Double transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst as well as preparation method and application thereof

Abstract

The invention relates to a double transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst and a preparation method and application thereof, and the stoichiometric general formula of the formula of the catalyst is ZnM1M2S3-CD, wherein M1 and M2 are respectively and independently selected from Fe, Co, Ni, Cu or Mn, and CD is selected from one or a composition of more of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin; the preparation method comprises the following steps: S1, in an inert gas atmosphere, suspending CD in an ethanol solution containing Zn < 2 + >, M < 12 + > and M < 2 + >, carrying out a stirring reaction, and after the reaction is finished, carrying out post-treatment to obtain a cyclodextrin component adsorbed with Zn < 2 + >, M < 12 + > and M < 2 + >; and S2, carrying out a hydrothermal reaction on the cyclodextrin component and thiourea in the presence of hexadecyl trimethyl ammonium bromide, and after the reaction is finished, carrying out post-treatment to obtain the double transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst, the catalyst is applied to preparation of ethylene through photocatalytic reduction of carbon dioxide. The catalyst has the advantages of efficiently catalyzing CO2 reduction and directionally generating ethylene.

Description

Technical Field

[0001] This invention relates to the technical field of catalysts, and in particular to a dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst, its preparation method, and its application. Background Technology

[0002] The chemical industry is a crucial foundation and pillar of the national economy, providing indispensable raw materials for key sectors such as agriculture, energy, materials, and pharmaceuticals. It drives technological innovation and industrial upgrading, and effectively safeguards the integrity of the national industrial system and the normal operation of society. Currently, organic chemicals dominate the chemical industry, with their raw materials, catalysts, solvents, auxiliaries, and final products primarily composed of carbon, which mainly comes from non-renewable fossil resources such as coal, oil, and natural gas. As fossil resources become increasingly depleted, and as carbon flows unidirectionally and ultimately is released into the atmosphere as carbon dioxide (CO2), the greenhouse effect intensifies and environmental pressure continues to rise. The chemical industry's heavy reliance on fossil resources and the CO2 emission problem have become urgent challenges that need to be addressed.

[0003] Converting CO2 into organic chemical feedstocks or intermediates not only helps mitigate greenhouse gas emissions but also provides the chemical industry with new carbon resource channels, reduces dependence on fossil fuels, and promotes carbon recycling and sustainable social development, possessing both significant economic value and profound social implications. Currently, CO2 conversion primarily utilizes catalytic reduction as its technological pathway, producing a series of key chemical intermediates including carbon monoxide (CO), methane (CH4), methanol (CH3OH), formic acid (HCOOH), ethylene (C2H4), ethane (C2H6), and ethanol (C2H5OH). Catalytic methods for achieving this process encompass thermocatalysis, electrocatalysis, photocatalysis, biocatalysis, photothermal catalysis, photoelectrocatalysis, and photoenzyme catalysis. Among these, visible light-driven CO2 catalytic reduction is considered a promising green conversion pathway due to its mild reaction conditions, ability to operate at room temperature, and utilization of renewable solar energy.

[0004] Among the many CO2 reduction products, ethylene is one of the basic raw materials of the chemical industry, widely used in the production of bulk chemicals such as synthetic fibers, synthetic rubber, polyethylene (PE), polyvinyl chloride (PVC), and ethanol. Its output is considered a key indicator of a country's chemical industry development level. Since the annual ethylene production is close to 35 million tons, if all of it were derived from CO2 reduction, it would consume approximately 110 million tons of CO2. Therefore, developing visible light-driven CO2 to ethylene technology can not only realize the high-value resource utilization of industrial by-product CO2 and mitigate the greenhouse effect, but also provide an alternative carbon source for the chemical industry, promoting carbon cycling and sustainable economic development.

