A method for preparing a transition metal sulfide-covalent organic framework hollow double-shell structure material

Abstract

This invention discloses a method for preparing a hollow double-shell structured material composed of transition metal sulfides and covalent organic frameworks (COFs). The method includes the following steps: adding a hollow transition metal sulfide, a COF precursor, a first organic solvent, and an aqueous solution of an inorganic acid to a Schlenk tube; ultrasonically treating the resulting mixture for 10-60 minutes to remove air; and reacting at 100-200°C for 3-7 days; washing and vacuum drying the resulting solid powder to obtain a hollow double-shell structured material formed by the composite of transition metal sulfides and COFs. The hollow double-shell structured material obtained by this invention effectively integrates the advantages of COFs and transition metal sulfides, enhancing the visible light absorption range, accelerating the separation and migration of photogenerated carriers, and increasing the number of active sites for proton reduction, thereby improving the performance of photocatalytic reactions.

Description

Technical Field

[0001] This invention belongs to the field of new energy materials, specifically relating to the preparation of a hollow double-shell structure material of transition metal sulfide and covalent organic framework (COFs) and its application in photocatalytic reactions. Background Technology

[0002] Photocatalysis is a catalytic process that utilizes light energy to convert substances under the action of a catalyst. It has advantages such as being green, environmentally friendly, and having low energy consumption. Although various semiconductor materials are used as photocatalysts, most photocatalytic systems suffer from low photocatalytic activity due to problems such as low separation efficiency and slow migration rate of photogenerated carriers.

[0003] Covalently bonded elements (COFs) are crystalline porous materials with a network topology, assembled from organic units bound by covalent bonds. Due to their large specific surface area, tunable composition, and structural stability, they show great promise for photocatalytic reactions. However, since most COFs lack active sites in their main framework, metal-containing cocatalysts are typically required to provide catalytic active sites to achieve high photocatalytic efficiency. To achieve rapid transfer of photogenerated electrons from COFs to the active sites of the cocatalyst, designing and synthesizing COF-cocatalyst composites with strong interfacial effects and short-distance contact is essential for improving photocatalytic efficiency.

[0004] Transition metal sulfides possess advantages such as low cost, diverse valence states, and excellent catalytic performance. They exhibit good compatibility with COFs, and combining transition metal sulfides with COFs can leverage the strengths of both, promoting photocatalytic reactions and thus attracting widespread attention. Xu et al. (G.Sun, J.Zhang, B.Cheng, H.Yu, J.Yu, J.Xu, Bifunctional CdS / COF S-scheme photocatalyst for enhanced H2 evolution and organic synthesis, Chem. Eng.J. 2023.476.146818.) prepared a two-dimensional heterojunction of CdS sheets and COFs via electrostatic self-assembly. The composite material exhibited a 15.10 mmol g⁻¹ of... -1 h -1The photocatalytic activity of the composite material was enhanced while maintaining redox capabilities to increase ascorbic acid content. Xu et al. (L.Sun, L.Li, J.Yang, J.Fan, Q.Xu, Fabricating covalent organic framework / CdS S-scheme heterojunctions for improved solar hydrogen generation, Chinese J.Catal. 2022, 43, 350-358.) combined hollow CdS cubes with hollow COFs spheres to form a heterojunction composite material, achieving a photocatalytic hydrogen evolution rate of 8.67 mmol g / L. -1 h -1 It is pure CdS (4.11 mmol g) -1 h -1 The efficiency of the photocatalytic activity was 2.1 times that of COFs, achieving a significant performance improvement. Although the combination of transition metal sulfides and COFs improved the photocatalytic activity, the efficiency of directional separation and migration of photogenerated carriers could not meet the requirements of photocatalytic reactions because these composite materials could not effectively suppress the recombination of photogenerated electrons and holes. Therefore, the design and synthesis of novel photocatalytic materials is the key to efficient photocatalytic hydrogen evolution.

[0005] Currently, there are still relatively few materials involving transition metal sulfides and COFs composites applied in the field of photocatalysis. Developing transition metal sulfide-COFs composite materials with high photocatalytic activity, simple preparation, and low cost has become an urgent problem to be solved to expand their photocatalytic applications. Summary of the Invention

[0006] This invention addresses the problems existing in current photocatalytic reactions by providing a method for preparing a hollow double-shell structure material composed of transition metal sulfides and COFs, and applying it to photocatalytic reactions. The method involves uniformly coating COFs onto a transition metal sulfide, and then forming a hollow double-shell structure material of "transition metal sulfide and COF" through in-situ growth. The hollow double-shell structure material obtained by this invention effectively integrates the advantages of COFs and transition metal sulfides, enhancing the visible light absorption range, accelerating the separation and migration of photogenerated carriers, and increasing the number of active sites for proton reduction, thereby improving the performance of photocatalytic reactions.

