Transition metal doped manganese sulfide-cyclodextrin mimic enzyme as well as preparation method and application thereof

Abstract

The invention discloses transition metal doped manganese sulfide-cyclodextrin mimic enzyme as well as a preparation method and application thereof. The method comprises the following steps: suspending cyclodextrin in an ethanol solution containing Mn < 2 + > and M < 2 + >, and carrying out a stirring reaction in an N2 atmosphere to obtain a cyclodextrin solid adsorbed with Mn < 2 + > and M < 2 + >; mixing the solid with thiourea, hexadecyl trimethyl ammonium bromide and absolute ethyl alcohol, stirring at room temperature in an N2 atmosphere, and performing hydrothermal reaction to obtain transition metal doped manganese sulfide-cyclodextrin mimic enzyme (MnMS2-CD); mnMS2-CD can be used for preparing ethylene by reducing CO2 driven by visible light, the reaction is carried out at room temperature, visible light is used as an energy source, water is used as a solvent and a hydrogen source, and the method has the characteristics of environmental protection, energy conservation and emission reduction; meanwhile, the reduction product generation efficiency is high, the ethylene selectivity is good, the practicability is high, and the method is a green and efficient CO2 resource utilization way with a practical application prospect.

Description

Technical Field

[0001] This invention belongs to the fields of industrial catalysis and biomimetic catalysis, specifically relating to a transition metal-doped manganese sulfide-cyclodextrin enzyme (MnMS2-CD) and its preparation method, as well as its application as a catalyst in the reduction of carbon dioxide (CO2) to produce ethylene. Background Technology

[0002] The chemical industry is one of the important foundations and pillar industries of the national economy. It provides essential raw materials for many industries such as agriculture, energy, materials, and pharmaceuticals, promotes technological innovation and industrial upgrading, strongly supports the integrity of the national industrial system, and ensures the normal operation of society and people's lives. By 2025, the total output value of China's chemical industry is expected to account for 12% of the national GDP and more than 40% of the global chemical market, highlighting its pillar status. Currently, organic chemicals account for a large proportion of the chemical industry. The raw materials, catalysts, solvents, additives, and final products used in organic chemicals are all based on carbon. These carbon elements mainly come from non-renewable fossil resources such as coal, oil, and natural gas. Not only are carbon resources themselves increasingly depleted, but the unidirectional flow of carbon also leads to its eventual emission into the atmosphere as carbon dioxide (CO2), exacerbating the greenhouse effect and putting serious pressure on the environment. Given the chemical industry's high dependence on fossil resources and the environmental challenges posed by CO2 emissions, converting CO2 into organic chemical raw materials or intermediates is of great significance. This approach can not only alleviate environmental problems caused by CO2 emissions and help my country achieve its goal of "carbon peaking and carbon neutrality", but also provide new carbon resource sources for organic chemical industry, reduce dependence on fossil resources, realize the recycling of carbon elements, and promote sustainable social development. It has significant economic value and far-reaching social significance.

[0003] The conversion of carbon dioxide (CO2) into chemical raw materials or intermediates is currently mainly achieved through catalytic reduction. Reduction products include carbon monoxide (CO), methane (CH4), methanol (CH3OH), formic acid (HCOOH), ethylene (CH2=CH2), ethane (CH3-CH3), and ethanol (CH3CH2OH), all of which are important chemical raw materials and intermediates. Catalytic methods for achieving this conversion include thermocatalysis, electrocatalysis, photocatalysis, biocatalysis, photothermal catalysis, photoelectrocatalysis, and photoenzyme catalysis. Among these, visible light-driven CO2 catalytic reduction is considered a promising CO2 conversion pathway due to its mild reaction conditions, ability to proceed at room temperature, and utilization of abundant renewable solar energy. Ethylene, one of the most basic raw materials in the chemical industry, is essential for the production of synthetic fibers, synthetic rubber, synthetic plastics such as polyethylene (PE), high-density polyethylene (HDPE), polyvinyl chloride (PVC), and synthetic ethanol. Ethylene production is an indicator of a country's level of chemical industry development. In 2024, my country's ethylene production approached 35 million tons. If all ethylene production came from CO2 reduction, it would consume approximately 110 million tons of CO2. Therefore, developing visible light-driven CO2 reduction technology for ethylene production not only helps to efficiently utilize industrial by-product CO2 and mitigate the greenhouse effect, but also provides a new carbon source for the chemical industry, promoting carbon cycling and sustainable social development.

