TiO2 / NiSe-coated ReS < 2 + x > photocatalytic material with high hydrogen evolution activity and preparation method of TiO2 / NiSe-coated ReS < 2 + x > photocatalytic material

Abstract

The invention belongs to the technical field of photocatalytic hydrogen production, and particularly relates to a TiO2 / NiSe-coated ReS2 + x photocatalytic material with high hydrogen evolution activity and a preparation method thereof. According to the method, nickel selenide (NiSe) is firstly modified on the surface of TiO2, then rhenium sulfide (ReS2 + x) is directionally photodeposited on the surface of NiSe, the NiSe and ReS2 + x cocatalyst which has a core-shell structure and is uniformly dispersed is obtained, and the hydrogen production performance of the TiO2 photocatalyst is greatly enhanced.

Description

Technical Field

[0001] The present invention belongs to the technical field of photocatalytic hydrogen production, and particularly relates to a TiO2 / NiSe@ReS photocatalytic material with high hydrogen evolution activity and a preparation method thereof. 2+x Background Art

[0002] Developing clean and low-carbon new energy is the only way to achieve future sustainable development. In recent years, hydrogen energy, as a renewable new energy, has the advantages of rich sources and high calorific value. As a low-cost and green hydrogen production method, solar photocatalytic hydrogen production technology has great development potential. As an important photocatalytic material, TiO2 shows broad application prospects in the field of photocatalytic hydrogen production. However, the photo-generated electrons and holes of a single TiO2 photocatalyst are easily recombined quickly due to Coulomb attraction, and there are few catalytic active sites on its surface, resulting in low photocatalytic hydrogen production performance. Therefore, it is necessary to explore and develop simple and efficient modification methods to significantly improve the hydrogen production performance of TiO2 photocatalytic materials.

[0003] As an effective modification strategy, promoter modification can not only quickly capture photo-generated charges, inhibit the recombination of electron-hole pairs, but also provide a large number of catalytic active sites, effectively reduce the energy barrier for hydrogen formation, and accelerate the catalytic reaction kinetics. Therefore, promoter modification can significantly improve the hydrogen production performance of photocatalysts. At present, researchers have explored a variety of promoters (including metals, chalcogenides, carbides, phosphides, etc.) and can effectively improve the hydrogen production performance of different photocatalytic materials. However, traditional promoters often show an unsatisfactory intrinsic microstructure environment, such as uneven distribution of active sites and mainly concentrated at rare edges, and the microstructure properties of active sites do not match the electron environment required for the hydrogen evolution reaction, resulting in limited improvement in photocatalytic hydrogen production performance. Therefore, developing effective promoter modification and its synthesis method to optimize its microstructure is of great significance for the development of highly active photocatalytic hydrogen evolution promoters.

[0004] ​Among various additives, sulfide additives have attracted extensive attention from researchers due to their diverse types, adjustable elemental composition, excellent catalytic performance, etc. Although sulfide additives have great development potential, their enhancing effect on photocatalytic hydrogen production performance is still limited. The reasons lie in the following two key scientific problems of sulfide additives. One is the small number of active sites of sulfides: mainly because the active unsaturated sulfur atoms are usually located at fewer edges, and a high proportion of saturated sulfur atoms in the bulk or basal plane are inactive. In addition, traditional preparation methods usually involve high-temperature and high-pressure conditions (such as hydrothermal method, chemical vapor deposition method, high-temperature reduction method, etc.), resulting in larger particle sizes or easy aggregation of sulfides, further restricting the exposure of active sulfur sites. The other is the low catalytic efficiency of a single active sulfur atom of sulfide additives: the main reason is the inappropriate electronic structure of the active sulfur atoms, which leads to strong adsorption of hydrogen atoms, is not conducive to the desorption of hydrogen, and thus reduces the photocatalytic hydrogen evolution efficiency. Therefore, if a simple and efficient preparation method of sulfide additives can be developed to simultaneously increase the number of active sulfur sites and improve the catalytic hydrogen evolution efficiency of a single sulfur atom, it is expected to achieve excellent photocatalytic hydrogen production performance, but this still has great challenges. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to propose a simple preparation method of a highly hydrogen-evolving active TiO2 / NiSe@ReS 2+x photocatalyst in view of the above-mentioned prior art. This method first modifies NiSe on the surface of TiO2, and then directionally photo-deposits amorphous rhenium sulfide ReS on the surface of NiSe 2+x , obtaining a NiSe@ReS 2+x cocatalyst with a core-shell structure and uniform dispersion, which greatly enhances the hydrogen production performance of the TiO2 photocatalyst.