[0007] The technical solution of this invention is as follows:

[0008] A method for preparing a transition metal sulfide-covalent organic framework hollow double-shell structure material, the method comprising the following steps:

[0009] (1) Hollow transition metal sulfide, COF precursor, first organic solvent and inorganic acid aqueous solution are added to a Schlenk tube. The resulting mixture is ultrasonically treated for 10-60 minutes to remove air, and then reacted at 100-200℃ for 3-7 days. The resulting solid powder is washed and vacuum dried to obtain a transition metal sulfide-covalent organic framework hollow double-shell structure material.

[0010] The mass ratio of transition metal sulfide to COF precursor is 1:1 to 10; 1 to 20 mL of first organic solvent is added for every 1 mmol of COF precursor; the volume ratio of inorganic acid to first organic solvent is 1:3 to 10.

[0011] (2) The hollow double-shell structure material obtained in step (1) is added to the second organic solvent and extracted by Soxhlet for 1 to 3 days. The obtained solid powder is then vacuum dried to obtain the purified transition metal sulfide-covalent organic framework hollow double-shell structure material.

[0012] In step (2), 100-300 mL of a second organic solvent is added to each gram of hollow double-shell structure material.

[0013] The COF precursors mentioned in step (1) are classified according to their functional groups, including aromatic aldehydes, aromatic amines, aromatic hydrazides, aromatic anhydrides, and aromatic nitriles. Among them, aromatic aldehydes include 2,4,6-tricarboxymethyl phloroglucinol, 2,2'-bipyridine-5,5'-dicarboxaldehyde, 1,3,6,8-tetra(4-carboxyphenyl)pyrene, etc.; aromatic amines include 1,4-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 1,3,5-tris(4-aminophenyl)benzene, etc.; aromatic hydrazides include 2,5-dimethoxyterephthalohydrazide, dihydrazide p-dibenzoate, p-aminobenzoylhydrazide, etc.; aromatic anhydrides include 1,4,5,8-naphthalenetetracarboxylic anhydride, pyromellitic dianhydride, triphenylhexacarboxylic anhydride, etc.; aromatic nitriles include 1,4-dicyanophenylene, 2,2'-([2,2'-bipyridine]-5,5'-diyl)acetonitrile, 2,4,6-trimethylbenzene-1,3,5-tricarboxitrile, etc.

[0014] The hollow transition metal sulfide mentioned in step (1) is a monometallic sulfide or a bimetallic sulfide; the monometallic sulfide is specifically Co9S8, CdS, MoS2 or WS2, etc.; the bimetallic sulfide is specifically NiCo2S4, ZnIn2S4 or CuCo2S4, etc.

[0015] The COFs precursor used in step (1) is assembled in situ on the surface of a hollow transition metal sulfide.

[0016] The first organic solvent mentioned in step (1) is any one or more of the following: mesitylene, dioxane, o-dichlorobenzene, n-butanol, N,N-dimethylformamide, toluene, and N-methylpyrrolidone; the second organic solvent mentioned in step (2) is any one of the following: acetone, tetrahydrofuran, dichloromethane, or acetonitrile.

[0017] The inorganic acid aqueous solution mentioned in step (1) is hydrochloric acid, acetic acid, and nitric acid, with a concentration of 1–10 mol / L. -1 .

[0018] The application of the hollow double-shell structure material obtained by the method in photocatalytic reaction is as follows: weigh the hollow double-shell structure material and sacrificial reagent and add them to the reaction flask, add deionized water to the above system, and irradiate with visible light for 1 to 10 hours under an inert gas or reaction atmosphere.

[0019] The mass ratio of hollow double-shell structure material to sacrificial reagent is 1:10 to 100; 1 to 20 mg of hollow double-shell structure material is added to every 10 mL of deionized water.

[0020] The sacrificial agent is any one of L-ascorbic acid, sodium ascorbate, triethylamine, triethanolamine, ethanol, lactic acid, and methanol.

[0021] The application described is any one of the following photocatalytic reactions: photocatalytic hydrogen evolution reaction, photocatalytic carbon dioxide reduction reaction, photocatalytic oxygen evolution reaction, and photocatalytic hydrogen peroxide synthesis.