[0004] Although visible light-driven CO2 reduction to ethylene is considered a highly efficient pathway to achieve carbon neutrality, carbon peaking, and carbon cycle strategies, possessing the dual potential of emission reduction and resource regeneration, this technology currently suffers from low conversion efficiency and a significant gap between its current performance and practical application requirements. Therefore, developing efficient visible light photocatalytic systems to achieve highly selective and efficient conversion of CO2 to ethylene with industrial application value has become an urgent need for the chemical industry and an inevitable direction for promoting sustainable social development. Summary of the Invention

[0005] To overcome the shortcomings of existing visible light-driven CO2 catalytic reduction technology for ethylene production, this invention provides a transition metal-doped manganese sulfide-cyclodextrin biomimetic enzyme (MnMS2-CD) and its preparation method, as well as its application as a catalyst in the reduction of carbon dioxide (CO2) to ethylene.

[0006] This invention achieves the highly efficient catalytic reduction of CO2 to ethylene by mimicking natural enzymes. It utilizes transition metal M... 2+Adjusting the ionic radius (124 pm) is suitable for CC-coupled Mn 2+ The electronic environment forms a biomimetic bimetallic synergistic catalytic center, promoting the formation of C-C bonds during CO2 reduction and facilitating the efficient generation of ethylene. The polyhydroxy structure of cyclodextrin promotes proton transfer and electron transport during CO2 reduction. By utilizing the hydrophobic cavity structure of cyclodextrin, it simulates the hydrophobic pocket of natural enzymes, providing a microscopic confined catalytic environment and enhancing the enrichment of hydrophobic species during CO2 reduction. These three methods promote the coupling of C-C bonds to form ethylene.

[0007] The visible light-driven CO2 reduction method for preparing ethylene provided by this invention is a room temperature reaction that uses visible light as an energy source, water as a solvent and hydrogen source. It is not only green and environmentally friendly, energy-saving and emission-reducing, but also has high efficiency in generating reduction products, high selectivity for ethylene, and strong practicality. It is a green, efficient and practical method for preparing ethylene by CO2 reduction.

[0008] The technical solution of the present invention is as follows: A transition metal-doped manganese sulfide-cyclodextrin biomimetic enzyme was prepared by the following method: (1) Suspend cyclodextrin in a solution containing Mn 2+ and M 2+ In an ethanol solution, under a N2 atmosphere, the reaction was stirred at 0–60 °C (20–30 °C) for 2.0–24.0 h (preferably 8.0–16.0 h), followed by filtration and washing (with ethanol) to obtain the product adsorbed with Mn. 2+ and M 2+ cyclodextrin solids; Cyclodextrin is one or more of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin; Contains Mn 2+ and M 2+ In ethanol solution, Mn 2+ Manganese chloride (MnCl2) and its hydrate, manganese sulfate (MnSO4) and its hydrate, and manganese nitrate (Mn(NO3)2) and its hydrate are provided; M 2+ Provided by its hydrochloride, sulfate, nitrate and hydrate, M 2+ For Fe 2+ Co 2+ Ni 2+ Cu 2+ or Zn 2+ ; Contains Mn 2+ and M 2+ In ethanol solution, Mn 2+ Concentration 0.01~2.00 mol / L, preferably 0.1~1.00 mol / L; M 2+Concentration 0.01~1.00 mol / L, preferably 0.1~0.80 mol / L; M 2+ With Mn 2+ The molar concentration ratio is 1:100~1:1, preferably 1:5~1:2; Cyclodextrin, containing Mn 2+ and M 2+ The mass-to-volume ratio of the ethanol solution is 1:10~1:500, g / mL; preferably 1:100~1:200, g / mL. (2) The adsorbed Mn obtained in step (1) 2+ and M 2+ The solid cyclodextrin was mixed with thiourea, hexadecyltrimethylammonium bromide, and anhydrous ethanol. The mixture was stirred at room temperature under a N2 atmosphere for 2.0–5.0 h, followed by a hydrothermal reaction at 100–200 °C for 8.0–48.0 h. The mixture was then filtered, washed (with ethanol and deionized water), and vacuum dried (at 80 °C) to obtain a transition metal-doped manganese sulfide-cyclodextrin enzyme (denoted as MnMS2-CD). The preferred mass ratio of thiourea, hexadecyltrimethylammonium bromide, and cyclodextrin used in step (1) is 0.25:0.10:1; The preferred hydrothermal reaction temperature is 150~180 °C, and the time is 12.0~30.0 h.

