application of (1).

Example 1

Preparing a precursor solution, wherein the preparation method comprises the following steps: slowly dripping 25mL of tetrabutyl titanate into 15mL of HF solution with the mass fraction of 24 wt.%, stirring for 30 minutes to enable the tetrabutyl titanate to fully react to obtain a light yellow precursor solution, and transferring the light yellow precursor solution into a 100mL polytetrafluoroethylene autoclave;

preparation of TiO exposing high-energy {001} crystal face₂The preparation method of the precursor comprises the following steps: and (3) sealing the high-pressure autoclave filled with the precursor solution, putting the high-pressure autoclave into an oven, and carrying out hydrothermal reaction at 175 ℃ for 24 hours. After the reaction is finished and cooled to room temperature, taking out the solution, centrifuging, washing and centrifuging by using ethanol and deionized water respectively, and finally drying in a drying oven at 60 ℃ to obtain TiO exposed with high-energy {001} crystal face₂A precursor;

preparation of H-TiO with hydrogen-doped crystal face exposing high-energy {001}₂The preparation method comprises the following steps: 0.025g of TiO₂The precursor was dispersed in 20mL of deionized water and gently sonicated, and 20mL of a 37% by mass hydrochloric acid solution was added to the mixed solution under continuous magnetic stirring, and finally 0.5g of Zn powder was added. After Zn powder is completely dissolved, centrifugally separating the precipitate, then repeatedly cleaning the precipitate for three times by using water and ethanol, and finally drying the precipitate at the temperature of 60 ℃ in vacuum to obtain the target material H-TiO with hydrogen-doped exposed high-energy {001} crystal face₂。

For TiO prepared in example 1 of the invention₂And H-TiO₂The electrocatalyst is detected by a high-angle annular dark-field scanning transmission electron microscope, the detection result is shown in figure 1, and H-TiO can be seen from figure 1₂The interplanar spacing of (a) is 0.363nm, is obviously larger than that of TiO₂The interplanar spacing of (2) nm indicates that hydrogen doping changes TiO₂The interplanar spacing of (a).

For the H-TiO prepared in example 1₂And non-hydrogen-doped TiO₂XRD diffraction detection is carried out on the material, the detection result is shown in figure 2, and it can be seen that no redundant impurity peak exists in the figure, which indicates that the purity of the sample is high; H-TiO treated by hydrogen doping₂The diffraction peak of (A) shows obvious shift, which indicates that the successful incorporation of hydrogen atoms enables H-TiO₂The interplanar spacing of (a) increases.

For the H-TiO prepared in example 1₂And non-hydrogen-doped TiO₂The nuclear magnetic resonance hydrogen spectrum detection is carried out on the material, the detection result is shown in figure 3, and it can be seen that the material is compared with TiO₂，H-TiO₂An additional peak appears in the hydrogen spectrum image of (A), indicating that in H-TiO₂Forms a hydrogen atom with different coordination environments, and also proves that the hydrogen atom is successfully doped into TiO₂In (1).

For the H-TiO prepared in example 1₂And non-hydrogen-doped TiO₂The material was used as cathode for a ring-disk electrode polarization current test (LSV) using chenhua electrochemical workstation CHI760E and a rotating ring-disk electrode: dispersing 2mg of catalyst material into a mixed solution of 390 mu L of deionized water and 390 mu L of ethanol, adding 20 mu L of Nafion binder, and carrying out ultrasonic treatment for 15min to uniformly disperse the catalyst material; dripping 8 mu L of dispersion liquid onto a glassy carbon electrode, and carrying out a polarization current test of a ring disc electrode after the glassy carbon electrode is slowly dried; taking a glassy carbon electrode loaded with a catalyst as a working electrode, a saturated AgCl electrode as a reference electrode, a carbon rod as a counter electrode, and 0.1mol/L KOH solution as an electrolyte; subjecting the electrolyte solution to O treatment for 30min₂Aerating to enable the solution to reach an oxygen saturation condition, and performing a ring disk electrode test of electrochemical ORR at room temperature; the potential interval of the ring plate current test is-0.2-0.8 (V, RHE), and the rotating speed is 1600 revolutions per minute. The detection result is shown in FIG. 4, and it can be seen that H-TiO was doped with hydrogen₂The cathode shows much larger amount than TiO₂Ring current and disk current of cathode, illustrating hydrogen doping to make TiO₂The electrocatalytic activity of the catalyst is greatly improved.

For the H-TiO prepared in example 1₂And non-hydrogen-doped TiO₂Electrocatalytic oxygen reduction synthesis of H by using material as cathode₂O₂Selective test of (2), electrocatalytic synthesis of H₂O₂The selectivity of (A) is calculated from the data of the polarization current of the ring disk electrode according to the following formula:

wherein, I_ringRepresents the loop current, I_diskRepresenting the disc current, N-0.37 represents the collection efficiency of the platinum ring in the glassy carbon electrode. The detection results are shown in FIG. 5, and H-TiO₂Two-electron oxygen reduction synthesis of H₂O₂The selectivity of (A) is kept above 95% and close to 100%, while TiO₂The two-electron oxygen reduction selectivity of (2) is only 60%.