[0005] Although visible light-driven CO2 reduction to ethylene is considered an important pathway to advance the carbon cycle strategy, offering the dual benefits of emission reduction and resource regeneration, the technology currently faces challenges such as low conversion efficiency and a significant gap between its performance and practical industrial application requirements. Therefore, developing efficient and highly selective visible light photocatalytic systems to achieve the economical and efficient conversion of CO2 to ethylene and promote its industrial application has become an urgent need for the chemical industry and an inevitable direction for promoting sustainable social development. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the first objective of this invention is to provide a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which introduces two transition metal ions M1 2+ and M2 2+ For Zn with suitable ionic radius C–C coupling 2+ By regulating the electronic environment, a biomimetic trimetallic synergistic catalytic center is constructed to promote the formation of C–C bonds during CO2 reduction and improve the efficiency of ethylene production. At the same time, the polyhydroxy structure of cyclodextrin is used to promote proton transfer and electron transport during the reaction process, and its hydrophobic cavity structure is used to simulate the hydrophobic pocket of natural enzymes to provide a microscopic confined catalytic environment and enhance the enrichment of hydrophobic reaction intermediates. The above three methods work synergistically to promote C–C coupling and achieve efficient synthesis of ethylene.

[0007] The second objective of this invention is to provide a method for preparing a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which uses visible light as an energy source, water as a solvent and hydrogen source at room temperature, and has the advantages of being green and environmentally friendly, energy-saving and emission-reducing, having high reduction efficiency, good ethylene selectivity and strong practicality.

[0008] The third objective of this invention is to provide an application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which has the advantages of highly efficient catalytic reduction of CO2 and directional generation of ethylene.

[0009] To achieve the first objective mentioned above, the present invention provides the following technical solution: A dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, wherein the stoichiometric formula of the catalyst is ZnM1M2S3-CD; wherein M1 and M2 are each independently selected from Fe, Co, Ni, Cu or Mn, and CD is selected from one or a combination of several of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

[0010] To achieve the second objective mentioned above, the present invention provides the following technical solution: A method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst includes the following steps: S1 suspends CD in a Zn-containing atmosphere in an inert gas atmosphere. 2+ M1 2+ and M2 2+ The reaction was carried out in an ethanol solution with stirring. After the reaction was completed, post-treatment was performed to obtain the product with adsorbed Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; S2 involves a hydrothermal reaction of the cyclodextrin component obtained in S1 and thiourea in the presence of hexadecyltrimethylammonium bromide. After the reaction is completed, post-treatment is performed to obtain a bitransition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst.

[0011] Furthermore, in S1, Zn 2+ M1 is provided by a hydrate of one or more of zinc chloride, zinc sulfate, and zinc nitrate. 2+ and M2 2+ Each is provided independently by a hydrate of one or more of the following: ferrous chloride, ferrous sulfate, ferrous nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate, nickel chloride, nickel sulfate, nickel nitrate, copper chloride, copper sulfate, copper nitrate, manganese chloride, manganese sulfate, and manganese nitrate.

[0012] Furthermore, in S1, Zn is controlled. 2+ The concentration is 0.01~2.00 mol / L, M1 2+ The concentration is 0.01~1.00 mol / L, M2 2+ The concentration is 0.01~1.00 mol / L, Zn 2+ M1 2+ and M2 2+ The molar ratio is 1:(1~100):(1~100), CD and containing Zn 2+ M1 2+ and M2 2+ The mass-to-volume ratio of the ethanol solution is 1g:(10~500)mL.

[0013] Furthermore, in S1, Zn is controlled. 2+ The concentration is 0.10~1.00mol / L, M1 2+ The concentration is 0.10~0.80 mol / L, M2 2+ The concentration is 0.10~0.80 mol / L, Zn 2+ M1 2+ and M2 2+ The molar ratio is 1:(2~5):(2~5), CD and containing Zn 2+ M1 2+ and M2 2+The mass-to-volume ratio of the ethanol solution is 1g:(100~200)mL.

[0014] Furthermore, in S1, the reaction temperature is controlled at 0~60℃ and the reaction time is controlled at 2.0~24.0h.

[0015] Furthermore, in S1, the reaction temperature is controlled at 20~30℃ and the reaction time is 8.0~16.0h.

[0016] Furthermore, in S1, after the reaction is completed, the reactants are sequentially subjected to suction filtration and washing with ethanol.