[0006] A preparation method of a highly hydrogen-evolving active TiO2 / NiSe@ReS 2+x photocatalytic material, comprising the following steps:

[0007] S1. Under continuous stirring conditions, add TiO2 solid powder into an ethanol aqueous solution. After stirring evenly, add nickel nitrate solution and selenourea solution to obtain a uniform reaction solution;

[0008] S2. Remove the residual oxygen in the reaction solution, and then carry out a photo-deposition reaction. After the reaction is completed, centrifuge, wash and dry the product to obtain a solid TiO2 / NiSe photocatalyst;

[0009] S3. Disperse the TiO2 / NiSe photocatalyst in 80 mL of an ethanol aqueous solution to obtain a reaction system. Mix a 0.10 mol / L sodium perrhenate solution and a dibenzyl disulfide solution to form a complex solution of sodium perrhenate - dibenzyl disulfide. Subsequently, under stirring and an atmosphere condition, add the above complex solution to the reaction system solution, and then carry out a directional photodeposition reaction to obtain TiO2 / NiSe@ReS 2+x photocatalyst, where x = 1 - 1.7.

[0010] Furthermore, in S1, the dosage of the TiO2 solid powder is 0.05 g, the dosage of the ethanol aqueous solution is 80 mL; the dosage of the nickel nitrate solution is 258 μL, and the dosage of the selenourea solution is 258 μL.

[0011] Furthermore, in S1, in the ethanol aqueous solution, by volume ratio, ethanol:water = 1:3, and the concentrations of both the nickel nitrate solution and the selenourea solution are 0.10 mol / L.

[0012] Furthermore, in S2, the conditions for photodeposition are: carried out under irradiation with 365 nm ultraviolet light, and the time condition is 2 h.

[0013] Furthermore, in S3, the dosage of the TiO2 / NiSe photocatalyst is 0.05 g, the concentration of the sodium perrhenate solution is 0.10 mol / L, and the concentration of the dibenzyl disulfide solution is 0.01 mol / L.

[0014] Furthermore, in S3, the volume of the added sodium perrhenate solution is 2.70 - 27.00 μL.

[0015] Furthermore, in S3, the volume of the added dibenzyl disulfide solution is 135 - 1350 μL.

[0016] Furthermore, in S3, the time for the directional photodeposition reaction is 30 - 210 min.

[0017] The TiO2 / NiSe@ReS 2+x photocatalytic material obtained by the above preparation method.

[0018] The above TiO2 / NiSe@ReS 2+x Application of the photocatalytic material in the field of hydrogen production photocatalysts.

[0019] The beneficial effects of the present invention are as follows:

[0020] The present invention proposes a simple two - step photodeposition method for preparing TiO2 / NiSe@ReS with high hydrogen evolution activity 2+xPhotocatalytic material. First, NiSe nanoparticles are loaded on the surface of TiO2 by photodeposition, and then through a further directional photodeposition process, amorphous ReS is selectively modified on the surface of NiSe 2+x , thereby modifying a NiSe@ReS cocatalyst with a uniform dispersion and a core-shell structure on the surface of the TiO2 photocatalyst, and finally realizing the preparation of a TiO2 / NiSe@ReS 2+x photocatalytic material with high hydrogen evolution activity. The TiO2 / NiSe@ReS 2+x photocatalytic material prepared by this method shows higher photocatalytic hydrogen evolution performance compared with the TiO2 / ReS 2+x or TiO2 / NiSe materials loaded with ReS 2+x or NiSe alone. This synthesis method has the advantages of environmental friendliness, simplicity of operation, mild reaction conditions, and low equipment requirements, and is expected to generate good social and economic benefits. 2+x BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The present invention will be further described below with reference to the accompanying drawings.

[0022] Figure 1 is the preparation route of the TiO2 / NiSe@ReS 2+x photocatalytic material with high hydrogen evolution activity in Example 1;

[0023] Figure 2 is the TEM and EDS-Mapping diagrams of the TiO2 / NiSe@ReS 2+x photocatalytic material with high hydrogen evolution activity in Example 1;

[0024] Figure 3 is the XRD pattern of TiO2, TiO2 / ReS 2+x , TiO2 / NiSe@ReS 2+x and TiO2 / NiSe in Example 1;

[0025] Figure 4 is the Raman spectrum of TiO2, TiO2 / ReS 2+x , TiO2 / NiSe@ReS 2+x and TiO2 / NiSe in Example 1;

