Cyclodextrin modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD as well as preparation method and application thereof

Abstract

The invention discloses a cyclodextrin modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD as well as a preparation method and application thereof. The preparation method of the biomimetic catalyst comprises the following steps: suspending cyclodextrin in an ethanol solution containing ternary transition metal ions, and carrying out a stirring adsorption reaction in an N2 atmosphere to obtain a cyclodextrin suspension adsorbing transition metal ions M < 2 + >; dropwise adding an ethanol solution into the suspension liquid, stirring and reacting in a dark place, and centrifuging, washing and vacuum drying the obtained suspension liquid to obtain the biomimetic catalyst. According to the method for preparing ethylene through visible-light-driven CO2 reduction, visible light serves as an energy source at the room temperature, water serves as a solvent and a hydrogen source at the same time, and the method is environmentally friendly, saves energy, reduces emission, is high in reduction product generation efficiency and high in ethylene selectivity, and can be applied to preparation of ethylene through visible-light-driven CO2 reduction. The method is high in practicability, and is a green, efficient and practical method for preparing ethylene through CO2 reduction.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of industrial catalysis and biomimetic catalysis, and particularly relates to a cyclodextrin modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD, a preparation method thereof and application of the catalyst in preparation of ethylene from carbon dioxide reduction. BACKGROUND

[0002] The carbon element in organic chemical industry mainly comes from fossil resources such as coal, petroleum and natural gas. The carbon element is not only non-renewable, but also flows in one direction and is finally discharged into the atmosphere in the form of carbon dioxide (CO2), causing serious greenhouse effect. In view of the current over-reliance of chemical industry on non-renewable fossil resources and the environmental problems caused by CO2 emission, if CO2 can be converted into organic chemical raw materials or intermediates, not only can the environmental problems caused by CO2 emission be alleviated, helping to achieve "carbon peak and carbon neutralization", but also can provide new "carbon resources" for the development of organic chemical industry, avoid the dependence of chemical industry on non-renewable fossil resources, realize the recycling of carbon elements, promote social sustainable development, and have great economic value and social significance.

[0003] Carbon dioxide (CO2) can be converted into ethylene. At present, the more commonly used conversion is visible light driven CO2 catalytic reduction, which not only realizes the reduction conversion of CO2 at room temperature, has mild conditions, and has the potential to use abundant renewable solar energy as energy source, is a promising conversion way of CO2 catalytic reduction. Therefore, visible light driven CO2 reduction to prepare ethylene can not only effectively utilize the CO2 byproduct of industry, alleviate the greenhouse effect, but also provide new "carbon source" for chemical industry, promote carbon cycle and social sustainable development.

[0004] Although visible light driven CO2 reduction to prepare ethylene is a promising way to efficiently utilize CO2, alleviate the greenhouse effect caused by it, provide new "carbon source" for chemical industry and realize social sustainable development, but there is a wide gap between the conversion rate of visible light driven CO2 catalytic reduction to prepare ethylene and the actual application demand. Therefore, developing an efficient visible light catalytic way to realize the efficient generation of ethylene from CO2 is the urgent demand of current chemical industry and the inevitable way of social sustainable development. SUMMARY

[0005] In order to overcome the deficiencies of the existing visible light driven CO2 catalytic reduction to prepare ethylene technology, the purpose of the present application is to provide a cyclodextrin modified cobalt copper manganese ternary alloy particle biomimetic catalyst CoCuMn-CD and its preparation method and its application as a catalyst in the reduction of carbon dioxide (CO2) to prepare ethylene. The present application constructs a space structure and an electronic environment suitable for C-C coupling with ternary transition metals, forms a biomimetic three-metal synergistic catalytic center, promotes the formation of C-C bond in the CO2 reduction process, and promotes the efficient generation of ethylene; with the multi-hydroxyl structure of cyclodextrin, the proton transfer and electron transfer in the CO2 reduction process are promoted; with the help of the hydrophobic cavity structure of cyclodextrin, the hydrophobic pocket of natural enzymes is simulated to provide a micro-limited catalytic environment, and the enrichment of hydrophobic species in the CO2 reduction process is strengthened, and the three methods promote the coupling of C-C bond to form ethylene.

[0006] The present application discloses a cyclodextrin modified cobalt copper manganese ternary alloy particle biomimetic catalyst CoCuMn-CD, which contains ternary transition metals cobalt, copper and manganese and cyclodextrin combined with ternary alloy particles, and cyclodextrin as a carrier adsorbs metal ions.

[0007] Further, the present application limits the cyclodextrin to be one or any combination of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.

[0008] Further, the present application limits the molar ratio of ternary transition metals cobalt, copper and manganese to be 1:0.1-100:0.1-100.

[0009] Further, the present application limits the preparation method of the cyclodextrin modified cobalt copper manganese ternary alloy particle biomimetic catalyst CoCuMn-CD, which specifically comprises the following steps:

[0010] 1) adsorption: suspend cyclodextrin in an ethanol solution containing Co 2+ , Cu 2+ and Mn 2+ , stir and adsorb under an inert atmosphere at 0-60 DEG C in the dark for 1.0-12.0 h to obtain a cyclodextrin suspension adsorbed with metal ions;

[0011] 2) reduction: under an inert atmosphere and in the dark, add sodium borohydride ethanol solution dropwise to the cyclodextrin suspension adsorbed with metal ions obtained in step 1) at 0-60 DEG C for 3.0-24.0 h to carry out reduction reaction;

[0012] 3) post-treatment: centrifuge, wash and vacuum dry the reduction product suspension obtained in step 2) to obtain the cyclodextrin modified cobalt copper manganese ternary alloy particle biomimetic catalyst CoCuMn-CD.

[0013] Further, the present application limits the cyclodextrin in step 1) to one or any combination of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin; the concentration of the transition metal ions Co2 + , Cu2 + , and Mn2 + is 0.01 mol / L to 1.00 mol / L, preferably 0.1 mol / L to 0.50 mol / L; the molar ratio of the transition metal ions Co2+, Cu2+, and Mn2+ is 1:0.1-100:0.1-100, preferably 1:1-10:1-10; and the ratio of the mass of the cyclodextrin to the volume of the transition metal ion ethanol solution is 1:10-500, preferably 1:100-200.