[0017] Furthermore, in S2, the reaction temperature is controlled at 100~200℃ and the reaction time is 8.0~48.0h.

[0018] Furthermore, in S2, the reaction temperature is controlled at 150~180℃ and the reaction time is 12.0~30.0h.

[0019] Further, in step S2, the reactants are sequentially washed with ethanol, washed with deionized water, and dried under vacuum at 70-90°C.

[0020] To achieve the third objective mentioned above, the present invention provides the following technical solution: Application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst in the photocatalytic reduction of carbon dioxide to ethylene.

[0021] Furthermore, the specific implementation method of the photocatalytic carbon dioxide reduction to prepare ethylene is as follows: after dispersing the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst in deionized water, carbon dioxide is introduced into the reactor, a visible light source is turned on, and the reaction is stirred at room temperature to obtain ethylene, carbon monoxide and methane.

[0022] Furthermore, during the reaction process, the power of the visible light source is controlled to be 10~500W.

[0023] Furthermore, during the reaction process, the power of the visible light source is controlled to be 100~300W.

[0024] Furthermore, during the reaction process, the mass ratio of the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst to deionized water is controlled to be 1:(100~100000).

[0025] Furthermore, during the reaction process, the mass ratio of the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst to deionized water is controlled to be 1:(1000~10000).

[0026] Furthermore, during the reaction process, the gas pressure is controlled at 0.05~0.15MPa.

[0027] Furthermore, during the reaction process, the gas pressure is controlled at 0.08~0.10 MPa.

[0028] In summary, the beneficial technical effects of the present invention are as follows: 1. The dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst of the present invention promotes C-C bond coupling by mimicking natural enzymes such as chlorophyll and biomimetic catalysis of CO2 reduction to ethylene through the efficient reduction of CO2. 2. The dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst of the present invention uses transition metal Fe 2+ Co 2+ Ni 2 + Cu 2+ or Mn 2+ Regulating Zn 2+ The electronic environment forms a biomimetic trimetallic synergistic catalytic center, promoting the formation of C-C bonds during CO2 reduction and facilitating the efficient generation of ethylene. 3. The dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst of the present invention provides a carrier for proton transfer and electron transport in the CO2 reduction process with the polyhydroxy structure of cyclodextrin, further promoting the formation of CC bonds in the CO2 reduction process and promoting the efficient generation of ethylene. 4. The dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst of the present invention utilizes the hydrophobic cavity structure of cyclodextrin to simulate the hydrophobic pocket of natural enzymes, providing a microscopic confined catalytic environment for CC coupling during CO2 reduction, enhancing the enrichment of hydrophobic species during CO2 reduction, and promoting the formation of ethylene through CC bond coupling in a triple manner. 5. The preparation method of this invention is not only green and environmentally friendly, energy-saving and emission-reducing, but also has high efficiency in generating reduction products, high ethylene selectivity, and strong practicality. It is a green, efficient and practical method for CO2 reduction to prepare ethylene, with considerable potential for industrial application. The method of improving the efficiency of CO2 reduction to prepare ethylene through biomimetic strategies in this invention also has certain guiding value for improving the catalytic efficiency of other catalytic systems. 6. This invention employs an innovatively designed dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst (ZnM1M2S3-CD) to catalyze the reduction of CO2 to ethylene. This catalyst has a novel structure, high stability, and low cost. Under visible light-driven conditions, with water as the solvent and hydrogen source, and at room temperature and mild reaction conditions, it exhibits high ethylene selectivity and product formation efficiency, significantly reducing separation energy consumption and carbon emissions. It requires no organic solvents, conforms to the principles of green chemistry, and combines energy-saving and emission-reduction advantages with industrial application potential. It provides an efficient, practical, and promising new strategy for the resource utilization of CO2. Attached Figure Description

[0029] Figure 1 The Fourier transform infrared (FT-IR) spectra of the catalysts FeCoZnS3-βCD, β-cyclodextrin, and FeCoZnS3 prepared in Example 1 of this invention are shown.

[0030] Figure 2 This is a gas chromatogram of the product obtained in Example 53 of the present invention.

