Preparation method and application of molecular sieve-sulfur indium zinc heterogeneous material for photo-thermal driven CO2 cycloaddition

Abstract

The invention belongs to the technical field of heterogeneous catalysis, and relates to a preparation method and application of a molecular sieve-sulfur indium zinc heterogeneous material for photo-thermal driven CO2 cycloaddition, and the preparation method comprises the following steps: adding a certain amount of TS-1 molecular sieve into absolute ethyl alcohol, and stirring for 0.5-1.5 h; the preparation method comprises the following steps: respectively weighing anhydrous zinc chloride, indium trichloride tetrahydrate and thioacetamide according to a molar ratio of 1: 2: (6-10), mixing, adding into ethanol dispersed with a TS-1 molecular sieve, and stirring for 20-40 minutes; and heating the molecular sieve-sulfur indium zinc heterogeneous material TS-ZIS at 140-180 DEG C for 10-14 hours, cooling to room temperature, centrifugally washing and drying to obtain the molecular sieve-sulfur indium zinc heterogeneous material TS-ZIS. The prepared heterogeneous material can catalyze CO2 cycloaddition reaction in a photo-thermal concerted mode under the mild condition, the catalytic performance is good, the performance is not obviously reduced after multiple times of circulation, and the stability is good.

Description

Technical Field

[0001] The present invention belongs to the technical field of heterogeneous catalysis, and specifically relates to a preparation method and application of a molecular sieve-indium zinc sulfur heterogeneous material for photothermal driven CO2 cycloaddition. Background Art

[0002] Due to the massive burning of fossil fuels, global CO2 levels are increasing, triggering a series of environmental problems, such as the melting of glaciers and rising sea levels caused by the greenhouse effect. Therefore, how to efficiently and greenly reduce CO2 emissions or convert it into other usable resources has become a concern for all countries.

[0003] As a green and non-toxic C1 resource, CO2 can be used to synthesize some high value-added products through reduction, cycloaddition, hydrogenation and other methods, such as the copolymerization of CO2 with epoxides to form polycarbonates. Among them, the CO2 cycloaddition reaction has attracted widespread attention due to its 100% atom economy. Since the mid-20th century, the application of cyclic carbonates in lithium battery electrolytes has been developed and studied. In addition, it has also been used in many industries such as medicine. At present, people have explored a variety of catalysts for CO2 cycloaddition reactions. However, homogeneous catalysts generally have low catalytic activity, are difficult to recycle, and generally require high temperature and high pressure reaction conditions. In contrast, heterogeneous catalysts have low activity, poor stability, and more harsh reaction conditions. Therefore, the preparation of efficient and reproducible heterogeneous catalysts under mild conditions is a prerequisite for the large-scale industrialization of CO2 cycloaddition reactions.

[0004] The current energy shortage crisis can be alleviated by using photothermal catalytic CO2 cycloaddition reactions. However, existing thermal catalytic reactions generally require high reaction temperatures, which are costly, and high temperatures may also lead to catalyst deactivation. Photocatalytic reactions, on the other hand, have low light utilization rates and cannot be put into practical production on a large scale. Using photothermal synergistic catalysis, the reaction temperature is lowered, the actual cost of the reaction is reduced, and large-scale production can be achieved. However, the currently available photothermal catalysts have poor stability and low catalyst yields.

[0005] Based on this, the present invention prepares a new photothermal catalytic material that can synergistically photothermally catalyze CO2 cycloaddition reactions under mild conditions. Summary of the Invention

[0006] The purpose of the present invention is to solve the above-mentioned problems existing in the prior art, and proposes a preparation method and application of a molecular sieve-indium zinc sulfur heterogeneous material for photothermal driven CO2 cycloaddition. The prepared heterogeneous material can photothermally catalyze the CO2 cycloaddition reaction under relatively mild conditions, with good catalytic performance. In addition, the performance of the heterogeneous material does not decrease significantly after multiple cycles, and it has good stability and is easy to recycle. In experiments with industrial simulated gas, the performance is still relatively excellent.

[0007] The technical solution of the present invention is:

[0008] A method for preparing a molecular sieve-indium zinc sulfide heterogeneous material for photothermal driven CO2 cycloaddition, comprising the following steps:

[0009] (1) Add a certain amount of TS-1 molecular sieve to anhydrous ethanol and stir for 0.5 to 1.5 hours;

[0010] (2) Anhydrous zinc chloride (ZnCl2), indium trichloride tetrahydrate (InCl3·4H2O), and thioacetamide (TAA) were weighed in a molar ratio of 1:2:(6-10), mixed, and added to ethanol dispersed with TS-1 molecular sieves, and stirred for 20-40 minutes;

[0011] (3) heating the mixture at 140-180° C. for 10-14 h, cooling the mixture to room temperature, centrifuging, washing, and drying the mixture to obtain a molecular sieve-sulfur indium zinc heterogeneous material TS-ZIS.

[0012] Furthermore, the molar ratio of the anhydrous zinc chloride, indium trichloride tetrahydrate and thioacetamide is 1:2:8.