[0014] Further, the present application limits the concentration of sodium borohydride in step 2) to 0.01 mol / L to 1.00 mol / L, preferably 0.1 mol / L to 0.50 mol / L; the molar ratio of the total number of transition metal ions to sodium borohydride is 1:0.5-10, preferably 1:1-1:5; the reaction temperature is 20℃ to 40℃; and the reaction time is 6.0h to 18.0h.

[0015] Further, the present application limits Co 2+ , Cu 2+ , and Mn 2+ to be provided by their hydrochloride salts and hydrates, sulfate salts and hydrates, or nitrate salts and hydrates.

[0016] Further, the present application limits the use of the cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD in the visible light-driven reduction of carbon dioxide to prepare ethylene.

[0017] Further, the present application limits the application method to be: dispersing the cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD in deionized water which is also a solvent and a hydrogen source, replacing the air in the reactor with CO2, adjusting the CO2 pressure to 0.05MPa to 0.15MPa, and reacting under the irradiation of a 10W to 500W LED light source to obtain the reduction product ethylene; the mass ratio of the cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD to the deionized water is 1:100 to 1:100000, preferably 1:1000 to 1:10000; the power of the visible light source is 100W to 300W; and the reaction pressure is 0.08MPa to 0.10MPa.

[0018] By using the above-mentioned technology, the present application has the following advantages compared with the prior art:

[0019] The present application simulates natural enzymes such as chlorophyll to promote C-C bond coupling by simulating enzyme structure to prepare ethylene by efficient reduction of CO2: (1) transition metals cobalt (Co), copper (Cu) and manganese (Mn) are used to regulate the spatial structure and electronic environment of C-C coupling, and a biomimetic three-metal synergistic catalytic center is formed to promote the formation of C-C bond in the CO2 reduction process and promote the efficient generation of ethylene; (2) the multi-hydroxyl structure of cyclodextrin is used to provide a carrier for proton transfer and electron transport in the CO2 reduction process, further promoting the formation of C-C bond in the CO2 reduction process and promoting the efficient generation of ethylene; (3) the hydrophobic cavity structure of cyclodextrin is used to simulate the hydrophobic pocket of natural enzymes to provide a micro-limited catalytic environment for C-C coupling in the CO2 reduction process, and to strengthen the enrichment of hydrophobic species in the CO2 reduction process. The three methods promote the coupling of C-C bond to form ethylene; the method for preparing ethylene by visible light driven CO2 reduction provided by the present application is not only green, energy-saving and emission-reducing, but also has high reduction product generation efficiency and high ethylene selectivity, and has strong practicability. It is a green, efficient and practical method for preparing ethylene by CO2 reduction, which has great industrial application potential.

[0020] The present application uses cyclodextrin to modify cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD as a biomimetic catalyst for preparing ethylene by CO2 reduction. The catalyst has clever design, novel structure, stable properties and low cost, and has wide application range. Moreover, in the reaction of preparing ethylene by CO2 reduction, the reduction product generation efficiency is high, the ethylene selectivity is high, the energy consumption caused by the separation of the reduction product is effectively reduced, carbon emission and cost investment are reduced, and the present application is a green, efficient and practical technology for preparing ethylene by CO2 reduction, which has great industrial application potential. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The Fourier transform infrared (FT-IR) spectra of the biomimetic catalyst CoCuMn-βCD prepared in Example 1 and its raw materials β-cyclodextrin and CoCuMn. DETAILED DESCRIPTION

[0022] The present application will be further described below in combination with the drawings and specific examples, but the protection scope of the present application is not limited thereto.

[0023] The naming rules of the cyclodextrin modified cobalt-copper-manganese ternary alloy particle (CoCuMn-CD) biomimetic catalyst. CoCuMn-βCD@0.1M@0.1M@0.2M@0.1M@300@25@2h@30@24h, indicates that the molar concentration of transition metal in the ethanol solution during sample preparation is Co2+ 0.1 mol / L, Cu 2+ 0.1 mol / L, Mn 2+ 0.2 mol / L; the molar concentration of the sodium borohydride ethanol solution was 0.1 mol / L; the mass of the β-cyclodextrin to the volume of the ethanol solution was 300; 2 h of stirring at 25 °C in the dark; 24 h of stirring at 30 °C in the dark.

[0024] Example 1 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ 0.1 mol / L, Cu 2+ 0.1 mol / L and Mn 2+ mol / L ethanol solution (150 mL) under N2atmosphere, 2.0 h of stirring at 25 °C in the dark. Freshly prepared NaBH4(0.1 mol / L) ethanol solution was added dropwise under stirring, and nitrogen was purged for 5.0 min. 12.0 h of stirring at 25 °C in the dark. The resulting solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried at 80 °C under vacuum for 8.0 h to obtain a gray-black solid, 0.5587 g. The resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h, and the Fourier transform infrared (FT-IR) spectrum of the resulting biomimetic catalyst CoCuMn-βCD and CoCuMn is shown in FIG. 1. Figure 1 The elemental composition analysis (ICP) of the biomimetic catalyst CoCuMn-βCD prepared in Example 1 is shown in Table 1.

[0025] Figure 1 In the infrared spectrum of the CoCuMn-βCD biomimetic catalyst shown in FIG. 1, characteristic absorption signals from both components of β-cyclodextrin (βCD) and CoCuMn alloy particles can be clearly identified. The absorption peak at 600 cm -1 belongs to the characteristic vibration of the CoCuMn alloy particle component, and β-cyclodextrin has no obvious absorption in this wave number range, indicating that the CoCuMn alloy particle component exists in the catalyst system; at the same time, at about 1025 cm -1 , 1150 cm -1 , and 2900 cm -1The characteristic structural vibration of β-cyclodextrin is the apparent absorption peak at the same position, which is clearly visible in the spectrum of the CoCuMn-βCD biomimetic catalyst, but not particularly obvious in the spectrum of the single CoCuMn component. Therefore, the appearance of the above characteristic absorption indicates that the FT-IR spectrum of the biomimetic catalyst CoCuMn-βCD not only contains the characteristic absorption peaks of the CoCuMn alloy particles (600 cm -1 nearby), but also contains the characteristic absorption peaks of β-cyclodextrin (1025 cm -1 , 1150 cm -1 , 2900 cm -1 , etc.), indicating that β-cyclodextrin has been successfully introduced into the biomimetic catalyst material. The infrared spectrum analysis result shows that the CoCuMn-βCD biomimetic catalyst is a composite composed of CoCuMn alloy particles and β-cyclodextrin, and the successful synthesis of the biomimetic catalyst CoCuMn-βCD.