[0009] This invention relates to a transition metal-doped manganese sulfide-cyclodextrin enzyme that can be used in a visible light-driven carbon dioxide reduction reaction to produce ethylene. Specific application methods are as follows: Transition metal-doped manganese sulfide-cyclodextrin biomimetic enzyme and deionized water are added to a CO2 photocatalytic reactor and dispersed evenly. CO2 is introduced into the reactor to replace the air, and the CO2 pressure is adjusted to 0.05~0.15 MPa (preferably 0.08~0.10 MPa). A 10~500 W (preferably 100~300 W) LED incandescent lamp is turned on as a visible light source, and the reaction is stirred at room temperature. The generated reduction product ethylene (the reduction product also includes a small amount of carbon monoxide and methane) is detected by online gas chromatography. The mass ratio of transition metal-doped manganese sulfide-cyclodextrin imitator and deionized water is 1:100~1:100000, preferably 1:1000~1:10000.

[0010] The technical concept of this invention includes: This invention mimics natural enzymes such as chlorophyll, promotes C-C bond coupling by mimicking enzyme structure, and biomimeticly catalyzes the efficient reduction of CO2 to produce ethylene.

[0011] 1. Using transition metal Fe 2+ Co 2+ Ni 2+Cu 2+ and Zn 2+ Regulation of Mn 2+ The electronic environment forms a biomimetic bimetallic synergistic catalytic center, promoting the formation of C-C bonds during CO2 reduction and facilitating the efficient generation of ethylene.

[0012] 2. The polyhydroxy structure of cyclodextrin provides a carrier for proton transfer and electron transport during CO2 reduction, further promoting the formation of C-C bonds during CO2 reduction and promoting the efficient generation of ethylene.

[0013] 3. By utilizing the hydrophobic cavity structure of cyclodextrin, mimicking the hydrophobic pocket of natural enzymes, a microscopic confined catalytic environment is provided for CC coupling during CO2 reduction, thereby enhancing the enrichment of hydrophobic species during CO2 reduction.

[0014] The above three methods promote the coupling of C-C bonds to form ethylene. The visible light-driven CO2 reduction method for ethylene production provided by this invention is not only green and environmentally friendly, energy-saving and emission-reducing, but also has high reduction product generation efficiency, high ethylene selectivity, and strong practicality. It is a green, efficient, and practical method for CO2 reduction to ethylene production with potential for actual industrial application. The biomimetic strategy used in this invention to improve the efficiency of CO2 reduction to ethylene production also has certain guiding value for improving the catalytic efficiency of other catalytic systems.

[0015] The beneficial effects of this invention are mainly reflected in: This invention utilizes a transition metal-doped manganese sulfide-cyclodextrin imitator (MnMS2-CD) as a catalyst for the reduction of CO2 to ethylene. This catalyst is ingeniously designed, novel in structure, and possesses excellent stability and low cost, showing broad application prospects. In the CO2 reduction to ethylene reaction, this catalyst exhibits high efficiency in the formation of reduction products, demonstrating good potential for industrial application. Simultaneously, its high ethylene selectivity significantly reduces energy consumption, carbon emissions, and cost inputs during product separation.

[0016] The reaction system of this invention uses visible light as an energy source, water as a solvent and hydrogen source, and operates at room temperature. The reaction conditions are mild, the operation is safe, and energy consumption is low. Furthermore, it eliminates the need for organic solvents, conforming to green chemistry principles and possessing both energy conservation, emission reduction, and industrial application potential. In addition, the biomimetic catalytic system of this invention provides a new strategy for the efficient reduction of CO2 to ethylene, and also offers valuable insights for improving the efficiency of related catalytic systems. Overall, this technology is green, efficient, and practical, representing a promising pathway for the resource utilization of CO2. Detailed Implementation

[0017] The present invention is further described below through specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0018] Examples 1-39 below describe the preparation of transition metal-doped manganese sulfide-cyclodextrin mimicry (MnMS2-CD); Examples 40-58 describe the application of transition metal-doped manganese sulfide-cyclodextrin mimicry (MnMS2-CD) in the visible light-driven reduction of carbon dioxide (CO2) to produce ethylene.