[0031] Figure 3 This is a standard gas chromatogram of ethylene, carbon monoxide, and methane according to the present invention. Detailed Implementation

[0032] To make the technical means, creative features, objectives and effects of this invention clearer and easier to understand, the invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

[0033] Example 1: A dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention. The stoichiometric formula of the catalyst is ZnM1M2S3-CD; wherein M1 and M2 are each independently selected from Fe, Co, Ni, Cu or Mn, and CD is selected from one or more of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

[0034] The following are the naming rules for the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst (ZnM1M2S3-CD). ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h indicates that during the catalyst preparation process, M1 and M2 are respectively Fe... 2+ and Co 2+ Zn in ethanol solution 2+ The concentration was 0.9 mol / L, Fe 2+ The concentration was 0.3 mol / L, Co 2+ The concentration of β-cyclodextrin was 0.3 mol / L, the mass ratio of β-cyclodextrin (g) to the volume ratio of ethanol solution (mL) was 1:150, the reaction was carried out by stirring at 25℃ for 12 h, and then by hydrothermal reaction at 170℃ for 24 h.

[0035] This invention also discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, comprising the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.66 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0036] Fourier transform infrared (FT-IR) spectra of catalysts FeCoZnS3-βCD, β-cyclodextrin, and FeCoZnS3 are shown below. Figure 1 As shown, from Figure 1 Characteristic absorption signals from β-cyclodextrin and FeCoZnS3 components can be clearly identified, located at 2845 cm⁻¹. -1 The absorption peak at 1035 cm⁻¹ is attributed to the characteristic vibration of FeCoZnS₃, indicating that the FeCoZnS₃ component exists in the biomimetic catalyst system. Meanwhile, at 1035 cm⁻¹... -1 The distinct absorption peaks at the specified positions originate from the characteristic structural vibrations of β-cyclodextrin. These absorption peaks are clearly identifiable in the spectrum of the FeCoZnS3-βCD biomimetic catalyst, while the corresponding signal is not particularly prominent in the spectrum of the single FeCoZnS3 component. Therefore, the appearance of these characteristic absorptions indicates that β-cyclodextrin has been successfully introduced into the biomimetic catalyst material. In summary, the infrared spectroscopy analysis results show that the FeCoZnS3-βCD biomimetic catalyst is a complex composed of FeCoZnS3 and β-cyclodextrin. The FT-IR spectrum of FeCoZnS3-βCD not only contains the characteristic absorption peak of FeCoZnS3 (2845 cm⁻¹), but also... -1 Near the location, it also contains the characteristic absorption peak of β-cyclodextrin (1035 cm⁻¹). -1 The presence of the sample in the vicinity (nearby area) indicates, to some extent, the successful synthesis of the FeCoZnS3-βCD biomimetic catalyst.

[0037] Table 1

[0038] Table 1 is an elemental composition analysis table of the biomimetic catalyst FeCoZnS3-βCD prepared in Example 1. As can be seen from Table 1, the average content of cobalt in the material is 20.22%, the average content of iron is 3.72%, and the average content of zinc is 7.52%. The three elements coexist relatively stably in the structure of the prepared dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst.

[0039] Example 2: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.1 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.18 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.1M@0.3M@0.3M@150@25@12h@170@24h.

[0040] Example 3: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 1.0 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.72 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@1.0M@0.3M@0.3M@150@25@12h@170@24h.

[0041] Example 4: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.01 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.12 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.01M@0.3M@0.3M@150@25@12h@170@24h.

[0042] Example 5: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 2.0 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 1.47 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@2.0M@0.3M@0.3M@150@25@12h@170@24h.

[0043] Example 6: This is a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention. The difference from Example 1 is that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.1 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.58 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.1M@0.3M@150@25@12h@170@24h.

[0044] Example 7: This is a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention. The difference from Example 1 is that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.8 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 1.06 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.8M@0.3M@150@25@12h@170@24h.

[0045] Example 8: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+Concentration of 0.01 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.16 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.01M@0.3M@150@25@12h@170@24h.

[0046] Example 9: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 1.0 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 1.63 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@1.0M@0.3M@150@25@12h@170@24h.