[0026] Figure 5 is the UV-Vis diffuse reflectance absorption spectrum of TiO2, TiO2 / ReS 2+x , TiO2 / NiSe@ReS 2+x and TiO2 / NiSe in Example 1;

[0027] Figure 6 is TiO2, TiO2 / ReS in Example 1​2+x , XPS spectra of TiO2 / NiSe@ReS 2+x and TiO2 / NiSe;

[0028] Figure 7 For TiO2, TiO2 / ReS in Example 1 2+x , TiO2 / NiSe@ReS 2+x and hydrogen production performance of TiO2 / NiSe photocatalysts;

[0029] Figure 8 For TiO2 / NiSe@ReS in Example 1 2+x Photocatalytic hydrogen production performance of photocatalytic materials in photocatalytic cycles. Specific implementation manners

[0030] In order to make the technical means, creative features, achieved purposes and effects of the present invention easy to understand, the present invention will be further described below in conjunction with specific implementation manners.

[0031] In the present invention, X-ray diffraction (XRD) spectroscopy is used to analyze the crystal structure and phase composition information of materials;

[0032] Transmission electron microscopy (TEM) is used to observe the morphology and structure of materials;

[0033] Raman spectroscopy is used to analyze the structure and composition information of materials;

[0034] X-ray photoelectron spectroscopy (XPS) is used to detect the chemical element composition and valence states on the surface of materials;

[0035] UV-vis diffuse reflection is used to test the optical properties of materials.

[0036] The first thing to be protected by the present invention is a preparation method of a TiO2 / NiSe@ReS photocatalytic material with high hydrogen evolution activity, including the following steps: 2+x 1) Prepare a nickel nitrate solution with a concentration of 0.1 mol / L, a selenourea solution with a concentration of 0.1 mol / L, a sodium perrhenate solution with a concentration of 0.1 mol / L, and a dibenzyl disulfide solution with a concentration of 0.01 mol / L respectively;

[0037] 2) Under strong stirring, add 0.05 g of TiO2 solid powder to 80 mL of an ethanol aqueous solution (volume ratio of ethanol / aqueous solution is 1:3) to form a uniformly dispersed suspension, and then add 258 μL of nickel nitrate solution and 258 μL of selenourea solution thereto; the stirring speed is 500 r / min and the stirring time is 20 min.

[0038] 2) Under strong stirring, add 0.05 g of TiO2 solid powder to 80 mL of an ethanol aqueous solution (volume ratio of ethanol / aqueous solution is 1:3) to form a uniformly dispersed suspension, and then add 258 μL of nickel nitrate solution and 258 μL of selenourea solution thereto; the stirring speed is 500 r / min and the stirring time is 20 min.

[0039] 3) The suspension obtained in step 2) is passed through high-purity N2 to remove O2 in the air, and then photo-deposited under visible light irradiation at 365 nm for 2 hours. The obtained product is centrifuged, washed, and dried to obtain the TiO2 / NiSe photocatalyst.

[0040] 4) The TiO2 / NiSe photocatalyst obtained in step 3) is dispersed in an ethanol aqueous solution. Under continuous stirring and N2 atmosphere, 0.1 mol / L sodium perrhenate solution and 0.01 mol / L dibenzyl disulfide solution in step 1) are taken. After mixing, a homogeneous sodium perrhenate-dibenzyl disulfide complex solution is formed, and then added to the above reaction system. During the directional photo-deposition process, NiSe rapidly captures the photo-generated electrons generated by TiO2, and induces the directional photo-deposition of amorphous ReS on the surface of NiSe nanoparticles. 2+x to obtain the TiO2 / NiSe@ReS 2+x photocatalyst, where x = 1 to 1.7.

[0041] In this step, the directional photo-deposition reaction time is 60 - 180 min. The added volume of the sodium perrhenate solution is 2.70 - 27.00 μL, and the added volume of the dibenzyl disulfide solution is 135.00 - 1350.00 μL. Preferably, the added volume of the sodium perrhenate solution is 8.10 - 19.60 μL, and preferably, the added volume of the dibenzyl disulfide solution is 405.00 - 980.00 μL.

[0042] The present invention proposes a simple preparation method of a TiO2 / NiSe@ReS 2+x photocatalytic material with high hydrogen evolution activity. First, NiSe nanoparticles are uniformly modified on the surface of the TiO2 photocatalytic material by the photo-deposition method to obtain TiO2 / NiSe. The sodium perrhenate-dibenzyl disulfide complex can simultaneously provide a certain amount of rhenium source and a large amount of sulfur source. When TiO2 / NiSe is dispersed in the above solution and irradiated, the NiSe nanoparticles can rapidly capture the photo-generated electrons of TiO2, and induce the release of rhenium ions and sulfur ions from the sodium perrhenate-dibenzyl disulfide, and directionally deposit amorphous ReS on the NiSe nanoparticles. 2+x Since the formation of ReS 2+x is induced by the NiSe nanoparticles capturing the photo-generated electrons of TiO2, finally a core-shell NiSe@ReS 2+x co-catalyst is obtained on TiO2. It should be noted that in the present invention, ReS 2+x refers to an amorphous rhenium disulfide product.