[0019] Nomenclature rules for transition metal-doped manganese sulfide-cyclodextrin enzyme-mimicking enzyme (MnMS2-CD) catalysts: MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@24h indicates that the transition metal in the sample preparation process was Fe. 2+ Mn in ethanol solution 2+ The molar concentration was 0.9 mol / L, Fe 2+ The molar concentration was 0.3 mol / L; the mass ratio of β-cyclodextrin to the volume of the ethanol solution was 150; the reaction was carried out with stirring at 25 °C for 12 h; and the reaction was carried out hydrothermally at 160 °C for 24 h.

[0020] Example 1

[0021] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ (Provided by manganese chloride tetrahydrate, the same below) Molar concentration is 0.9 mol / L, Fe 2+ (Provided by ferrous chloride tetrahydrate, the same below) The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. The resulting solid, along with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide, was dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed in the hydrothermal reactor and reacted hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was 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. The obtained material was named MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@24h.

[0022] Example 2

[0023] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.1 mol / L, Fe 2 +The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.24 g of a gray-black solid, named MnFeS2-βCD@0.1M@0.3M@150@25@12h@160@24h.

[0024] Example 3

[0025] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 1.0 mol / L, Fe 2 + The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under N2 atmosphere. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.91 g of a gray-black solid, named MnFeS2-βCD@1.0M@0.3M@150@25@12h@160@24h.

[0026] Example 4

[0027] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.01 mol / L, Fe 2+The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.11 g of a gray-black solid, named MnFeS2-βCD@0.01M@0.3M@150@25@12h@160@24h.

[0028] Example 5

[0029] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 2.0 mol / L, Fe 2 + The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under N2 atmosphere. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed and hydrothermally reacted at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 1.21 g of a grayish-black solid, named MnFeS2-βCD@2.0M@0.3M@150@25@12h@160@24h.

[0030] Example 6

[0031] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was reacted in 150 mL of a 0.1 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.43 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.1M@150@25@12h@160@24h.

[0032] Example 7

[0033] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was stirred in 150 mL of a 0.8 mol / L ethanol solution at 25 °C for 12.0 h under N2 atmosphere. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed and hydrothermally reacted at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.72 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.8M@150@25@12h@160@24h.

[0034] Example 8

[0035] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was reacted in 150 mL of a 0.01 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.18 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.01M@150@25@12h@160@24h.

[0036] Example 9

[0037] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was reacted in 150 mL of a 1.0 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 1.31 g of a gray-black solid, named MnFeS2-βCD@0.9M@1.0M@150@25@12h@160@24h.

[0038] Example 10

[0039] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was reacted in 150 mL of a 0.16 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out in a sealed hydrothermal reactor at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.42 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.16M@150@25@12h@160@24h.

[0040] Example 11

[0041] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was reacted in 150 mL of a 0.45 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol, and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed in the hydrothermal reactor and reacted hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.46 g of a gray-black solid, which was named MnFeS2-βCD@0.9M@0.45M@150@25@12h@160@24h.

[0042] Example 12

[0043] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was reacted in 150 mL of a 0.009 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.22 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.009@150@25@12h@160@24h.

[0044] Example 13

[0045] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was reacted in 150 mL of a 0.9 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 1.02 g of a grayish-black solid, named MnFeS2-βCD@0.9M@0.9M@150@25@12h@160@24h.

[0046] Example 14

[0047] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The reaction mixture was stirred for 12.0 h at 25 °C under a nitrogen atmosphere in 100 mL of 0.3 mol / L ethanol solution with a stirring temperature. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under a nitrogen atmosphere. The reaction mixture was then sealed in the hydrothermal reactor and hydrothermally reacted at 160 °C for 24.0 h under a nitrogen atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.62 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.3M@100@25@12h@160@24h.

[0048] Example 15

[0049] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The reaction was carried out in 200 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol, and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out in a sealed hydrothermal reactor at 160 °C for 24.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.66 g of a gray-black solid, which was named MnFeS2-βCD@0.9M@0.3M@200@25@12h@160@24h.