[0047] Example 10: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The solution was stirred in 150 mL of a 0.1 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the solution was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.61 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.1M@150@25@12h@170@24h.

[0048] Example 11: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The solution was stirred in 150 mL of a 0.8 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the solution was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 1.23 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.8M@150@25@12h@170@24h.

[0049] Example 12: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The sample was stirred in 150 mL of a 0.01 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the sample was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a sample with adsorbed Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.25 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.01M@150@25@12h@170@24h.

[0050] Example 13: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+Concentration of 0.3 mol / L, Co 2+ The solution was stirred in 150 mL of a 1.0 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the solution was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 1.86 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@1.0M@150@25@12h@170@24h.

[0051] Example 14: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.18 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.97 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.18M@0.3M@150@25@12h@170@24h.

[0052] Example 15: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.45 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.43 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.45M@0.3M@150@25@12h@170@24h.

[0053] Example 16: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.009 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 1.92 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.009M@0.3M@150@25@12h@170@24h.

[0054] Example 17: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.9 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.41 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.9M@0.3M@150@25@12h@170@24h.

[0055] Example 18: This is a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention. The difference from Example 1 is that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+Concentration of 0.3 mol / L, Co 2+ The solution was stirred in 150 mL of a 0.18 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the solution was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.72 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.18M@150@25@12h@170@24h.

[0056] Example 19: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The solution was stirred in 150 mL of a 0.45 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the solution was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.36 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.45M@150@25@12h@170@24h.

[0057] Example 20: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The solution was stirred in 150 mL of a 0.009 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the solution was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 1.85 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.009M@150@25@12h@170@24h.

[0058] Example 21: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The solution was stirred in 150 mL of a 0.9 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the solution was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.06 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.9M@150@25@12h@170@24h.

[0059] Example 22: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ In a 0.3 mol / L ethanol solution (100 mL), the mixture was stirred at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.62 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@100@25@12h@170@24h.

[0060] Example 23: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+Concentration of 0.3 mol / L, Co 2+ In a 0.3 mol / L ethanol solution (200 mL), the mixture was stirred at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.69 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@200@25@12h@170@24h.

[0061] Example 24: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1: In a 50 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn... 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The solution was stirred in 10 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the solution was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.46 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@10@25@12h@170@24h.

[0062] Example 25: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1: In a 1000 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn... 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 500 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.59 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@500@25@12h@170@24h.

[0063] Example 26: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The sample was stirred in 150 mL of a 0.3 mol / L ethanol solution at 20 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the sample was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a sample with adsorbed Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.63 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@20@12h@170@24h.

[0064] Example 27: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The solution was stirred in 150 mL of a 0.3 mol / L ethanol solution at 30 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the solution was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.68 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@30@12h@170@24h.

[0065] Example 28: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 0 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.03 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@0@12h@170@24h.

[0066] Example 29: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The sample was stirred in 150 mL of a 0.3 mol / L ethanol solution at 60 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the sample was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a sample with adsorbed Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.38 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@60@12h@170@24h.

[0067] Example 30: This is a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention. The difference from Example 1 is that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The solution was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 8.0 h under a N2 atmosphere. After the reaction was completed, the solution was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.45 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@8h@170@24h.

[0068] Example 31: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 16.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.75 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@16h@170@24h.

[0069] Example 32: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 2.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.23 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@2h@170@24h.

[0070] Example 33: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+Concentration of 0.3 mol / L, Co 2+ The solution was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 24.0 h under a N2 atmosphere. After the reaction was completed, the solution was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.93 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@24h@170@24h.

[0071] Example 34: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 150 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.42 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@150@24h.

[0072] Example 35: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 180 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.71 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@180@24h.

[0073] Example 36: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 100 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.25 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@100@24h.

[0074] Example 37: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 200 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.81 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@200@24h.

[0075] Example 38: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 12.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.31 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@12h.

[0076] Example 39: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 30.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.78 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@30h.

[0077] Example 40: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 8.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.21 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@8h.

[0078] Example 41: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 48.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.97 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@48h.