For the H-TiO prepared in example 1₂And non-hydrogen-doped TiO₂The material is used as the electron transfer number change in the cathode electrocatalytic oxygen reduction process for detection, and the result of the electron transfer number of oxygen reduction is calculated by the data of the ring disk electrode polarization current according to the following formula:

wherein n represents the electron transfer number, I_ringRepresents the loop current, I_diskRepresenting the disc current, N-0.37 represents the collection efficiency of the platinum ring in the glassy carbon electrode. The results are shown in FIG. 6, which shows that H-TiO₂The electron transfer number of the material is close to 2, which shows that the material is subjected to a two-electron oxygen reduction process in the electrocatalytic process and is beneficial to H₂O₂Synthesizing; and TiO 2₂The electron transfer number of the material is close to 3, which shows that the material can simultaneously carry out two-electron oxygen reduction and four-electron oxygen reduction in the electrocatalysis process and is not beneficial to H₂O₂And cause a loss of energy.

For the H-TiO prepared in example 1₂Materials are respectively in O₂Performing Cyclic Voltammetry (CV) test in saturated and Ar saturated electrolytePerformed with chenhua electrochemical workstation CHI760E and glassy carbon rotating ring disk electrodes: dispersing 2mg of catalyst material into a mixed solution of 390 mu L of deionized water and 390 mu L of ethanol, adding 20 mu L of Nafion binder, and carrying out ultrasonic treatment for 15min to uniformly disperse the catalyst material; dripping 8 mu L of dispersion liquid onto a glassy carbon electrode, and performing a ring disk electrode test after the glassy carbon electrode is slowly dried; taking a glassy carbon electrode loaded with a catalyst as a working electrode, a saturated AgCl electrode as a reference electrode, a carbon rod as a counter electrode, and 0.1mol/L KOH solution as an electrolyte; respectively subjecting the electrolyte solution to O treatment for 30min₂Aerating and Ar aerating for 30min to make the solution reach O₂Performing saturation and Ar saturation conditions, and then performing electrochemical cyclic voltammetry at room temperature; the potential range of the cyclic voltammetry test is-0.4-1.2 (V, RHE), and the rotating speed is 0 r/min. The results are shown in FIG. 7, and indicate that the concentration of oxygen in the sample is O₂Under the saturated condition, a CV image has an obvious oxygen reduction peak, and under the Ar saturated condition, the CV image does not have the reduction peak; this indicates that H-TiO₂As the cathode, oxygen reduction reaction occurs in the electrocatalytic process, and the possibility of other reduction reactions is eliminated.

For the H-TiO prepared in example 1₂The material was subjected to long-term stability electrocatalysis testing of loop current and disk current using Chenghua electrochemistry workstation CHI760E and glassy carbon rotating ring disk electrodes: dispersing 2mg of catalyst material into a mixed solution of 390 mu L of deionized water and 390 mu L of ethanol, adding 20 mu L of Nafion binder, and carrying out ultrasonic treatment for 15min to uniformly disperse the catalyst material; dripping 8 mu L of dispersion liquid onto a glassy carbon electrode, and performing a ring disk electrode test after the glassy carbon electrode is slowly dried; taking a glassy carbon electrode loaded with a catalyst as a working electrode, a saturated AgCl electrode as a reference electrode, a carbon rod as a counter electrode, and 0.1mol/L KOH solution as an electrolyte; subjecting the electrolyte solution to O treatment for 30min₂Aerating to make solution reach O₂Performing electrochemical cyclic voltammetry at room temperature under a saturation condition; the disk electrode potential was set to 0.6(V, RHE), the ring electrode potential was 1.23(V, RHE), and the rotational speed was 1600 revolutions/min. The results of the measurements are shown in fig. 8, from which it can be seen that, in a stability test up to 20000s, the magnitudes of the ring current and the disc current hardly change,this indicates that H-TiO₂Has excellent stability as a cathode electro-catalytic material.

For the H-TiO prepared in example 1₂And non-hydrogen-doped TiO₂H actually synthesized by material as cathode in a double-chamber reactor₂O₂The change in concentration was detected: dispersing 8mg of catalyst into 1mL of ethanol, adding 20 mu L of Nafion binder, performing ultrasonic treatment for 30min, uniformly dropwise adding the dispersion liquid on 2X 2cm carbon paper, naturally drying the dispersion liquid to serve as a working electrode, taking a saturated AgCl electrode as a reference electrode, taking a platinum wire as a counter electrode, and taking 0.1mol/L KOH solution as electrolyte; subjecting the electrolyte solution to O treatment for 30min₂Aerating to make solution reach oxygen saturation condition, then making electrocatalytic oxygen reduction synthesis of H at room temp₂O₂Detecting the actual yield; setting the electrocatalytic cathode potential to-0.2 (V, RHE), and detecting H within 20H₂O₂The actual resulting amount of change. The detection result is shown in FIG. 9, and it can be seen that H is generated during the reaction period of 20H₂O₂The concentration is a continuously increasing process, the last H-TiO₂The high H of the electrocatalyst which can reach 77mmol/L₂O₂Concentration, indicating H-TiO₂Can be used for the actual electrocatalytic synthesis of H₂O₂And (6) carrying out the process.

As can be seen from the above examples, the hydrogen-doped H-TiO prepared by the invention exposes the high-energy {001} crystal face₂The Ti source reserves needed by the electrocatalyst are rich and environment-friendly, and are common chemical raw materials, and the price is far lower than that of a noble metal catalyst; preparation of H-TiO₂The electrocatalyst has high yield, pure crystal phase, stable structure, uniform distribution of the layered porous nanosheets, large specific surface area and many catalytic sites; preparation of electric H-TiO₂The catalyst has excellent electrochemical activity and high selectivity, and can be used for preparing H by efficient electrocatalytic oxygen reduction₂O₂The method has great significance for practical application; preparation of electric H-TiO₂The catalyst has good stability, can maintain high electrocatalytic activity for a long time, and is beneficial to electrocatalytic synthesis of H₂O₂The practical application of (1).

While only the preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.