[0043] The second thing the present invention wants to protect is the TiO2 / NiSe@ReS 2+xPhotocatalytic material, the photocatalytic material is based on TiO2, NiSe nanoparticles are loaded on the surface of TiO2, and then through a further directional photodeposition process, amorphous ReS is selectively modified on the surface of NiSe 2+x , thereby modifying NiSe@ReS with a uniform dispersion and a core-shell structure on the surface of the TiO2 photocatalyst 2+x co-catalyst, and finally obtaining a high hydrogen evolution activity TiO2 / NiSe@ReS 2+x photocatalytic material.

[0044] The third aspect of the present invention to be protected is the application of TiO2 / NiSe@ReS 2+x photocatalytic material in the field of hydrogen production. Specifically, the photocatalytic hydrogen production performance of the TiO2 / NiSe@ReS 2+x photocatalytic material with high hydrogen evolution activity is evaluated by the amount of hydrogen gas evolved from the decomposition of water under ultraviolet light. The detailed experimental process is as follows: Disperse the TiO2 / NiSe@ReS 2+x photocatalyst (0.05 g) synthesized by the method of the present invention into a flat-bottomed three-necked flask containing 80 mL of ethanol sacrificial agent (the volume ratio of ethanol / water solution is 1:3). Then, nitrogen is introduced for 15 minutes to remove the oxygen in the reaction system. Finally, the photocatalytic hydrogen production reaction is carried out under stirring and illumination. In the above photocatalytic hydrogen production experiment, 4 LED lights (3 W, 365 nm) are used as the irradiation source. Every 1 hour, 400 μL of gas is extracted with a micro gas sampler and injected into a gas chromatograph (Shimadzu, GC-14C, Japan) for the detection of hydrogen content.

[0045] <Comparative Example 1>

[0046] A preparation method of a TiO2 / ReS 2+x photocatalyst mainly includes the following steps:

[0047] Disperse 0.05 g of TiO2 in 80 mL of ethanol aqueous solution (the volume ratio of ethanol / water solution is 1:3) to form a uniform suspension. Then, under the protection of N2 atmosphere, 14 μL of sodium perrhenate solution (0.10 mol / L) and 700 μL of dibenzyl disulfide solution (0.01 mol / L) are mixed evenly and dropped into the above reaction solution. After the above reaction solution is directionally photodeposited for 120 min, the reaction product is centrifuged, washed, and dried in sequence to obtain TiO2 / ReS 2+x comparative sample. It should be noted that according to the detection results of the inductively coupled plasma emission spectrometer, the actual atomic ratio of Re to S in TiO2 / ReS 2+x is 1:3.40, that is, x = 1.40.

[0048] <Example 1>

[0049] Preparation method of a TiO2 / NiSe@ReS photocatalytic material with high hydrogen evolution activity, comprising the following steps: 2+x (1) Disperse 0.05 g of TiO2 solid powder in 80 mL of an ethanol aqueous solution (volume ratio of ethanol / aqueous solution is 1:3) to form a uniform suspension;

[0050] (2) Under stirring, add 258 μL of nickel nitrate solution (0.1 mol / L) and 258 μL of selenourea solution (0.1 mol / L) to the above suspension system. After purging with nitrogen for 15 min, irradiate with ultraviolet light at 365 nm for 2 h to uniformly photodeposit NiSe nanoparticles on the surface of TiO2, obtaining a TiO2 / NiSe product;

[0051] (3) Uniformly disperse the obtained TiO2 / NiSe product (0.05 g) in an ethanol aqueous solution (80 mL). Subsequently, under the protection of a N2 atmosphere, mix 14 μL of sodium perrhenate solution (0.10 mol / L) and 700 μL of dibenzyl disulfide solution (0.01 mol / L) evenly and then drop them into the above reaction solution. After the above reaction solution is directionally photodeposited for 120 min, centrifuge, wash, and dry the reaction product in sequence to finally obtain the TiO2 / NiSe@ReS

[0052] photocatalytic material. It should be noted that according to the detection results of an inductively coupled plasma optical emission spectrometer, the atomic ratio of Re to S in TiO2 / NiSe@ReS 2+x is 1:3.69, that is, x = 1.69. 2+x

[0053] Figure 1 is the preparation process schematic diagram of the TiO2 / NiSe@ReS 2+x photocatalytic material in this example.