[0050] Example 16

[0051] In a 50 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2+The mixture was stirred in 10 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under N2 atmosphere. After filtration, the solid was washed with 3 × 20 mL of anhydrous ethanol. The resulting solid, along with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide, was dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed and hydrothermally reacted at 160 °C for 24.0 h under N2 atmosphere. After filtration, the solid was washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.34 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.3M@10@25@12h@160@24h.

[0052] Example 17

[0053] In a 1000 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2+ The mixture was reacted in 500 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.75 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.3M@500@25@12h@160@24h.

[0054] Example 18

[0055] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 20 °C for 12.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol, and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed in the hydrothermal reactor and reacted hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.61 g of a gray-black solid. This material was named MnFeS2-βCD@0.9M@0.3M@150@20@12h@160@24h.

[0056] Example 19

[0057] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 30 °C under N2 atmosphere with stirring for 12.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol, and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed in the hydrothermal reactor and reacted hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.72 g of a gray-black solid. This material was named MnFeS2-βCD@0.9M@0.3M@150@30@12h@160@24h.

[0058] Example 20

[0059] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 0 °C under a N2 atmosphere for 12.0 h. After filtration, the solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under a N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under a N2 atmosphere. After filtration, the solid was washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.09 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.3M@150@0@12h@160@24h.

[0060] Example 21

[0061] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 60 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.81 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.3M@150@60@12h@160@24h.

[0062] Example 22

[0063] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 8.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol, and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed in the hydrothermal reactor and reacted hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.54 g of a gray-black solid. This material was named MnFeS2-βCD@0.9M@0.3M@150@25@8h@160@24h.

[0064] Example 23

[0065] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 16.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.75 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.3M@150@25@16h@160@24h.

[0066] Example 24

[0067] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 2.0 h under N2 atmosphere. After filtration, the solid was washed with 3 × 20 mL of anhydrous ethanol. The resulting solid, along with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide, was dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed and hydrothermally reacted at 160 °C for 24.0 h under N2 atmosphere. After filtration, the solid was washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.34 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.3M@150@25@2h@160@24h.

[0068] Example 25

[0069] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 24.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out in a sealed hydrothermal reactor at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.81 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.3M@150@25@24h@160@24h.

[0070] Example 26

[0071] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol, and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed in the hydrothermal reactor and reacted hydrothermally at 150 °C for 24.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.63 g of a gray-black solid. This material was named MnFeS2-βCD@0.9M@0.3M@150@25@12h@150@24h.

[0072] Example 27

[0073] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 180 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.71 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.3M@150@25@12h@180@24h.

[0074] Example 28

[0075] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 100 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.48 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.3M@150@25@12h@100@24h.

[0076] Example 29

[0077] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed in the hydrothermal reactor and reacted hydrothermally at 200 °C for 24.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.73 g of a gray-black solid. This material was named MnFeS2-βCD@0.9M@0.3M@150@25@12h@200@24h.

[0078] Example 30

[0079] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol, and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed in the hydrothermal reactor and reacted hydrothermally at 160 °C for 12.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.51 g of a gray-black solid. This material was named MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@12h.

[0080] Example 31

[0081] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol, and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed in the hydrothermal reactor and reacted hydrothermally at 160 °C for 30.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.70 g of a gray-black solid, which was named MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@30h.

[0082] Example 32

[0083] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed in the hydrothermal reactor and reacted hydrothermally at 160 °C for 8.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.49 g of a gray-black solid. This material was named MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@8h.

[0084] Example 33

[0085] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 + The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 48.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The mixture was dried at 80 °C for 8.0 h to obtain 0.78 g of a gray-black solid, named MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@48h.

[0086] Example 34

[0087] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Co 2 +(Provided by cobalt chloride hexahydrate) The reaction was carried out in 150 mL of 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. The resulting solid, along with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide, was dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere with a sealed hydrothermal reactor. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.91 g of a gray-black solid, which was named MnCoS2-βCD@0.9M@0.3M@150@25@12h@160@24h.

[0088] Example 35

[0089] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Ni 2 + (Provided by nickel chloride hexahydrate) The reaction was carried out in 150 mL of 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. The resulting solid, along with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide, was dispersed in 50 mL of anhydrous ethanol in a 100 mL hydrothermal reactor at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere with a sealed hydrothermal reactor. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol, and then washed with 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.42 g of a gray-black solid. The resulting material was named MnNiS2-βCD@0.9M@0.3M@150@25@12h@160@24h.