[0022] The inert gas refers to nitrogen or argon, and the corresponding reaction in an inert atmosphere is photocatalytic hydrogen evolution reaction or photocatalytic oxygen evolution reaction; the reaction atmosphere is carbon dioxide, air or oxygen, and the corresponding reaction is photocatalytic carbon dioxide reduction reaction or photocatalytic hydrogen peroxide synthesis.

[0023] The essential features of this invention are:

[0024] Most hollow double-shell structures are currently made of different inorganic materials.

[0025] This invention uniformly coats COFs onto the surface of a hollow transition metal sulfide, creating a hollow double-shell structure material combining transition metal sulfide and COFs. Due to its unique structure, this hollow double-shell material allows for closer contact between the two materials, shortening the migration distance of photogenerated electrons from the COFs to the transition metal sulfide surface. It induces an internal electric field between the two materials, accelerating the separation and migration of photogenerated carriers. The large specific surface area of ​​the COFs promotes mass transfer while exposing more reactive sites in the transition metal sulfide for the reaction. The hollow shell of the transition metal sulfide provides more reactive sites for the entire reaction, while also promoting light reflection and scattering between the double shells, improving light utilization efficiency. When this structure is applied to the photocatalytic hydrogen evolution reaction, the close contact between the two materials facilitates the induction of a built-in electric field, accelerating photogenerated electron migration. The multiple light scattering and reflection in the hollow double-shell structure enhance light absorption. The synergistic effect of these factors results in significantly enhanced photocatalytic performance, superior to many existing photocatalysts, and it can serve as a substitute for noble metal catalysts.

[0026] The beneficial effects of this invention are as follows:

[0027] (1) This invention provides a method for preparing hollow double-shell structured materials by compositing transition metal sulfides with COFs. The well-defined structures of transition metal sulfides and COFs provide an ideal platform for understanding the relationship between photocatalyst structure and photocatalytic performance.

[0028] (2) The hollow double-shell structure material prepared by combining transition metal sulfides and COFs provided by this invention benefits from the hollow double-shell structure, achieving a hydrogen evolution rate as high as 23145 μmol g in the photocatalytic hydrogen evolution reaction. -1 h -1 Compared with the COF analogue alone (35 μmol g) -1 h -1 The hydrogen evolution performance of the hollow double-shell structure material was improved by 661 times.

[0029] (3) The hollow double-shell structure material prepared by combining transition metal sulfides and COFs provided by this invention has a hydrogen evolution rate that is approximately twice that of the hydrogen evolution rate of the loaded Pt counterpart (11835 μmol g). -1 h -1 Its co-catalyst can be used as a substitute for the precious metal platinum. Attached Figure Description

[0030] Figure 1 This is a schematic diagram illustrating the preparation of the hollow double-shell structure material in Embodiment 1 of the present invention.

[0031] Figure 2 The images shown are scanning electron microscope (SEM) and transmission electron microscope (TEM) images of the hollow double-shell structure material of Embodiment 1 of the present invention. Figure 2 (a) is a scanning electron microscope image of the hollow double-shell structure material. Figure 2 (b) is a transmission electron microscope image of the hollow double-shell structure material;

[0032] Figure 3 This is a graph showing the hydrogen evolution rate performance of a typical sample in the hollow double-shell structure material of Example 1 of the present invention.

[0033] Figure 4 The image shows the ultraviolet-visible diffuse reflectance spectrum of the hollow double-shell structure material in Embodiment 1 of the present invention.

[0034] Figure 5 This is the steady-state fluorescence emission spectrum of the hollow double-shell structure material in Embodiment 1 of the present invention.

[0035] Figure 6 This is the electrochemical impedance spectroscopy of the hollow double-shell structure material of Example 1 of the present invention. Detailed Implementation

[0036] To further illustrate the method of the present invention, specific embodiments are described below with reference to the accompanying drawings. The following embodiments are merely specific preparation methods of the present invention and do not limit the scope of the invention.