[0079] Example 42: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Ni 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.52 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeNiS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0080] Example 43: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+Concentration of 0.3 mol / L, Cu 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.72 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCuS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0081] Example 44: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Mn 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.81 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeMnS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0082] Example 45: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Co 2+ Concentration of 0.3 mol / L, Ni 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.92 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnCoNiS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0083] Example 46: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Co 2+ Concentration of 0.3 mol / L, Cu 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.84 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnCoCuS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0084] Example 47: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Co 2+ Concentration of 0.3 mol / L, Mn 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.45 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnCoMnS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0085] Example 48: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Ni 2+Concentration of 0.3 mol / L, Cu 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.57 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnNiCuS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0086] Example 49: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Ni 2+ Concentration of 0.3 mol / L, Mn 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.41 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnNiMnS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0087] Example 50: This is a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention. The difference from Example 1 is that it includes the following steps: S1 In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Cu 2+ Concentration of 0.3 mol / L, Mn 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.72 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnCuMnS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0088] Example 51: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1 In a 250 mL single-necked flask, α-cyclodextrin (1.00 g) was suspended in Zn 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.66 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-αCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0089] Example 52: This invention discloses a method for preparing a dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, which differs from Example 1 in that it includes the following steps: S1: In a 250 mL single-necked flask, γ-cyclodextrin (1.00 g) was suspended in Zn... 2+ Concentration of 0.9 mol / L, Fe 2+ Concentration of 0.3 mol / L, Co 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under a N2 atmosphere. After the reaction was completed, the mixture was filtered and washed with 3 × 20 mL of anhydrous ethanol to obtain a solution adsorbed with Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; In S2, the cyclodextrin component obtained in S1, thiourea (0.25 g), and hexadecyltrimethylammonium bromide (0.10 g) were dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The hydrothermal reactor was then sealed and the reaction was carried out at 170 °C for 24.0 h under N2 atmosphere. After the reaction was completed, the solid was successively filtered, washed with 3 × 20 mL of anhydrous ethanol, washed with 3 × 20 mL of deionized water, and dried at 80 °C for 8.0 h to obtain 0.66 g of gray-black solid, which is the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst ZnFeCoS3-γCD@0.9M@0.3M@0.3M@150@25@12h@170@24h.

[0090] Example 53: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent light source was turned on. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 671 μmol / (g). Cat. (·h), of which ethylene selectivity is 97%, carbon monoxide selectivity is 2%, and methane selectivity is 1%.

[0091] Combination Figure 3 The standard product peak position, from Figure 2 It can be seen that the peak at about 9.6 min is ethylene, the peak at about 14 min is methane, and the peak at 17.5 min is carbon monoxide. The gas chromatogram confirms the presence of the catalytic product.

[0092] Example 54: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, specifically, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 10 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent light source was turned on. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 512 μmol / (g). Cat. (·h), of which ethylene selectivity is 95%, carbon monoxide selectivity is 3%, and methane selectivity is 2%.

[0093] Example 55: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, specifically, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 100 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200 W LED incandescent lamp was turned on as a visible light source. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 532 μmol / (g). Cat. (·h), of which ethylene selectivity is 94%, carbon monoxide selectivity is 4%, and methane selectivity is 2%.

[0094] Example 56: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 1 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent lamp was turned on as a visible light source. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 415 μmol / (g). Cat. (·h), of which ethylene selectivity is 90%, carbon monoxide selectivity is 5%, and methane selectivity is 5%.

[0095] Example 57: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 1000 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent lamp was turned on for visible light. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 449 μmol / (g). Cat.(·h), of which ethylene selectivity is 89%, carbon monoxide selectivity is 6%, and methane selectivity is 5%.

[0096] Example 58: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was then sealed. A 100W LED incandescent light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 443 μmol / (g). Cat. (·h), of which ethylene selectivity is 90%, carbon monoxide selectivity is 4%, and methane selectivity is 6%.

[0097] Example 59: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was then sealed. A 300W LED incandescent lamp was turned on as a visible light source, and the reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 502 μmol / (g). Cat. (·h), of which ethylene selectivity is 92%, carbon monoxide selectivity is 3%, and methane selectivity is 5%.