[0026] Table 1 Element composition analysis (ICP) of the biomimetic catalyst CoCuMn-βCD prepared in Example 1

[0027]

[0028]

[0029] The results in Table 1 show that the average content of cobalt element in the material is 11.4094%, the average content of copper element is 11.5636%, and the average content of manganese element is 8.0487%, and the three elements are relatively stably coexisting in the biomimetic catalyst material, which proves that cobalt, copper and manganese have been successfully introduced into the structure of the synthesized biomimetic catalyst as multi-metal active centers.

[0030] In Example 2, β-cyclodextrin (0.50 g) was suspended in Co 2+ , Cu 2+ and Mn 2+ ethanol solutions (150 mL) with a molar concentration of 0.01 mol / L, 0.01 mol / L and 0.01 mol / L respectively, under N2 atmosphere, at 25°C, and stirred in the dark for 2.0 h. Freshly prepared NaBH4 (0.1 mol / L) ethanol solution was added dropwise under stirring, and nitrogen was blown for 5.0 min. The reaction was stirred in the dark at 25°C for 12.0 h. The obtained solid was centrifuged, washed with 3×20 mL of anhydrous ethanol, washed with 5×20 mL of deionized water, and dried at 80°C under vacuum for 8.0 h to obtain a gray-black solid 0.5313 g, which was named as CoCuMn-βCD@0.01M@0.01M@0.01M@0.1M@300@25@2h@25@12h.

[0031] Example 3 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molar concentration of 0.05 mol / L, Cu 2+ at a molar concentration of 0.05 mol / L and Mn 2+ in ethanol (150 mL) at a molar concentration of 0.05 mol / L, under N2atmosphere, at 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 mol / L) in ethanol was added dropwise while stirring, with nitrogen purging for 5.0 min. The reaction was stirred in the dark at 25 °C for 12.0 h. The resulting solid was washed with 3 x 20 mL of anhydrous ethanol, 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a dark gray solid, 0.5427 g, which was named CoCuMn-βCD@0.05M@0.05M@0.05M@0.1M@300@25@2h@25@12h.

[0032] Example 4 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molar concentration of 0.5 mol / L, Cu 2+ at a molar concentration of 0.5 mol / L and Mn 2+ in ethanol (150 mL) at a molar concentration of 0.5 mol / L, under N2atmosphere, at 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 mol / L) in ethanol was added dropwise while stirring, with nitrogen purging for 5.0 min. The reaction was stirred in the dark at 25 °C for 12.0 h. The resulting solid was washed with 3 x 20 mL of anhydrous ethanol, 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a dark gray solid, 0.5559 g, which was named CoCuMn-βCD@0.5M@0.5M@0.5M@0.1M@300@25@2h@25@12h.

[0033] Example 5 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molar concentration of 1.0 mol / L, Cu 2+ at a molar concentration of 1.0 mol / L and Mn 2+In a 1.0 mol / L ethanol solution (150 mL), under a N2 atmosphere, at 25 °C, the mixture was stirred in the dark for 2.0 h. Freshly prepared NaBH4 (0.1 mol / L) ethanol solution was added dropwise with stirring, and the mixture was purged with nitrogen for 5.0 min. The reaction was continued at 25 °C with stirring in the dark for 12.0 h. After centrifugation, the solid was washed with 3 × 20 mL of anhydrous ethanol and 5 × 20 mL of deionized water. The solid was then dried under vacuum at 80 °C for 8.0 h to obtain 0.5579 g of a gray-black solid. The obtained material was named CoCuMn-βCD@1.0M@1.0M@1.0M@0.1M@300@25@2h@25@12h.

[0034] Example 6: In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co... 2+ The molar concentration is 0.1 mol / L, Cu 2+ The molar concentration was 0.01 mol / L and Mn 2+ In a 0.1 mol / L ethanol solution (150 mL), under a N2 atmosphere, at 25 °C, the mixture was stirred in the dark for 2.0 h. Freshly prepared NaBH4 (0.1 mol / L) ethanol solution was added dropwise with stirring, and the mixture was purged with nitrogen for 5.0 min. The reaction was continued at 25 °C with stirring in the dark for 12.0 h. After centrifugation, the solid was washed with 3 × 20 mL of anhydrous ethanol and 5 × 20 mL of deionized water. The solid was then dried under vacuum at 80 °C for 8.0 h to obtain 0.5453 g of a gray-black solid. The obtained material was named CoCuMn-βCD@0.1M@0.01M@0.1M@0.1M@300@25@2h@25@12h.

[0035] Example 7: In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co... 2+ The molar concentration is 0.1 mol / L, Cu 2+ The molar concentration was 0.05 mol / L and Mn 2+ In a 0.1 mol / L ethanol solution (150 mL), under a N2 atmosphere, at 25 °C, the mixture was stirred in the dark for 2.0 h. Freshly prepared NaBH4 (0.1 mol / L) ethanol solution was added dropwise with stirring, and the mixture was purged with nitrogen for 5.0 min. The reaction was continued at 25 °C with stirring in the dark for 12.0 h. After centrifugation, the solid was washed with 3 × 20 mL of anhydrous ethanol and 5 × 20 mL of deionized water. The solid was then dried under vacuum at 80 °C for 8.0 h to obtain 0.5487 g of a gray-black solid. The obtained material was named CoCuMn-βCD@0.1M@0.05M@0.1M@0.1M@300@25@2h@25@12h.

[0036] Example 8: In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co... 2+0.1 M, Cu 2+ 0.5 M, and Mn 2+ in ethanol (150 mL) at 0.1 M, under N2atmosphere, at 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise while stirring, with a nitrogen purge for 5.0 min. The reaction was stirred in the dark at 25 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a dark gray solid, 0.5566 g, which was named CoCuMn-βCD@0.1M@0.5M@0.1M@0.1M@300@25@2h@25@12h.

[0037] Example 9 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ 0.1 M, Cu 2+ 1.0 M, and Mn 2+ in ethanol (150 mL) at 0.1 M, under N2atmosphere, at 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise while stirring, with a nitrogen purge for 5.0 min. The reaction was stirred in the dark at 25 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a dark gray solid, 0.5571 g, which was named CoCuMn-βCD@0.1M@1.0M@0.1M@0.1M@300@25@2h@25@12h.