[0037] The hollow transition metal sulfides involved in this invention are all materials known in the art. For example, hollow Co9S8 was prepared by a one-step solvothermal reaction method. Cobalt sulfate heptahydrate (78.7 mg, 2.80 mmol) and thiourea (63.9 mg, 8.40 mmol) were dissolved in ethylene glycol (15 mL) and N,N-dimethylformamide (60 mL). After stirring at room temperature for 30 min, the mixture was transferred to a 100 mL reaction vessel and heated at 160 °C for 12 h. After cooling to room temperature, the mixture was washed with deionized water and ethanol. Hollow Co9S8 was obtained after vacuum drying at 60 °C for 6 h. (X. Feng, Q. Jiao, T. Liu, Q. Li, M. Yin, Y. Zhao, H. Li, C. Feng, W. Zhou, Facilitated Synthesis of Co9S8 Hollow Spheres as a High-Performance Electrocatalyst for the Oxygen Evolution Reaction, ACS Sustain. Chem. Eng. 2017, 6, 1863-1871.). Other methods for preparing hollow materials are similar, but not limited to these.

[0038] Example 1

[0039] Hollow Co9S8 (24 mg, 0.03 mmol), 2,4,6-tricarboxymethyl phloroglucinol (31.5 mg, 0.15 mmol), 2,5-dichloro-1,4-phenylenediamine (39.8 mg, 0.225 mmol), mesitylene (0.75 mL), dioxane (0.75 mL), and acetic acid aqueous solution (0.25 mL, 6 M) were added to a Schlenk tube. The resulting mixture was sonicated for 30 minutes, and then the air in the tube was removed by three cycles of "freezing-vacuuming-thawing" with liquid nitrogen. The Schlenk tube was sealed and heated at 120 °C for 3 days. The resulting solid powder was washed multiple times with N, N-dimethylacetamide, and acetone, respectively. The collected powder was dried under vacuum at 140 °C for 12 h to obtain a hollow double-shell structure material composed of transition metal sulfides and imine COFs.

[0040] The freezing temperature is -196℃, the vacuum pressure is -0.1MPa, the thawing temperature is 25℃, and the freezing, vacuuming, and thawing times are all two minutes.

[0041] 1 g of hollow double-shell structured material was added to acetone (100 mL), and after Soxhlet extraction for 2 days, the obtained solid powder was vacuum dried to obtain a purified hollow double-shell structured material composed of transition metal sulfides and imine COFs.

[0042] Figure 1 The diagram below illustrates the preparation of the hollow double-shell structure material in Example 1 of this invention. Visible light-responsive COFs, such as the COF obtained by the condensation reaction of 2,4,6-tricarboxymethyl phloroglucinol and 2,5-dichloro-1,4-phenylenediamine (TP-CPA-COF), are uniformly coated onto the surface of a hollow Co9S8 cocatalyst to obtain the hollow double-shell structure material.

[0043] Figure 2 The image shows a scanning electron microscope (SEM) image (2a) and a transmission electron microscope (TEM) image (2b) of the hollow double-shell structure material of Example 1 of this invention. The SEM image was tested on a TESCAN MIRA LMS, and the TEM image was tested on a JEOL JEM 2100F, Japan. In the SEM image (2a), it can be observed that TP-CPA-COF is uniformly grown on the surface of the hollow Co9S8 spheres. Further observation of the structure by the TEM image (2b) clearly shows the hollow double-shell structure and the tight interface connection between TP-CPA-COF and Co9S8. The above images prove the successful preparation of the hollow double-shell structure.

[0044] Figure 3In Example 1 of this invention, the hydrogen evolution rate of a typical sample from the hollow double-shell structure material was tested using a GC9790 PIUS instrument. Hollow double-shell structure material (10 mg), L-ascorbic acid (1.0 g), and deionized water (10 mL) were added sequentially to the reaction flask. The flask was irradiated at room temperature under nitrogen and a xenon lamp MC-PF300C (Beijing Merry Change) (wavelength ≥ 420 nm) at a distance of approximately 12 cm. Samples were taken every hour, and the generated gas was qualitatively and quantitatively analyzed. Under the same conditions, the hydrogen evolution rate of the pure Co9S8 sample was 116 μmol / g. -1 h -1 The hydrogen evolution rate of the pure TP-CPA-COF sample was 35 μmol g. - 1 h -1 The hollow double-shell structure material Co9S8@COF exhibits a hydrogen evolution rate as high as 23145 μmol g. -1 h -1 .

[0045] Figure 4 In Example 1 of this invention, the UV-Vis diffuse reflectance spectrum of the hollow double-shell structure material was measured using a UV-26001 (Shimadzu, China) instrument with BaSO4 as a reference. The UV-Vis diffuse reflectance spectrum (UV-Vis DRS) of Co9S8 shows negligible light absorption in the visible light range, while TP-CPA-COF and the hollow double-shell structure material exhibit broader visible light responses. The absorption edge of the hollow double-shell structure material is redshifted by 50 nm compared to TP-CPA-COF, and this wider visible light absorption range is more conducive to photocatalytic reactions.