[0090] Example 36

[0091] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Cu 2 +(Provided by copper chloride dihydrate) The reaction was carried out in 150 mL of 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with thiourea (0.25 g) and hexadecyltrimethylammonium bromide (0.10 g) in 50 mL of anhydrous ethanol, and stirred at room temperature under N2 atmosphere for 3.0 h. The hydrothermal reactor was then sealed and reacted hydrothermally at 160 °C under N2 atmosphere for 24.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.81 g of a gray-black solid, named MnCuS2-βCD@0.9M@0.3M@150@25@12h@160@24h.

[0092] Example 37

[0093] In a 250 mL single-necked flask, β-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Zn 2 + The reaction mixture was stirred for 12.0 h at 25 °C in 150 mL of 0.3 mol / L ethanol solution (provided by anhydrous zinc chloride salt) under N2 atmosphere. The solid was then filtered and washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the solid was dispersed with thiourea (0.25 g) and hexadecyltrimethylammonium bromide (0.10 g) in 50 mL of anhydrous ethanol and stirred at room temperature for 3.0 h under N2 atmosphere. The reaction mixture was then sealed in the hydrothermal reactor and hydrothermally reacted at 160 °C for 24.0 h under N2 atmosphere. The solid was filtered, washed with 3 × 20 mL of anhydrous ethanol and then with 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.73 g of a gray-black solid, named MnZnS2-βCD@0.9M@0.3M@150@25@12h@160@24h.

[0094] Example 38

[0095] In a 250 mL single-necked flask, α-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2 +The mixture was reacted in 150 mL of a 0.3 mol / L ethanol solution at 25 °C under N2 atmosphere with stirring for 12.0 h. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol, and stirred at room temperature for 3.0 h under N2 atmosphere. The mixture was then sealed in the hydrothermal reactor and reacted hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.58 g of a gray-black solid. This material was named MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@24h.

[0096] Example 39

[0097] In a 250 mL single-necked flask, γ-cyclodextrin (1.00 g) was suspended in Mn... 2+ The molar concentration is 0.9 mol / L, Fe 2+ The mixture was stirred in 150 mL of a 0.3 mol / L ethanol solution at 25 °C for 12.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol. In a 100 mL hydrothermal reactor, the resulting solid was dispersed with 0.25 g of thiourea and 0.10 g of hexadecyltrimethylammonium bromide in 50 mL of anhydrous ethanol. The mixture was stirred at room temperature for 3.0 h under N2 atmosphere. The reaction was then carried out hydrothermally at 160 °C for 24.0 h under N2 atmosphere. The mixture was filtered, and the resulting solid was washed with 3 × 20 mL of anhydrous ethanol and 3 × 20 mL of deionized water. The solid was dried at 80 °C for 8.0 h to obtain 0.43 g of a gray-black solid. This material was named MnFeS2-γCD@0.9M@0.3M@150@25@12h@160@24h.

[0098] Example 40

[0099] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD catalyst (0.9 M 0.3 M 150 25 12 h 160 24 h) 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 200 W 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 overall reduction product formation efficiency was 591 μmol / (g). Cat.(·h), of which ethylene selectivity is 97%, carbon monoxide selectivity is 2%, and methane selectivity is 1%.

[0100] Example 41

[0101] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD catalyst (0.9 M 0.3 M 150 25 12 h 160 24 h) 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 then sealed. A 200 W LED incandescent light source was turned on, 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 overall reduction product formation efficiency was 521 μmol / (g). Cat. ·h), of which ethylene selectivity is 95%, carbon monoxide selectivity is 3%, and methane selectivity is 2%.

[0102] Example 42

[0103] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD catalyst (0.9 M 0.3 M 150 25 12 h 160 24 h) 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 then sealed. A 200 W 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 overall reduction product formation efficiency was 536 μmol / (g). Cat. ·h), of which ethylene selectivity is 94%, carbon monoxide selectivity is 3%, and methane selectivity is 3%.