[0038] Example 10 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ 0.1 M, Cu 2+ 0.1 M, and Mn 2+ in ethanol (150 mL) at 0.01 M, under N2atmosphere, at 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise while stirring, with a nitrogen purge for 5.0 min. The reaction was stirred in the dark at 25 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a dark gray solid, 0.5432 g, which was named CoCuMn-βCD@0.1M@0.1M@0.01M@0.1M@300@25@2h@25@12h.

[0039] Example 11 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+ in ethanol (150 mL) at a molarity of 0.05 mol / L, under N2atmosphere, at 25 °C, stirred for 2.0 h in the dark. Freshly prepared NaBH4(0.1 mol / L) in ethanol was added dropwise under stirring, purged with nitrogen for 5.0 min. The reaction was stirred for 12.0 h at 25 °C in the dark. The solid was centrifuged, washed with 3 x 20 mL of absolute ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a grey-black solid of 0.5481 g, the resulting material was named CoCuMn-βCD@0.1M@0.1M@0.05M@0.1M@300@25@2h@25@12h.

[0040] Example 12 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+ in ethanol (150 mL) at a molarity of 0.5 mol / L, under N2atmosphere, at 25 °C, stirred for 2.0 h in the dark. Freshly prepared NaBH4(0.1 mol / L) in ethanol was added dropwise under stirring, purged with nitrogen for 5.0 min. The reaction was stirred for 12.0 h at 25 °C in the dark. The solid was centrifuged, washed with 3 x 20 mL of absolute ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a grey-black solid of 0.5557 g, the resulting material was named CoCuMn-βCD@0.1M@0.1M@0.5M@0.1M@300@25@2h@25@12h.

[0041] Example 13 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+In a 1.0 mol / L ethanol solution (150 mL), under a N2 atmosphere, at 25 °C, the mixture was stirred in the dark for 2.0 h. Freshly prepared NaBH4 (0.1 mol / L) ethanol solution was added dropwise with stirring, and the mixture was purged with nitrogen for 5.0 min. The reaction was continued at 25 °C with stirring in the dark for 12.0 h. After centrifugation, the solid was washed with 3 × 20 mL of anhydrous ethanol and 5 × 20 mL of deionized water. The solid was then dried under vacuum at 80 °C for 8.0 h to obtain 0.5569 g of a gray-black solid. The obtained material was named CoCuMn-βCD@0.1M@0.1M@1.0M@0.1M@300@25@2h@25@12h.

[0042] Example 14: In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co... 2+ The molar concentration is 0.1 mol / L, Cu 2+ The molar concentration was 0.1 mol / L and Mn 2+ In a 0.1 mol / L ethanol solution (150 mL), under a N2 atmosphere, at 25 °C, the mixture was stirred in the dark for 2.0 h. Freshly prepared NaBH4 (0.01 mol / L) ethanol solution was added dropwise with stirring, and the mixture was purged with nitrogen for 5.0 min. The reaction was continued at 25 °C with stirring in the dark for 12.0 h. After centrifugation, the solid was washed with 3 × 20 mL of anhydrous ethanol and 5 × 20 mL of deionized water. The solid was then dried under vacuum at 80 °C for 8.0 h to obtain 0.5109 g of a gray-black solid. The obtained material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.01M@300@25@2h@25@12h.

[0043] Example 15: In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co... 2+ The molar concentration is 0.1 mol / L, Cu 2+ The molar concentration was 0.1 mol / L and Mn 2+ In a 0.1 mol / L ethanol solution (150 mL), under a N2 atmosphere, at 25 °C, the mixture was stirred in the dark for 2.0 h. Freshly prepared NaBH4 (0.02 mol / L) ethanol solution was added dropwise with stirring, and the mixture was purged with nitrogen for 5.0 min. The reaction was continued at 25 °C with stirring in the dark for 12.0 h. After centrifugation, the solid was washed with 3 × 20 mL of anhydrous ethanol and 5 × 20 mL of deionized water. The solid was then dried under vacuum at 80 °C for 8.0 h to obtain 0.5213 g of a gray-black solid. The obtained material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.02M@300@25@2h@25@12h.

[0044] Example 16: In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co... 2+0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 150 mL of ethanol solution with 0.1 Molar concentration, under N2atmosphere, 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.05 Molar) ethanol solution was added dropwise with stirring, nitrogen purging for 5.0 min. 25 °C, stirring in the dark for 12.0 h. Centrifugation, 3 x 20 mL of anhydrous ethanol washing the resulting solid, 5 x 20 mL of deionized water washing the resulting solid, 80 °C vacuum drying for 8.0 h, 0.5321 g of gray-black solid was obtained, the resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.05M@300@25@2h@25@12h.

[0045] Example 17 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ 0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 150 mL of ethanol solution with 0.1 Molar concentration, under N2atmosphere, 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.08 Molar) ethanol solution was added dropwise with stirring, nitrogen purging for 5.0 min. 25 °C, stirring in the dark for 12.0 h. Centrifugation, 3 x 20 mL of anhydrous ethanol washing the resulting solid, 5 x 20 mL of deionized water washing the resulting solid, 80 °C vacuum drying for 8.0 h, 0.5447 g of gray-black solid was obtained, the resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.08M@300@25@2h@25@12h.

[0046] Example 18 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ 0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 150 mL of ethanol solution with 0.1 Molar concentration, under N2atmosphere, 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.2 Molar) ethanol solution was added dropwise with stirring, nitrogen purging for 5.0 min. 25 °C, stirring in the dark for 12.0 h. Centrifugation, 3 x 20 mL of anhydrous ethanol washing the resulting solid, 5 x 20 mL of deionized water washing the resulting solid, 80 °C vacuum drying for 8.0 h, 0.5538 g of gray-black solid was obtained, the resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.2M@300@25@2h@25@12h.

[0047] Example 19 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+ in ethanol (150 mL) at a molarity of 0.1 mol / L, under N2atmosphere, at 25 °C, stirred for 2.0 h in the dark. Freshly prepared NaBH4(0.5 mol / L) in ethanol was added dropwise while stirring, with a nitrogen purge for 5.0 min. The reaction was stirred for 12.0 h at 25 °C in the dark. The resulting solid was washed with 3 x 20 mL of anhydrous ethanol, 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a grey-black solid, 0.5564 g, which was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.5M@300@25@2h@25@12h.