[0098] Example 60: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was then sealed. A 10W LED incandescent light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 162 μmol / (g). Cat. (·h), of which ethylene selectivity is 82%, carbon monoxide selectivity is 16%, and methane selectivity is 2%.

[0099] Example 61: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was then sealed. A 500W LED incandescent lamp was turned on as a visible light source, and the reaction was carried out at room temperature with stirring for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 418 μmol / (g). Cat. (·h), of which ethylene selectivity is 85%, carbon monoxide selectivity is 13%, and methane selectivity is 2%.

[0100] Example 62: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, specifically, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.08 MPa. The reactor was sealed, and a 200W LED incandescent lamp was turned on for visible light. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 552 μmol / (g). Cat.(·h), of which ethylene selectivity is 95%, carbon monoxide selectivity is 3%, and methane selectivity is 2%.

[0101] Example 63: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.10 MPa. The reactor was sealed, and a 200W LED incandescent lamp was turned on for visible light. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 541 μmol / (g). Cat. (·h), of which ethylene selectivity is 94%, carbon monoxide selectivity is 3%, and methane selectivity is 3%.

[0102] Example 64: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.05 MPa. The reactor was sealed, and a 200W LED incandescent lamp was turned on for visible light. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 457 μmol / (g). Cat. (·h), of which ethylene selectivity is 90%, carbon monoxide selectivity is 4%, and methane selectivity is 6%.

[0103] Example 65: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, specifically, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.15 MPa. The reactor was sealed, and a 200W LED incandescent light source was turned on. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 511 μmol / (g). Cat. (·h), of which ethylene selectivity is 88%, carbon monoxide selectivity is 6%, and methane selectivity is 6%.

[0104] Example 66: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeNiS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent lamp was turned on for visible light. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 415 μmol / (g). Cat. (·h), of which ethylene selectivity is 78%, carbon monoxide selectivity is 21%, and methane selectivity is 11%.

[0105] Example 67: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, specifically, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCuS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent light source was turned on. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 312 μmol / (g). Cat.(·h), of which ethylene selectivity is 74%, carbon monoxide selectivity is 12%, and methane selectivity is 14%.

[0106] Example 68: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of ZnFeMnS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200 W LED incandescent lamp was turned on as a visible light source. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 368 μmol / (g). Cat. (·h), of which ethylene selectivity is 71%, carbon monoxide selectivity is 14%, and methane selectivity is 15%.

[0107] Example 69: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, specifically, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnCoNiS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent light source was turned on. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 246 μmol / (g). Cat. (·h), of which ethylene selectivity is 70%, carbon monoxide selectivity is 18%, and methane selectivity is 12%.

[0108] Example 70: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, specifically, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnCoCuS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent light source was turned on. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 223 μmol / (g). Cat. (·h), of which ethylene selectivity is 71%, carbon monoxide selectivity is 17%, and methane selectivity is 12%.

[0109] Example 71: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of the ZnCoMnS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent light source was turned on. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 215 μmol / (g). Cat. (·h), of which ethylene selectivity is 73%, carbon monoxide selectivity is 15%, and methane selectivity is 12%.

[0110] Example 72: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, specifically, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnNiCuS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent light source was turned on. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 172 μmol / (g). Cat.(·h), of which ethylene selectivity is 73%, carbon monoxide selectivity is 18%, and methane selectivity is 9%.

[0111] Example 73: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of ZnNiMnS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent lamp was turned on for visible light. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 156 μmol / (g). Cat. (·h), of which ethylene selectivity is 74%, carbon monoxide selectivity is 14%, and methane selectivity is 12%.

[0112] Example 74: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, specifically, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnCuMnS3-βCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent light source was turned on. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 134 μmol / (g). Cat. (·h), of which ethylene selectivity is 70%, carbon monoxide selectivity is 13%, and methane selectivity is 17%.

[0113] Example 75: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 is that, in a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-αCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent light source was turned on. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 431 μmol / (g). Cat. (·h), of which ethylene selectivity is 90%, carbon monoxide selectivity is 2%, and methane selectivity is 8%.