[0046] Figure 5 This is the steady-state fluorescence emission spectrum of the hollow double-shell structure material in Example 1 of this invention. The spectrum was measured using an F-4600 spectrometer to investigate the separation and transfer of photogenerated carriers in the photocatalytic system. Compared to TP-CPA-COF, the peak intensity of the hollow double-shell structure material is significantly reduced, indicating a decreased probability of recombination between photogenerated electrons and holes. The hollow double-shell structure material is more conducive to electron transfer between TP-CPA-COF and Co9S8.

[0047] Figure 6This is the electrochemical impedance spectroscopy (EIS) diagram of the hollow double-shell structure material prepared in Example 1 of this invention. The separation and transport of photogenerated carriers are crucial to the photoelectric properties of materials. The size of the semicircle radius in the EIS diagram indicates the magnitude of the electron transport impedance; a smaller semicircle radius means a smaller electron transport impedance, which is more conducive to the separation and transport of photogenerated carriers. Since the hollow double-shell structure material exhibits a smaller semicircle radius compared to the pure TP-CPA-COF sample, its interfacial electron transport impedance is lower than that of the pure TP-CPA-COF sample. Therefore, the hollow double-shell structure material is more favorable for the separation and transport of photogenerated carriers. The electrochemical impedance spectroscopy was performed on a Chenhua CHI760E workstation. 5 mg of the hollow double-shell structure material was weighed and dispersed in an ethanol solution containing Nafion, and then ultrasonically dispersed until uniform. The conductive glass was ultrasonically cleaned with ethanol and dried. The dispersion was evenly dropped onto one end of the conductive glass with an area of ​​1 cm². 2 The remaining area was covered with epoxy resin. After drying, a test was conducted.

[0048] Example 2

[0049] Hollow NiCo2S4 (12 mg, 0.04 mmol), 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (12.6 mg, 0.032 mmol), 2,2'-([2,2'-bipyridine]-5,5'-diyl)acetonitrile (11.3 mg, 0.048 mmol), o-dichlorobenzene (0.8 mL), n-butanol (0.2 mL), and cesium carbonate (62 mg, 0.19 mmol) were added to a Schlenk tube. The air in the tube was then removed by three cycles of "freezing-vacuuming-thawing" with liquid nitrogen. The Schlenk tube was then sealed and heated at 120 °C for 3 days. The resulting solid powder was washed multiple times with tetrahydrofuran. The collected powder was dried under vacuum at 80 °C for 12 h to obtain a hollow double-shell structure material composed of transition metal sulfides and olefin COFs.

[0050] The freezing temperature is -196℃, the vacuum pressure is -0.1MPa, the thawing temperature is 25℃, and the freezing, vacuuming, and thawing times are all two minutes.

[0051] Hollow double-shell structure material (1g) was added to tetrahydrofuran (100mL), and after Soxhlet extraction for 1 day, the obtained solid powder was vacuum dried to obtain a purified hollow double-shell structure material composed of transition metal sulfides and olefin COFs.

[0052] Example 3

[0053] Hollow NiS (18 mg, 0.20 mmol), 1,3,5-tris(4-aminophenyl)benzene (35.1 mg, 0.10 mmol), pyromellitic dianhydride (32.7 mg, 0.15 mmol), mesitylene (0.50 mL), N-methylpyrrolidone (0.50 mL), and isoquinoline (0.05 mL) were added to a Schlenk tube. The air in the tube was then removed by three cycles of "freezing-vacuuming-thawing" with liquid nitrogen. The Schlenk tube was then sealed and heated at 200 °C for 5 days. The resulting solid powder was washed multiple times with tetrahydrofuran. The collected powder was dried under vacuum at 80 °C to obtain a hollow double-shell structure material composed of transition metal sulfides and imide COFs.

[0054] The freezing temperature is -196℃, the vacuum pressure is -0.1MPa, the thawing temperature is 25℃, and the freezing, vacuuming, and thawing times are all two minutes.

[0055] 1 g of hollow double-shell structured material was added to 100 mL of tetrahydrofuran and extracted with Soxhlet for 1 day. The resulting solid powder was then vacuum dried to obtain a hollow double-shell structured material composed of purified transition metal sulfides and imide COFs.