[0048] Example 20 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+ in ethanol (150 mL) at a molarity of 0.1 mol / L, under N2atmosphere, at 25 °C, stirred for 2.0 h in the dark. Freshly prepared NaBH4(0.8 mol / L) in ethanol was added dropwise while stirring, with a nitrogen purge for 5.0 min. The reaction was stirred for 12.0 h at 25 °C in the dark. The resulting solid was washed with 3 x 20 mL of anhydrous ethanol, 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a grey-black solid, 0.5566 g, which was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.8M@300@25@2h@25@12h.

[0049] Example 21 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+In a 0.1 mol / L ethanol solution (150 mL), under a N2 atmosphere, at 25 °C, the mixture was stirred in the dark for 2.0 h. Freshly prepared NaBH4 (1.0 mol / L) ethanol solution was added dropwise with stirring, and the mixture was purged with nitrogen for 5.0 min. The reaction was continued at 25 °C with stirring in the dark for 12.0 h. After centrifugation, the solid was washed with 3 × 20 mL of anhydrous ethanol and 5 × 20 mL of deionized water. The solid was then dried under vacuum at 80 °C for 8.0 h to obtain 0.5571 g of a gray-black solid. The obtained material was named CoCuMn-βCD@0.1M@0.1M@0.1M@1.0M@300@25@2h@25@12h.

[0050] Example 22: In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co... 2+ The molar concentration is 0.1 mol / L, Cu 2+ The molar concentration was 0.1 mol / L and Mn 2+ In a 0.1 mol / L ethanol solution (10 mL), under a N2 atmosphere, at 25 °C, the mixture was stirred in the dark for 2.0 h. Freshly prepared NaBH4 (0.1 mol / L) ethanol solution was then added dropwise while stirring, and the mixture was purged with nitrogen for 5.0 min. The reaction was continued at 25 °C with stirring in the dark for 12.0 h. After centrifugation, the solid was washed with 3 × 20 mL of anhydrous ethanol and 5 × 20 mL of deionized water. The solid was then dried under vacuum at 80 °C for 8.0 h to obtain 0.5248 g of a gray-black solid. This material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@20@25@2h@25@12h.

[0051] Example 23: In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co... 2+ The molar concentration is 0.1 mol / L, Cu 2+ The molar concentration was 0.1 mol / L and Mn 2+ In a 0.1 mol / L ethanol solution (50 mL), under a N2 atmosphere, at 25 °C, the mixture was stirred in the dark for 2.0 h. Freshly prepared NaBH4 (0.1 mol / L) ethanol solution was then added dropwise while stirring, and the mixture was purged with nitrogen for 5.0 min. The reaction was continued at 25 °C with stirring in the dark for 12.0 h. After centrifugation, the solid was washed with 3 × 20 mL of anhydrous ethanol and 5 × 20 mL of deionized water. The solid was then dried under vacuum at 80 °C for 8.0 h to obtain 0.5355 g of a gray-black solid. This material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@100@25@2h@25@12h.

[0052] Example 24: In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co... 2+0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 250 mL of ethanol (0.1 Molar concentration), under N2atmosphere, at 25 °C, stirred for 2.0 h. Freshly prepared NaBH4(0.1 Molar concentration) in ethanol was added dropwise under stirring, with nitrogen purging for 5.0 min. The reaction was stirred for 12.0 h at 25 °C in the dark. The solid was washed with 3 x 20 mL of anhydrous ethanol, 5 x 20 mL of deionized water, and dried at 80 °C under vacuum for 8.0 h to obtain a grey black solid, 0.5473 g. The material obtained was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@500@25@2h@25@12h.

[0053] Example 25 In a 500 mL four necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ 0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 250 mL of ethanol (0.1 Molar concentration), under N2atmosphere, at 25 °C, stirred for 2.0 h. Freshly prepared NaBH4(0.1 Molar concentration) in ethanol was added dropwise under stirring, with nitrogen purging for 5.0 min. The reaction was stirred for 12.0 h at 25 °C in the dark. The solid was washed with 3 x 20 mL of anhydrous ethanol, 5 x 20 mL of deionized water, and dried at 80 °C under vacuum for 8.0 h to obtain a grey black solid, 0.5473 g. The material obtained was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@500@25@2h@25@12h.

[0054] Example 26 In a 500 mL four necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ 0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 250 mL of ethanol (0.1 Molar concentration), under N2atmosphere, at 25 °C, stirred for 2.0 h. Freshly prepared NaBH4(0.1 Molar concentration) in ethanol was added dropwise under stirring, with nitrogen purging for 5.0 min. The reaction was stirred for 12.0 h at 25 °C in the dark. The solid was washed with 3 x 20 mL of anhydrous ethanol, 5 x 20 mL of deionized water, and dried at 80 °C under vacuum for 8.0 h to obtain a grey black solid, 0.5473 g. The material obtained was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@500@25@2h@25@12h.

[0055] Example 27 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+ in ethanol (150 mL) at a molarity of 0.1 mol / L, under N2atmosphere, 0 °C, stirred for 2.0 h in the dark. Freshly prepared NaBH4(0.1 mol / L) in ethanol was added dropwise while stirring, purging with nitrogen for 5.0 min. The reaction was stirred for 12.0 h at 25 °C in the dark. The solid was centrifuged, washed with 3 x 20 mL of absolute ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a dark gray solid, 0.5344 g, which was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@0@2h@25@12h.

[0056] Example 28 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+ in ethanol (150 mL) at a molarity of 0.1 mol / L, under N2atmosphere, 15 °C, stirred for 2.0 h in the dark. Freshly prepared NaBH4(0.1 mol / L) in ethanol was added dropwise while stirring, purging with nitrogen for 5.0 min. The reaction was stirred for 12.0 h at 25 °C in the dark. The solid was centrifuged, washed with 3 x 20 mL of absolute ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a dark gray solid, 0.5457 g, which was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@15@2h@25@12h.

[0057] Example 29 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+In 150 mL of ethanol (0.1 M), under N2atmosphere, at 50 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise with stirring, purging with N2for 5.0 min. The reaction was stirred in the dark at 25 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried at 80 °C under vacuum for 8.0 h to yield a gray-black solid, 0.5459 g, which was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@50@2h@25@12h.

[0058] Example 30 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 M, Cu 2+ at a molarity of 0.1 M, and Mn 2+ In 150 mL of ethanol (0.1 M), under N2atmosphere, at 60 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise with stirring, purging with N2for 5.0 min. The reaction was stirred in the dark at 25 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried at 80 °C under vacuum for 8.0 h to yield a gray-black solid, 0.5453 g, which was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@60@2h@25@12h.