[0054] Figure 2 is the TEM image and corresponding EDS-Mapping image of the TiO2 / NiSe@ReS 2+x photocatalytic material in this example. As can be clearly seen in Figure 2 a, the main TiO2 photocatalytic material has an irregular nanoparticle morphology, and there are many small particles with darker colors and uniform distribution on its surface. These small particles can be attributed to NiSe@ReS 2+x nanoparticles. After further magnifying these small particles, Figure 2 b and 2c show that the NiSe@ReS 2+x nanoparticles have an obvious core-shell structure, with a size of 25 - 30 nm, and the outer ReS 2+x is an amorphous structure. The above NiSe@ReS​2+x The structure of the nanoparticles can be further demonstrated by Figure 2 d-f. It can be seen from the figure that the distribution ranges of the elemental signals of Re and S are significantly larger than those of Ni and Se, indicating that ReS 2+x is wrapped on the outer layer of NiSe, effectively proving the core-shell structure of NiSe@ReS 2+x .

[0055] Figure 3 XRD patterns of TiO2, TiO2 / ReS 2+x (from Comparative Example 1), TiO2 / NiSe@ReS 2+x and TiO2 / NiSe (from step (2)) in this example are shown. Obviously, the TiO2 sample exhibits typical anatase diffraction peaks. The TiO2 samples modified with all additives show anatase diffraction peaks of the same intensity at the same positions, proving that the process of loading the core-shell NiSe@ReS 2+x additives by this method is relatively mild and does not change the intrinsic crystal structure of TiO2. In addition, since NiSe and ReS 2+x are amorphous, they cannot be analyzed by XRD.

[0056] Figure 4 Raman spectra of (1) TiO2, (2) TiO2 / ReS 2+x , (3) TiO2 / NiSe@ReS 2+x and (4) TiO2 / NiSe in this example are shown. It can be found that characteristic peaks of TiO2 appear at 398, 521 and 635 cm -1 . In addition, two additional signal peaks appear near 230 and 300 cm -1 , which are attributed to the characteristic peaks of NiSe and ReS 2+x respectively. It shows that the co-catalyst NiSe@ReS can be effectively photo-deposited on the surface of TiO2 by this method. 2+x

[0057] Figure 5 UV-Vis diffuse reflectance absorption spectra of TiO2, TiO2 / ReS 2+x , TiO2 / NiSe@ReS 2+x and TiO2 / NiSe photocatalytic materials in this example are shown. Compared with pure TiO2, TiO2 / ReS 2+x , TiO2 / NiSe@ReS 2+x and TiO2 / NiSe samples all show enhanced light absorption in the visible light region.

[0058] Figure 6 XRD patterns of TiO2, TiO2 / ReS2+x , the high-resolution XPS spectra of S2p (a), Ni2p (b), and Se 3d (d) of TiO2 / NiSe@ReS 2+x and TiO2 / NiSe. It can be seen from the figure that compared with TiO2 / NiSe, the Ni 2p and Se 3d peaks of TiO2 / NiSe@ReS 2+x shift 0.6 and 0.3 eV respectively towards higher binding energies. At the same time, compared with TiO2 / ReS 2+x , the S2p peak of TiO2 / NiSe@ReS 2+x shifts 0.6 eV towards lower binding energy, indicating that the free electrons of NiSe in the NiSe@ReS 2+x additive transfer to ReS 2+x . This effectively weakens the adsorption of sulfur atoms to hydrogen, thereby increasing the catalytic hydrogen evolution efficiency of sulfur sites.

[0059] Figure 7 are the photocatalytic hydrogen production performance diagrams of TiO2, TiO2 / ReS 2+x , TiO2 / NiSe@ReS 2+x and TiO2 / NiSe samples in this example. It can be seen that the photocatalytic hydrogen production performance of single TiO2 is relatively low (47 μmol h -1 g -1 ). When ReS 2+x is deposited on TiO2, the obtained TiO2 / ReS 2+x has a photocatalytic hydrogen production performance of 3250 μmol h -1 g -1 . When a core-shell additive is formed by directional photodeposition, the photocatalytic hydrogen production performance of the TiO2 / NiSe@ReS 2+x sample is significantly enhanced, reaching 7060 μmol h -1 g -1 . This activity is also significantly higher than that of the TiO2 / NiSe (3800 μmol h -1 g -1 ) sample.