[0114] Example 76: This example illustrates the application of a dual transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst disclosed in this invention in the photocatalytic reduction of carbon dioxide to ethylene. The difference from Example 1 lies in the specific implementation method: In a carbon dioxide photocatalytic reactor, 10 mg of the ZnFeCoS3-γCD@0.9M@0.3M@0.3M@150@25@12h@170@24h catalyst was dispersed in 50 g of deionized water. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.09 MPa. The reactor was sealed, and a 200W LED incandescent light source was turned on. The reaction was stirred at room temperature for 8.0 h. The reduction products were detected by online gas chromatography, and the total reduction product formation efficiency was 369 μmol / (g). Cat. (·h), of which ethylene selectivity is 88%, carbon monoxide selectivity is 6%, and methane selectivity is 6%.

[0115] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A dual-transition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst, comprising, characterized in that: The stoichiometric formula of the catalyst is ZnM1M2S3-CD; wherein M1 and M2 are each independently selected from Fe, Co, Ni, Cu or Mn, and CD is selected from one or more of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

2. The preparation method of the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst according to claim 1, characterized in that: Includes the following steps, S1 suspends CD in a Zn-containing atmosphere in an inert gas atmosphere. 2+ M1 2+ and M2 2+ The reaction was carried out in an ethanol solution with stirring. After the reaction was completed, post-treatment was performed to obtain the product with adsorbed Zn. 2+ M1 2+ and M2 2+ The cyclodextrin component; S2 involves a hydrothermal reaction of the cyclodextrin component obtained in S1 and thiourea in the presence of hexadecyltrimethylammonium bromide. After the reaction is completed, post-treatment is performed to obtain a bitransition metal-doped zinc sulfide-cyclodextrin biomimetic catalyst.

3. The preparation method of the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst according to claim 2, characterized in that: In S1, Zn 2+ M1 is provided by a hydrate of one or more of zinc chloride, zinc sulfate, and zinc nitrate. 2+ and M2 2+ Each is provided independently by a hydrate of one or more of the following: ferrous chloride, ferrous sulfate, ferrous nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate, nickel chloride, nickel sulfate, nickel nitrate, copper chloride, copper sulfate, copper nitrate, manganese chloride, manganese sulfate, and manganese nitrate.

4. The preparation method of the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst according to claim 2, characterized in that: In S1, Zn is controlled 2+ The concentration is 0.01~2.00 mol / L, M1 2+ The concentration is 0.01~1.00 mol / L, M2 2+ The concentration is 0.01~1.00 mol / L, Zn 2+ M1 2+ and M2 2+ The molar ratio is 1:(1~100):(1~100), CD and containing Zn 2+ M1 2+ and M2 2+ The mass-to-volume ratio of the ethanol solution is 1g:(10~500)mL.

5. The preparation method of a dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst according to claim 2, characterized in that: In S1, the reaction temperature is controlled at 0~60℃ and the reaction time is controlled at 2.0~24.0h.

6. The preparation method of a dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst according to claim 2, characterized in that: In S2, the reaction temperature is controlled at 50~180℃ and the reaction time is controlled at 12.0~30.0h.

7. The application of the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst according to claim 1 in the photocatalytic reduction of carbon dioxide to ethylene.

8. The preparation method of a dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst according to claim 7, characterized in that: The specific method for photocatalytic carbon dioxide reduction to prepare ethylene is as follows: a dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst is dispersed in deionized water, carbon dioxide is introduced into the reactor, a visible light source is turned on, and the reaction is stirred at room temperature to obtain ethylene, carbon monoxide, and methane.

9. The preparation method of a dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst according to claim 8, characterized in that: During the reaction process, the power of the visible light source is controlled to be 10~500W and the air pressure is 0.05~0.15MPa.

10. The application of the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst according to claim 8, characterized in that: During the reaction, the mass ratio of the dual transition metal doped zinc sulfide-cyclodextrin biomimetic catalyst to deionized water is controlled to be 1:(100~100000).

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