[0059] Example 31 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 M, Cu 2+ at a molarity of 0.1 M, and Mn 2+ In 150 mL of ethanol (0.1 M), under N2atmosphere, at 25 °C, stirring in the dark for 1.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise with stirring, purging with N2for 5.0 min. The reaction was stirred in the dark at 25 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried at 80 °C under vacuum for 8.0 h to yield a gray-black solid, 0.5364 g, which was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@1h@25@12h.

[0060] Example 32 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 150 mL of ethanol (0.1 Molar concentration) under N2atmosphere at 25 °C, the mixture was stirred in the dark for 4.0 h. Freshly prepared NaBH4(0.1 Molar concentration) in ethanol was added dropwise while stirring under a nitrogen purge for 5.0 min. The reaction was stirred in the dark at 25 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a dark gray solid, 0.5561 g. The resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@4h@25@12h.

[0061] Example 33 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ 0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 150 mL of ethanol (0.1 Molar concentration) under N2atmosphere at 25 °C, the mixture was stirred in the dark for 6.0 h. Freshly prepared NaBH4(0.1 Molar concentration) in ethanol was added dropwise while stirring under a nitrogen purge for 5.0 min. The reaction was stirred in the dark at 25 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a dark gray solid, 0.5552 g. The resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@6h@25@12h.

[0062] Example 34 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ 0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 150 mL of ethanol (0.1 Molar concentration) under N2atmosphere at 25 °C, the mixture was stirred in the dark for 8.0 h. Freshly prepared NaBH4(0.1 Molar concentration) in ethanol was added dropwise while stirring under a nitrogen purge for 5.0 min. The reaction was stirred in the dark at 25 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a dark gray solid, 0.5561 g. The resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@8h@25@12h.

[0063] Example 35 In a 500 mL four necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+ in ethanol (150 mL) at a molarity of 0.1 mol / L, under N2atmosphere, at 25 °C, stirred for 12.0 h in the dark. Freshly prepared NaBH4(0.1 mol / L) in ethanol was added dropwise while stirring, purged with nitrogen for 5.0 min. The reaction was stirred for 12.0 h at 25 °C in the dark. The solid was centrifuged, washed with 3 x 20 mL of absolute ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a grey black solid 0.5566 g, the resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@12h@25@12h.

[0064] Example 36 In a 500 mL four necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+ in ethanol (150 mL) at a molarity of 0.1 mol / L, under N2atmosphere, at 25 °C, stirred for 2.0 h in the dark. Freshly prepared NaBH4(0.1 mol / L) in ethanol was added dropwise while stirring, purged with nitrogen for 5.0 min. The reaction was stirred for 12.0 h at 0 °C in the dark. The solid was centrifuged, washed with 3 x 20 mL of absolute ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a grey black solid 0.5224 g, the resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@0@12h.

[0065] Example 37 In a 500 mL four necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 mol / L, Cu 2+ at a molarity of 0.1 mol / L and Mn 2+In 150 mL of ethanol (0.1 M), under N2atmosphere, at 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise with stirring, purging with N2for 5.0 min. The reaction was stirred in the dark at 15 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a gray-black solid, 0.5458 g. The resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@15@12h.

[0066] Example 38 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 M, Cu 2+ at a molarity of 0.1 M, and Mn 2+ In 150 mL of ethanol (0.1 M), under N2atmosphere, at 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise with stirring, purging with N2for 5.0 min. The reaction was stirred in the dark at 50 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a gray-black solid, 0.5349 g. The resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@50@12h.

[0067] Example 39 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 M, Cu 2+ at a molarity of 0.1 M, and Mn 2+ In 150 mL of ethanol (0.1 M), under N2atmosphere, at 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise with stirring, purging with N2for 5.0 min. The reaction was stirred in the dark at 60 °C for 12.0 h. The solid was centrifuged, washed with 3 x 20 mL of anhydrous ethanol, washed with 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a gray-black solid, 0.5347 g. The resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@60@12h.

[0068] Example 40 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 150 mL of ethanol solution with 0.1 Molar concentration, under N2atmosphere, 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 Molar) ethanol solution was added dropwise with stirring, and nitrogen was purged for 5.0 min. The reaction was stirred in the dark at 25 °C for 3.0 h. The obtained solid was washed with 3 x 20 mL of anhydrous ethanol, and then washed with 5 x 20 mL of deionized water. The obtained solid was dried at 80 °C under vacuum for 8.0 h to obtain a gray-black solid of 0.5232 g. The obtained material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@3h.

[0069] Example 41 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ 0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 150 mL of ethanol solution with 0.1 Molar concentration, under N2atmosphere, 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 Molar) ethanol solution was added dropwise with stirring, and nitrogen was purged for 5.0 min. The reaction was stirred in the dark at 25 °C for 6.0 h. The obtained solid was washed with 3 x 20 mL of anhydrous ethanol, and then washed with 5 x 20 mL of deionized water. The obtained solid was dried at 80 °C under vacuum for 8.0 h to obtain a gray-black solid of 0.5354 g. The obtained material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@6h.

[0070] Example 42 In a 500 mL four-necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ 0.1 Molar concentration of Cu 2+ 0.1 Molar concentration of Mn 2+ In 150 mL of ethanol solution with 0.1 Molar concentration, under N2atmosphere, 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 Molar) ethanol solution was added dropwise with stirring, and nitrogen was purged for 5.0 min. The reaction was stirred in the dark at 25 °C for 9.0 h. The obtained solid was washed with 3 x 20 mL of anhydrous ethanol, and then washed with 5 x 20 mL of deionized water. The obtained solid was dried at 80 °C under vacuum for 8.0 h to obtain a gray-black solid of 0.5468 g. The obtained material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@9h.

[0071] Example 43 In a 500 mL four necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molar concentration of 0.1 mol / L, Cu 2+ at a molar concentration of 0.1 mol / L and Mn 2+ in ethanol (150 mL) at a molar concentration of 0.1 mol / L, under N2atmosphere, at 25 °C, stirred for 2.0 h in the dark. Freshly prepared NaBH4(0.1 mol / L) in ethanol was added dropwise under stirring, purging with nitrogen for 5.0 min. The reaction was stirred for 15.0 h at 25 °C in the dark. The solid was centrifuged, washed with 3 x 20 mL of absolute ethanol, washed with 5 x 20 mL of deionized water, and dried at 80 °C under vacuum for 8.0 h to yield a grey-black solid, 0.5544 g, the resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@15h.