[0104] Example 43

[0105] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD catalyst (0.9 M 0.3 M 150 25 12 h 160 24 h) 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 then sealed. A 200 W 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 overall reduction product formation efficiency was 421 μmol / (g). Cat. ·h), of which ethylene selectivity is 90%, carbon monoxide selectivity is 6%, and methane selectivity is 4%.

[0106] Example 44

[0107] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@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 then sealed. A 200 W 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 overall reduction product formation efficiency was 451 μmol / (g). Cat. ·h), of which ethylene selectivity is 89%, carbon monoxide selectivity is 5%, and methane selectivity is 6%.

[0108] Example 45

[0109] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@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 100 W 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 overall reduction product formation efficiency was 471 μmol / (g). Cat. ·h), of which ethylene selectivity is 90%, carbon monoxide selectivity is 2%, and methane selectivity is 8%.

[0110] Example 46

[0111] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@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 300 W 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 overall reduction product formation efficiency was 510 μmol / (g). Cat. ·h), of which ethylene selectivity is 92%, carbon monoxide selectivity is 2%, and methane selectivity is 6%.

[0112] Example 47

[0113] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@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 10 W LED incandescent light source was turned on, 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 overall reduction product formation efficiency was 172 μmol / (g). Cat. (·h), of which ethylene selectivity is 82%, carbon monoxide selectivity is 12%, and methane selectivity is 6%.

[0114] Example 48

[0115] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@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 500 W 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 overall reduction product formation efficiency was 428 μmol / (g). Cat. (·h), of which ethylene selectivity is 85%, carbon monoxide selectivity is 11%, and methane selectivity is 4%.

[0116] Example 49

[0117] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@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 then sealed. A 200 W 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 overall reduction product formation efficiency was 561 μmol / (g). Cat. ·h), of which ethylene selectivity is 95%, carbon monoxide selectivity is 2%, and methane selectivity is 3%.

[0118] Example 50

[0119] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD catalyst (0.9 M 0.3 M 150 25 12 h 160 24 h) 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 then sealed. A 200 W 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 overall reduction product formation efficiency was 546 μmol / (g). Cat. ·h), of which ethylene selectivity is 94%, carbon monoxide selectivity is 2%, and methane selectivity is 4%.

[0120] Example 51

[0121] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD@0.9M@0.3M@150@25@12h@160@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 then sealed. A 200 W 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 overall reduction product formation efficiency was 467 μmol / (g). Cat. ·h), of which ethylene selectivity is 90%, carbon monoxide selectivity is 2%, and methane selectivity is 8%.

[0122] Example 52

[0123] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-βCD catalyst (0.9 M 0.3 M 150 25 12 h 160 24 h) 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 then sealed. A 200 W 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 overall reduction product formation efficiency was 521 μmol / (g). Cat. (·h), of which ethylene selectivity is 88%, carbon monoxide selectivity is 7%, and methane selectivity is 5%.

[0124] Example 53

[0125] In a CO2 photocatalytic reactor, 10 mg of MnCoS2-βCD catalyst (0.9 M 0.3 M 150 25 12 h 160 24 h) 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 200 W LED incandescent light source was turned on, 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 overall reduction product formation efficiency was 415 μmol / (g). Cat. (·h), of which ethylene selectivity is 78%, carbon monoxide selectivity is 22%, and methane selectivity is 10%.

[0126] Example 54

[0127] In a CO2 photocatalytic reactor, 10 mg of MnNiS2-βCD@0.9M@0.3M@150@25@12h@160@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 200 W 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 overall reduction product formation efficiency was 342 μmol / (g). Cat. (·h), of which ethylene selectivity is 74%, carbon monoxide selectivity is 22%, and methane selectivity is 4%.

[0128] Example 55

[0129] In a CO2 photocatalytic reactor, 10 mg of MnCuS2-βCD@0.9M@0.3M@150@25@12h@160@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 200 W 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 overall reduction product formation efficiency was 258 μmol / (g). Cat. (·h), of which ethylene selectivity is 71%, carbon monoxide selectivity is 24%, and methane selectivity is 5%.

[0130] Example 56

[0131] In a CO2 photocatalytic reactor, 10 mg of MnZnS2-βCD catalyst (0.9 M 0.3 M 150 25 12 h 160 24 h) 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 200 W LED incandescent light source was turned on, 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 overall reduction product formation efficiency was 146 μmol / (g). Cat. ·h), of which ethylene selectivity is 70%, carbon monoxide selectivity is 12%, and methane selectivity is 18%.