[0060] Figure 8 is the cycling stability of the photocatalytic hydrogen production performance of the high hydrogen evolution activity TiO2 / NiSe@ReS 2+x photocatalytic material in this example. As can be seen from Figure 8 , after eight photocatalytic hydrogen production cycle experiments, the photocatalytic hydrogen production activity of the TiO2 / NiSe@ReS 2+x sample does not show a significant decrease, indicating that the highly active TiO2 / NiSe@ReS 2+xThe material has excellent cyclic stability in photocatalytic hydrogen production applications.

[0061] <Example 2>

[0062] The difference between this example and Example 1: In the sodium perrhenate-dibenzyl disulfide complex mixed solution, the addition amount of the sodium perrhenate solution is 2.70 μL. According to the detection results of the inductively coupled plasma emission spectrometer, the TiO2 / NiSe@ReS prepared in this example 2+x In the photocatalytic material, the atomic ratio of Re to S is 1:3.00, that is, x = 1.00.

[0063] <Example 3>

[0064] The difference between this example and Example 1: In the sodium perrhenate-dibenzyl disulfide complex mixed solution, the addition amount of the sodium perrhenate solution is 8.10 μL. According to the detection results of the inductively coupled plasma emission spectrometer, the TiO2 / NiSe@ReS prepared in this example 2+x In the photocatalytic material, the atomic ratio of Re to S is 1:3.25, that is, x = 1.25.

[0065] <Example 4>

[0066] The difference between this example and Example 1: In the sodium perrhenate-dibenzyl disulfide complex mixed solution, the addition amount of the sodium perrhenate solution is 19.60 μL. The TiO2 / NiSe@ReS prepared in this example 2+x In the photocatalytic material, the atomic ratio of Re to S is 1:3.57, that is, x = 1.57.

[0067] <Example 5>

[0068] The difference between this example and Example 1: In the sodium perrhenate-dibenzyl disulfide complex mixed solution, the addition amount of the sodium perrhenate solution is 27.00 μL. According to the detection results of the inductively coupled plasma emission spectrometer, the TiO2 / NiSe@ReS prepared in this example 2+x In the photocatalytic material, the atomic ratio of Re to S is 1:3.66, that is, x = 1.66.

[0069] For the TiO2 / NiSe@ReS prepared in Examples 2 - 5 2+x The hydrogen production performance of the photocatalytic material was tested. Combining with the test results of Example 1, it was found that when the addition amounts of the sodium perrhenate solution were 2.70, 8.10, 14.00, 19.60, and 27.00 μL respectively, the hydrogen production performance of the TiO2 / NiSe@ReS 2+x photocatalyst was 4957, 6328, 7060, 5600, and 4811 μmol h -1 g-1 。As can be seen from the results, regardless of the addition amount of sodium perrhenate solution, the hydrogen production activity of the TiO2 / NiSe@ReS 2+x photocatalyst is always higher than that of TiO2 / ReS 2+x and TiO2 / NiSe, and its performance shows a trend of first increasing and then decreasing with the increase of the addition amount of sodium perrhenate solution. Therefore, in the preparation process of the TiO2 / NiSe@ReS 2+x photocatalyst, the optimal addition amount of sodium perrhenate solution is 8.10 - 19.60 μL.

[0070] <Example 6>

[0071] The difference between this example and Example 1: In step 3), the time for purging nitrogen is 5 min. It should be noted that according to the detection results of the inductively coupled plasma emission spectrometer, in the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in this example, the atomic ratio of Re to S is 1:3.54, that is, x = 1.54.

[0072] <Example 7>

[0073] The difference between this example and Example 1: In step 3), the time for purging nitrogen is 10 min. It should be noted that according to the detection results of the inductively coupled plasma emission spectrometer, in the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in this example, the atomic ratio of Re to S is 1:3.65, that is, x = 1.65.

[0074] <Example 8>

[0075] The difference between this example and Example 1: In step 3), the time for purging nitrogen is 30 min. It should be noted that according to the detection results of the inductively coupled plasma emission spectrometer, the atomic ratio of Re to S in TiO2 / NiSe@ReS 2+x is 1:3.69, that is, x = 1.69.

[0076] <Example 9>

[0077] The difference between this example and Example 1: In step 3), the time for purging nitrogen is 60 min. It should be noted that according to the detection results of the inductively coupled plasma emission spectrometer, in the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in this example, the atomic ratio of Re to S is 1:3.64, that is, x = 1.64.