[0072] Example 44 In a 500 mL four necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molar concentration of 0.1 mol / L, Cu 2+ at a molar concentration of 0.1 mol / L and Mn 2+ in ethanol (150 mL) at a molar concentration of 0.1 mol / L, under N2atmosphere, at 25 °C, stirred for 2.0 h in the dark. Freshly prepared NaBH4(0.1 mol / L) in ethanol was added dropwise under stirring, purging with nitrogen for 5.0 min. The reaction was stirred for 18.0 h at 25 °C in the dark. The solid was centrifuged, washed with 3 x 20 mL of absolute ethanol, washed with 5 x 20 mL of deionized water, and dried at 80 °C under vacuum for 8.0 h to yield a grey-black solid, 0.5557 g, the resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@18h.

[0073] Example 45 In a 500 mL four necked flask, β-cyclodextrin (0.50 g) was suspended in Co 2+ at a molar concentration of 0.1 mol / L, Cu 2+ at a molar concentration of 0.1 mol / L and Mn 2+In 150 mL of ethanol (0.1 M), under N2atmosphere, at 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise with stirring, purging with N2for 5.0 min. The reaction was stirred in the dark at 25 °C for 24.0 h. The solid was washed with 3 x 20 mL of anhydrous ethanol, 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a gray-black solid, 0.5563 g. The resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@60@24h.

[0074] Example 46 In a 500 mL four-necked flask, γ-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 M, Cu 2+ at a molarity of 0.1 M, and Mn 2+ In 150 mL of ethanol (0.1 M), under N2atmosphere, at 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise with stirring, purging with N2for 5.0 min. The reaction was stirred in the dark at 25 °C for 24.0 h. The solid was washed with 3 x 20 mL of anhydrous ethanol, 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a gray-black solid, 0.5563 g. The resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@60@24h.

[0075] Example 47 In a 500 mL four-necked flask, γ-cyclodextrin (0.50 g) was suspended in Co 2+ at a molarity of 0.1 M, Cu 2+ at a molarity of 0.1 M, and Mn 2+ In 150 mL of ethanol (0.1 M), under N2atmosphere, at 25 °C, stirring in the dark for 2.0 h. Freshly prepared NaBH4(0.1 M) in ethanol was added dropwise with stirring, purging with N2for 5.0 min. The reaction was stirred in the dark at 25 °C for 24.0 h. The solid was washed with 3 x 20 mL of anhydrous ethanol, 5 x 20 mL of deionized water, and dried under vacuum at 80 °C for 8.0 h to yield a gray-black solid, 0.5563 g. The resulting material was named CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@60@24h.

[0076] Catalyst performance studies

[0077] To evaluate its catalytic performance, the screening experiment of catalyst application conditions was carried out.

[0078] Example 48In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was introduced into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 100 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 581.12 μmol / (g Cat. ·h), wherein the ethylene selectivity was 97%, the carbon monoxide selectivity was 2%, and the methane was 1%.

[0079] Example 49In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (1 g), CO2 was introduced into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 100 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 345.32 μmol / (g Cat. ·h), wherein the ethylene selectivity was 91%, the carbon monoxide selectivity was 6%, and the methane was 3%.

[0080] Example 50In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (100 g), CO2 was introduced into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 100 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 540.62 μmol / (g Cat. ·h), wherein the ethylene selectivity was 93%, the carbon monoxide selectivity was 5%, and the methane was 2%.

[0081] Example 51In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (1 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 100 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 176.39 μmol / (g Cat. ·h), wherein the ethylene selectivity was 90%, the carbon monoxide selectivity was 8%, and the methane was 2%.

[0082] Example 52In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (5 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 100 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 343.10 μmol / (g Cat. ·h), wherein the ethylene selectivity was 92%, the carbon monoxide selectivity was 4%, and the methane was 4%.

[0083] Example 53In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (8 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 100 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 513.77 μmol / (g Cat. ·h), wherein the ethylene selectivity was 92%, the carbon monoxide selectivity was 5%, and the methane was 3%.

[0084] Example 54In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.05 MPa, and the reactor was sealed. A 100 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 442.73 μmol / (g Cat. ·h), wherein the ethylene selectivity was 89%, the carbon monoxide selectivity was 6%, and the methane was 5%.

[0085] Example 55In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.08 MPa, and the reactor was sealed. A 100 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 522.43 μmol / (g Cat. ·h), wherein the ethylene selectivity was 94%, the carbon monoxide selectivity was 4%, and the methane was 2%.

[0086] Example 56In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.1 MPa, and the reactor was sealed. A 100 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 543.19 μmol / (g Cat. ·h), wherein the ethylene selectivity was 95%, the carbon monoxide selectivity was 4%, and the methane was 1%.

[0087] Example 57In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.15 MPa, and the reactor was sealed. A 100 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 531.18 μmol / (g Cat. ·h), wherein the ethylene selectivity was 93%, the carbon monoxide selectivity was 6%, and the methane was 1%.

[0088] Example 58In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 10 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 431.51 μmol / (g Cat. ·h), wherein the ethylene selectivity was 87%, the carbon monoxide selectivity was 9%, and the methane was 4%.

[0089] Example 59In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 50 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 523.16 μmol / (g Cat. ·h), wherein the ethylene selectivity was 86%, the carbon monoxide selectivity was 11%, and the methane was 3%.

[0090] Example 60 In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 150 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 537.71 μmol / (g Cat. ·h), wherein the ethylene selectivity was 88%, the carbon monoxide selectivity was 9%, and the methane was 3%.

[0091] Example 61 In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 200 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 529.33 μmol / (g Cat. ·h), wherein the ethylene selectivity was 90%, the carbon monoxide selectivity was 9%, and the methane was 1%.

[0092] Example 62 In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was bubbled into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 300 W LED incandescent lamp visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 509.62 μmol / (g Cat. ·h), wherein the ethylene selectivity was 85%, the carbon monoxide selectivity was 12%, and the methane was 3%.

[0093] Example 63 In a CO2 photocatalytic reactor, CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was introduced into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 500 W LED white incandescent light visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 472.40 μmol / (g Cat. ·h), wherein the ethylene selectivity was 87%, the carbon monoxide selectivity was 10%, and the methane selectivity was 3%.