[0132] Example 57

[0133] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-αCD@0.9M@0.3M@150@25@12h@160@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 200 W 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 overall reduction product formation efficiency was 481 μmol / (g). Cat. (·h), of which ethylene selectivity is 93%, carbon monoxide selectivity is 6%, and methane selectivity is 1%.

[0134] Example 58

[0135] In a CO2 photocatalytic reactor, 10 mg of MnFeS2-γCD@0.9M@0.3M@150@25@12h@160@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 200 W 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 overall reduction product formation efficiency was 421 μmol / (g). Cat. ·h), of which ethylene selectivity is 92%, carbon monoxide selectivity is 6%, and methane selectivity is 2%.

Claims

1. A transition metal-doped manganese sulfide-cyclodextrin enzyme, characterized in that, It is prepared as follows: (1) Suspend cyclodextrin in a solution containing Mn 2+ and M 2+ In an ethanol solution, under a N2 atmosphere, the mixture was stirred at 0–60 °C for 2.0–24.0 h, followed by filtration and washing to obtain the product containing adsorbed Mn. 2+ and M 2+ cyclodextrin solids; M 2+ For Fe 2+ Co 2+ Ni 2+ Cu 2+ or Zn 2+ ; (2) The adsorbed Mn obtained in step (1) 2+ and M 2+ The solid cyclodextrin was mixed with thiourea, hexadecyltrimethylammonium bromide and anhydrous ethanol, and stirred at room temperature under N2 atmosphere for 2.0-5.0 h. Then, a hydrothermal reaction was carried out at 100-200 °C for 8.0-48.0 h. After that, the mixture was filtered, washed and vacuum dried to obtain transition metal doped manganese sulfide-cyclodextrin enzyme.

2. The transition metal-doped manganese sulfide-cyclodextrin enzyme as described in claim 1, characterized in that, In step (1), the cyclodextrin is one or more of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

3. The transition metal-doped manganese sulfide-cyclodextrin enzyme as described in claim 1, characterized in that, Step (1) contains Mn 2 + and M 2+ In ethanol solution, Mn 2+ Provided by manganese chloride and its hydrate, manganese sulfate and its hydrate, and manganese nitrate and its hydrate; M 2+ It is provided by its hydrochloride, sulfate, nitrate and hydrate.

4. The transition metal-doped manganese sulfide-cyclodextrin enzyme as described in claim 1, characterized in that, Step (1) contains Mn 2 + and M 2+ In ethanol solution, Mn 2+ Concentration 0.01~2.00 mol / L, M 2+ Concentration 0.01~1.00 mol / L; M 2+ With Mn 2+ The molar concentration ratio is 1:100~1:

1.

5. The transition metal-doped manganese sulfide-cyclodextrin enzyme as described in claim 1, characterized in that, In step (1), cyclodextrin containing Mn 2+ and M 2+ The mass-to-volume ratio of the ethanol solution is 1:10~1:500, g / mL.

6. The transition metal-doped manganese sulfide-cyclodextrin enzyme as described in claim 1, characterized in that, In step (2), the mass ratio of thiourea, hexadecyltrimethylammonium bromide and cyclodextrin used in step (1) is 0.25:0.10:

1.

7. The transition metal-doped manganese sulfide-cyclodextrin enzyme as described in claim 1, characterized in that, In step (2), the hydrothermal reaction temperature is 150~180 °C and the time is 12.0~30.0 h.

8. The application of the transition metal-doped manganese sulfide-cyclodextrin mimicry as described in claim 1 in the visible light-driven carbon dioxide reduction reaction to prepare ethylene.

9. The application as described in claim 8, characterized in that, The method is as follows: Transition metal-doped manganese sulfide-cyclodextrin enzyme and deionized water were added to a CO2 photocatalytic reactor and dispersed evenly. CO2 was introduced into the reactor to replace the air, and the CO2 pressure was adjusted to 0.05~0.15 MPa. A 10~500 W LED incandescent lamp was turned on as a visible light source, and the reaction was stirred at room temperature. The generated reduction product, ethylene, was detected by online gas chromatography. The mass ratio of transition metal-doped manganese sulfide-cyclodextrin imitator and deionized water is 1:100~1:100000.