[0078] For the TiO2 / NiSe@ReS prepared in Examples 6 - 9 2+xThe hydrogen production performance of the photocatalytic material was tested. Combining with the test results of Example 1, it was found that when the nitrogen purging time was 5, 10, 15, 30, and 60 min, the hydrogen production performance of TiO2 / NiSe@ReS 2+x photocatalyst was 5574, 6528, 7060, 7025, and 7091 μmol h -1 g -1 . It can be seen from this that when the nitrogen purging time was 5 or 10 min, the hydrogen evolution performance of TiO2 / NiSe@ReS 2+x was relatively low, which was mainly due to the fact that there was still some oxygen remaining in the reaction solution; while when the nitrogen purging time was 15 - 60 min, the hydrogen evolution activity of the TiO2 / NiSe@ReS 2+x photocatalyst reached the best and tended to be stable. Therefore, during the preparation process of the TiO2 / NiSe@ReS 2+x photocatalyst, the optimal nitrogen purging time was 15 - 30 min.

[0079] <Example 10>

[0080] The difference between this example and Example 1: In the sodium perrhenate - dibenzyl disulfide complex mixed solution, the addition amount of the dibenzyl disulfide solution was 135.00 μL. It should be noted that according to the detection results of the inductively coupled plasma emission spectrometer, in the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in this example, the atomic ratio of Re to S was 1:3.12, that is, x = 1.12.

[0081] <Example 11>

[0082] The difference between this example and Example 1: In the sodium perrhenate - dibenzyl disulfide complex mixed solution, the addition amount of the dibenzyl disulfide solution was 405.00 μL. It should be noted that according to the detection results of the inductively coupled plasma emission spectrometer, in the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in this example, the atomic ratio of Re to S was 1:3.68, that is, x = 1.68.

[0083] <Example 12>

[0084] The difference between this example and Example 1: In the sodium perrhenate - dibenzyl disulfide complex mixed solution, the addition amount of the dibenzyl disulfide solution was 980.00 μL. It should be noted that according to the detection results of the inductively coupled plasma emission spectrometer, in the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in this example, the atomic ratio of Re to S was 1:3.66, that is, x = 1.66.

[0085] <Example 13>

[0086] Difference between this example and Example 1: In the mixed solution of sodium perrhenate - dibenzyl disulfide complex, the addition amount of dibenzyl disulfide solution is 1350.00 μL. It should be noted that according to the test results of inductively coupled plasma emission spectrometer, in the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in this example, the atomic ratio of Re to S is 1:3.70, that is, x = 1.70.

[0087] The hydrogen production performance of the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in Examples 10 - 13 was tested. Combining with the test results of Example 1, it was found that when the addition amounts of dibenzyl disulfide solution were 135.00, 405.00, 700.00, 980.00 and 1350.00 μL, the hydrogen production performances of the obtained TiO2 / NiSe@ReS 2+x photocatalysts were 6169, 6898, 7060, 7032 and 7014 μmol h -1 g -1 respectively. It can be seen from the results that when the addition amount of dibenzyl disulfide solution gradually increases, the photocatalytic hydrogen evolution performance of TiO2 / NiSe@ReS 2+x also gradually increases and tends to be stable. Therefore, in the preparation process of TiO2 / NiSe@ReS 2+x photocatalyst, the optimal addition amount of dibenzyl disulfide solution is 405.00 - 980.00 μL.

[0088] <Example 14>

[0089] Difference between this example and Example 1: In step 3), the time of the directional photodeposition reaction is 30 min. It should be noted that according to the test results of inductively coupled plasma emission spectrometer, in the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in this example, the atomic ratio of Re to S is 1:3.32, that is, x = 1.32.

[0090] <Example 15>

[0091] Difference between this example and Example 1: In step 3), the time of the directional photodeposition reaction is 60 min. It should be noted that according to the test results of inductively coupled plasma emission spectrometer, in the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in this example, the atomic ratio of Re to S is 1:3.53, that is, x = 1.53.

[0092] <Example 16>

[0093] Differences between this embodiment and Embodiment 1: In step 3), the time of the directional photodeposition reaction is 180 min. It should be noted that according to the detection results of the inductively coupled plasma emission spectrometer, in the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in this embodiment, the atomic ratio of Re to S is 1:3.65, that is, x = 1.65.

[0094] <Example 17>

[0095] Differences between this embodiment and Embodiment 1: In step 3), the time of the directional photodeposition reaction is 210 min. It should be noted that according to the detection results of the inductively coupled plasma emission spectrometer, in the TiO2 / NiSe@ReS 2+x photocatalytic material prepared in this embodiment, the atomic ratio of Re to S is 1:3.68, that is, x = 1.68.