[0094] From the catalyst application in Examples 48-63, the optimal application condition of the catalyst was the condition of Example 48, and it was used as the reaction condition for the application examples of all the catalysts prepared in the application, and the specific operation was as follows:

[0095] In a CO2 photocatalytic reactor, 10 mg of cyclodextrin modified cobalt copper manganese ternary alloy particle biomimetic catalyst prepared in Examples 1-47 was dispersed in 50 g of deionized water, CO2 was introduced into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. A 100 W LED white incandescent light visible light source was turned on, and the reaction was stirred at room temperature for 8.0 h. The generated reduction products were detected by online gas chromatography, and the generation efficiency of ethylene, carbon monoxide and methane of each example was recorded respectively, and the total product generation efficiency and selectivity were calculated, and the results are shown in Table 2.

[0096] Table 2 Preparation and catalytic performance summary table of cyclodextrin modified cobalt copper manganese ternary alloy particle biomimetic catalyst

[0097]

[0098]

[0099]

[0100]

[0101] From the data in Table 2, it can be seen that the catalyst of the application has a certain catalytic effect in the preparation of ethylene by visible light driven carbon dioxide reduction. The catalysts obtained under different conditions have different catalytic effects. By comparing the data in Table 2, it can be found that the comprehensive performance of the CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst is the best, and the total product generation efficiency is the highest (587.12 μmol / (g Cat.• h) and the selectivity (97%) is the best.

[0102] Other light source embodiments To investigate the influence of light source type on catalytic performance, after determining the optimal catalyst preparation and application conditions described above, the following comparative experiments of other light sources are supplemented:

[0103] In the CO2 photocatalytic reactor, the CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was introduced into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. Turn on the 100W xenon lamp light source, stir at room temperature for 8.0h. The generated reduction products were detected by online gas chromatography, and the total generation efficiency of the reduction products was 356.19μmol / (g Cat. • h), wherein the ethylene selectivity is 63%, the carbon monoxide selectivity is 28%, and the methane is 9%.

[0104] Product comprehensive analysis In order to comprehensively evaluate the product guiding property of the catalyst, the liquid phase products were precisely analyzed, and the specific operation was as follows:

[0105] In the CO2 photocatalytic reactor, the CoCuMn-βCD@0.1M@0.1M@0.1M@0.1M@300@25@2h@25@12h catalyst (10 mg) obtained from Example 1 was dispersed in deionized water (50 g), CO2 was introduced into the reactor to replace the air therein, and the CO2 pressure was adjusted to 0.09 MPa, and the reactor was sealed. Turn on the 100W LED white incandescent lamp visible light source, stir at room temperature for 8.0h. The generation efficiency of ethanol was only 15.73μmol / (g Cat. • h). This is in sharp contrast to the high generation rate of ethylene (587.12μmol / (g Cat. • h) of the catalyst. The above data clearly indicate that the catalyst has significantly higher activity and path selectivity in the preparation of ethylene driven by visible light reduction of carbon dioxide, and its catalytic reaction path is more inclined to generate ethylene rather than ethanol, which proves the specific advantages and application potential of the catalyst in the efficient synthesis of ethylene.

Claims

1. A cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD, characterized in that... The cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst contains ternary transition metals cobalt, copper, and manganese, as well as cyclodextrin complexed with ternary alloy particles. The cyclodextrin acts as a carrier to adsorb metal ions.

2. The cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD as described in claim 1, characterized in that... The cyclodextrin is one or any combination of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

3. The cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD as described in claim 1, characterized in that... The molar ratio of the ternary transition metals cobalt, copper, and manganese is 1:0.1-100:0.1-100.

4. A method for preparing the cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD as described in any one of claims 1-3, characterized in that... Includes the following steps: 1) Adsorption: Cyclodextrin is suspended in a solution containing Co2 + Cu2 + and Mn2 + In an ethanol solution, under an inert atmosphere and at 0℃~60℃ in the dark, the mixture is stirred and adsorbed for 1.0h~12.0h to obtain a cyclodextrin suspension adsorbed with metal ions. 2) Reduction: Under an inert atmosphere and in the dark, sodium borohydride ethanol solution was added dropwise to the cyclodextrin suspension containing adsorbed metal ions obtained in step 1) at 0℃~60℃ for a reduction reaction of 3.0h~24.0h. 3) Post-processing: The reduction product suspension obtained in step 2) is centrifuged, washed and vacuum dried to obtain the cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD.

5. The preparation method of the cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD as described in claim 4, characterized in that... The cyclodextrin in step 1) is one or any combination of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin; the transition metal ion Co 2+ Cu 2+ and Mn 2+ The concentration is 0.01 mol / L to 1.00 mol / L, preferably 0.1 mol / L to 0.50 mol / L; transition metal ion Co 2+ Cu 2+ and Mn 2+ The molar ratio is 1:0.1 to 100:0.1 to 100, preferably 1:1 to 10:1 to 10; the ratio of the mass of cyclodextrin to the volume of the transition metal ion ethanol solution is 1:10 to 500, preferably 1:100 to 200.

6. The preparation method of the cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD as described in claim 4, characterized in that... In step 2), the concentration of sodium borohydride is 0.01 mol / L to 1.00 mol / L, preferably 0.1 mol / L to 0.50 mol / L; the molar ratio of the total number of transition metal ions to sodium borohydride is 1:0.5 to 10, preferably 1:1 to 1:5; the reaction temperature is 20℃ to 40℃; and the reaction time is 6.0 h to 18.0 h.

7. The preparation method of the cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD as described in claim 4, characterized in that... Co 2+ Cu 2+ and Mn 2+ It is provided by its hydrochloride and its hydrate, sulfate and its hydrate, or nitrate and its hydrate.

8. The application of the cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD according to claim 1 in the visible light-driven carbon dioxide reduction to ethylene production.

9. The application as described in claim 8, characterized in that... The application method is as follows: the cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD is dispersed in deionized water, which serves as both a solvent and a hydrogen source. CO2 is introduced into the reactor to replace the air, and the CO2 pressure is adjusted to 0.05MPa to 0.15MPa. The reaction is carried out under the illumination of a 10W to 500W LED light source to obtain the reduction product ethylene.

10. The application as described in claim 9, characterized in that... The mass ratio of the cyclodextrin-modified cobalt-copper-manganese ternary alloy particle biomimetic catalyst CoCuMn-CD to deionized water is 1:100 to 1:100000, preferably 1:1000 to 1:10000; the visible light source power is 100W to 300W; and the reaction pressure is 0.08MPa to 0.10MPa.

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