[0056] Example 4

[0057] Example 1 illustrates the application of hollow double-shell structured materials in the photocatalytic hydrogen evolution reaction. Specifically, hollow double-shell structured material (10 mg), L-ascorbic acid (1.0 g), and deionized water (10 mL) were added sequentially to a reaction flask. The flask was irradiated at room temperature under nitrogen and a xenon lamp (wavelength ≥ 420 nm) at a distance of approximately 12 cm. Samples were taken every hour, and the generated gas and liquid were qualitatively and quantitatively analyzed.

[0058] Matters not covered in this invention are common knowledge.

Claims

1. The use of a hollow double-shell structure material in a photocatalytic hydrogen evolution reaction, characterized in that, The preparation method of the hollow double-shell structure material comprises the following steps: The hollow transition metal sulfide, COF precursor, first organic solvent and aqueous inorganic acid are added in a Schlenk tube, the obtained mixture is ultrasonically treated for 10-60 minutes, and after removing air, the mixture is reacted at 100-200 o C for 3-7 days; the generated solid powder is washed and vacuum dried to obtain a hollow double-shell structure material formed by the transition metal sulfide and the COF. The mass ratio of the transition metal sulfide to the COFs precursor is 1:1-10; 1-20 mL of the first organic solvent is added per 1 mmol of the COFs precursor; and the volume ratio of the inorganic acid to the first organic solvent is 1:3-10. The COFs precursor is one or more of aromatic aldehyde compounds, aromatic amine compounds, aromatic hydrazine compounds, aromatic anhydride compounds and aromatic nitrile compounds. The hollow transition metal sulfide is Co9S8.

2. Use of the hollow double-shell structure material according to claim 1 in the photocatalytic hydrogen evolution reaction, characterized in that, The method further comprises the following steps: adding the obtained hollow double-shell structure material into a second organic solvent, Soxhlet extracting for 1-3 days, vacuum drying the obtained solid powder, and obtaining the purified hollow double-shell structure material formed by the transition metal sulfide and the COFs. 100-300 mL of the second organic solvent is added per gram of the hollow double-shell structure material.

3. Use of the hollow double-shell structure material according to claim 1 in the photocatalytic hydrogen evolution reaction, characterized in that, The aromatic aldehyde compound in the COFs precursor is 2,4,6-triformylphloroglucinol, 2,2'-bipyridine-5,5'-dicarboxaldehyde or 1,3,6,8-tetra(4-formylphenyl)pyrene; the aromatic amine compound is 1,4-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine or 1,3,5-tris(4-aminophenyl)benzene; the aromatic hydrazine compound is 2,5-dimethoxyterephthalic hydrazide or p-aminobenzhydrazide; the aromatic anhydride compound is 1,4,5,8-naphthalenetetracarboxylic anhydride or pyromellitic dianhydride; and the aromatic nitrile compound is 1,4-dicyanobenzene, 2,2'-([2,2'-bipyridine]-5,5'-diyl)diacetonitrile or 2,4,6-trimethylbenzene-1,3,5-tricyanide.

4. Use of the hollow double-shell structure material according to claim 1 in the photocatalytic hydrogen evolution reaction, characterized in that, The first organic solvent is any one or more of mesitylene, dioxane, o-dichlorobenzene, n-butanol, N,N-dimethylformamide, toluene and N-methylpyrrolidone.

5. Use of the hollow double-shell structure material according to claim 1 in the photocatalytic hydrogen evolution reaction, characterized in that, The inorganic acid aqueous solution is hydrochloric acid or nitric acid, and the concentration is 1-10 mol / L -1 .

6. Use of the hollow double-shell structure material according to claim 2 in the photocatalytic hydrogen evolution reaction, characterized in that, The second organic solvent is any one of acetone, tetrahydrofuran, dichloromethane and acetonitrile.

7. Use of the hollow double-shell structure material according to claim 1 in the photocatalytic hydrogen evolution reaction, characterized in that, The photocatalytic hydrogen evolution reaction comprises the following steps: weighing the hollow double-shell structure material and a sacrificial reagent, adding them into a reaction bottle, adding deionized water, and irradiating under visible light for 1-10 hours under nitrogen or argon. The mass ratio of the hollow double-shell structure material to the sacrificial reagent is 1:10-100; and 1-20 mg of the hollow double-shell structure material is added per 10 mL of the deionized water. The sacrificial reagent is L-ascorbic acid, sodium ascorbate, triethylamine, triethanolamine, ethanol, lactic acid or methanol.

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