[0096] The hydrogen production performance of the TiO2 / NiSe@ReS 2+x photocatalytic materials prepared in Examples 14 - 17 was tested. Combining with the test results of Example 1, it was found that when the directional photodeposition times were 30, 60, 120, 180, and 210 min respectively, the hydrogen production performances of the obtained TiO2 / NiSe@ReS 2+x photocatalysts were 5358, 6829, 7060, 7030, and 7026 μmol h -1 g -1 respectively. It can be seen from the results that when the directional photodeposition reaction time is 30 - 60 min, due to the incomplete reaction, the test results of its hydrogen production performance are relatively low. When the reaction time is extended to 120 - 210 min, the hydrogen production performance of TiO2 / NiSe@ReS 2+x reaches the best and tends to be stable. Therefore, in the preparation process of the TiO2 / NiSe@ReS 2+x photocatalyst, the optimal directional photodeposition time is 60 - 180 min.

[0097] The above shows and describes the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. What is described in the above embodiments and the specification only illustrates the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed. The scope of the present invention claimed is defined by the appended claims and their equivalents.

Claims

1. Preparation method of a TiO2 / NiSe@ReS photocatalytic material with high hydrogen evolution activity, characterized in that, 2+x It includes the following steps: S1. Under continuous stirring conditions, add TiO2 solid powder into the ethanol aqueous solution. After stirring evenly, add nickel nitrate solution and selenourea solution to obtain a uniform reaction solution; S2. Remove the residual oxygen in the reaction solution, and then carry out a photodeposition reaction. After the reaction is completed, centrifuge, wash and dry the product to obtain a solid TiO2 / NiSe photocatalyst; S3. Disperse the TiO2 / NiSe photocatalyst in 80 mL of an ethanol aqueous solution to obtain a reaction system. Mix the sodium perrhenate solution and the dibenzyl disulfide solution to form a complex solution of sodium perrhenate - dibenzyl disulfide. Subsequently, under stirring and atmosphere conditions, add the above complex solution to the reaction system solution, and then carry out a directional photodeposition reaction to obtain TiO2 / NiSe@ReS 2+x photocatalyst, where x = 1 to 1.

7.

2. The preparation method of the TiO2 / NiSe@ReS photocatalytic material with high hydrogen evolution activity according to claim 1, characterized in that, 2+x In S1, the dosage of TiO2 solid powder is 0.05 g, and the dosage of the ethanol aqueous solution is 80 mL; the dosage of nickel nitrate solution is 258 μL, and the dosage of selenourea solution is 258 μL. ​ 3. The preparation method of the TiO2 / NiSe@ReS photocatalytic material with high hydrogen evolution activity according to claim 2, characterized in that 2+x In S1, in the ethanol aqueous solution, by volume ratio, ethanol: water = 1:3, and the concentrations of both nickel nitrate solution and selenourea solution are 0.10 mol / L.

4. The preparation method of the TiO2 / NiSe@ReS photocatalytic material with high hydrogen evolution activity according to claim 1, characterized in that, 2+x In S2, the conditions for photodeposition are: carried out under irradiation of 365 nm ultraviolet light, and the time condition is 2 h. ​ 5. The preparation method of the TiO2 / NiSe@ReS photocatalytic material with high hydrogen evolution activity according to claim 1, characterized in that, 2+x In S3, the dosage of TiO2 / NiSe photocatalyst is 0.05 g, the concentration of sodium perrhenate solution is 0.10 mol / L, and the concentration of dibenzyl disulfide solution is 0.01 mol / L.

6. The preparation method of the TiO2 / NiSe@ReS photocatalytic material with high hydrogen evolution activity according to claim 5, characterized in that 2+x In S3, the volume of the added sodium perrhenate solution is 2.70 - 27.00 μL.

7. The preparation method of the TiO2 / NiSe@ReS photocatalytic material with high hydrogen evolution activity according to claim 5, characterized in that, 2+x In S3, the volume of the added dibenzyl disulfide solution is 135 - 1350 μL. ​ 8. The preparation method of the TiO2 / NiSe@ReS photocatalytic material with high hydrogen evolution activity according to claim 1, characterized in that 2+x In S3, the time for the directional photodeposition reaction is 30 - 210 min.

9. The TiO2 / NiSe@ReS photocatalytic material obtained by the preparation method according to any one of claims 1-8 2+x ​ 10. Application of the TiO2 / NiSe@ReS 2+x photocatalytic material in the field of hydrogen production photocatalysts.

Images