[0013] Furthermore, the mass ratio of the molecular sieve to the sulfur indium zinc in preparing the molecular sieve-sulfur indium zinc heterogeneous material is 1:(3-20).

[0014] Furthermore, the mass ratio of the TS-1 molecular sieve to zinc indium sulfide ZIS is TS-1:ZIS=1:5.

[0015] Furthermore, the molecular sieve used in the present invention is TS-1 molecular sieve, and other molecular sieve materials with different pores can also be selected, such as MCM-41 molecular sieve with a pore size of 1.5 to 10 nm or SBA-15 molecular sieve with a pore size of 6 to 7 nm.

[0016] The present invention also provides an application of a molecular sieve-sulfur indium zinc heterogeneous material prepared according to the preparation method according to any one of claims 1 to 5 in driving CO2 cycloaddition.

[0017] Furthermore, the molecular sieve-sulfur indium zinc heterogeneous material TS-ZIS is used as a photothermal catalyst to drive the CO2 cycloaddition reaction at 60-90°C and normal pressure.

[0018] Furthermore, the application method comprises the following steps:

[0019] In a 1.0 MPa CO2 atmosphere, TS-ZIS catalyst, tetrabutylammonium bromide as a co-catalyst, and epoxide were added. The reaction temperature was set to 80 °C, the speed was set to 20 rpm, and the light intensity was set to 300-600 mW / cm 2 The cycloaddition reaction was carried out under visible light irradiation, and the reaction time was 3.5 to 4.5 hours;

[0020] The epoxides include epichlorohydrin, epibromohydrin, 1,2-epoxyhexane, 1,2-epoxybutylene, and styrene oxide.

[0021] The molecular sieve-sulfur indium zinc heterogeneous material TS-ZIS prepared by the present invention is used as a photothermal catalyst in the CO2 cycloaddition reaction. The photothermal catalytic reaction can be carried out under relatively mild conditions (low temperature and normal pressure), reducing energy consumption; at the same time, light excites the catalyst to produce more free electrons, thereby increasing the catalytic rate.

[0022] Furthermore, the molecular sieve-sulfur indium zinc heterogeneous material TS-ZIS can be used as a photothermal catalyst and can also use industrial flue gas (air containing 10% CO2) as a carbon source to drive the cycloaddition reaction at a lower reaction temperature of 80°C and pressure (normal pressure).

[0023] Beneficial effects of the present invention:

[0024] (1) The present invention adopts a one-step method to synthesize the photothermal catalyst of TS-ZIS heterogeneous materials. In the photothermal catalytic material, ZnIn2S4 itself has a large number of Lewis acid-base sites, and multiple properties are relatively superior, which is beneficial to the ring-opening speed in CO2 cycloaddition. By combining it with the porous molecular sieve TS-1 to prepare the photothermal catalyst, the shortcomings of both can be compensated, and the adsorption capacity of the photothermal catalyst for CO2 molecules is improved, and the stability is higher. It is used to catalyze the CO2 cycloaddition reaction under photothermal catalytic conditions, which is beneficial to reducing energy consumption.

[0025] (2) The preparation method provided by the present invention has simple steps, low production cost, and is conducive to large-scale production.

[0026] (3) The present invention innovatively uses TS-1 molecular sieve as a carrier to combine with ZnIn2S4, which has zinc Lewis acid sites. The reaction is efficiently driven by the synergistic effect of light and heat energy fields, greatly reducing the reaction activation energy.

[0027] (4) Compared with the existing thermal catalytic process, which has the defects of high temperature, high pressure and high energy consumption, the CO2 cycloaddition reaction of the present invention has 100% atom economy, which is conducive to green chemical process; the carbonate produced by the reaction is one of the components of battery electrolyte solvent and fine chemicals, and has high economic added value. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is the TEM image of the 20% TS-ZIS prepared in Example 1.

[0029] Figure 2 XRD patterns of TS-ZIS with different mass ratios.

[0030] Figure 3 The yield of CO2 cycloaddition reaction catalyzed by photothermal TS-ZIS catalysts with different mass ratios.

[0031] Figure 4 The yield of the cycloaddition reaction after multiple cycles of 20% TS-ZIS catalyst.

[0032] Figure 5 The yields of different epoxides in the photothermal catalytic CO2 cycloaddition reaction with 20% TS-ZIS; the horizontal axis on the figure represents the cycloaddition reaction products from left to right: chloropropylene carbonate; 1,2-butenyl carbonate; 4-butyl-1,3-dioxolane-2-one; 1,3-dioxolane-2-one, 4-(bromomethyl)-; propylene carbonate; styrene carbonate.

[0033] Figure 6 The yield of cycloaddition under the conditions of selecting industrial simulated gas as the carbon source. DETAILED DESCRIPTION

[0034] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0035] In order to further understand the present invention, the present invention will be further described with reference to the accompanying drawings and embodiments.

[0036] If no specific techniques or conditions are specified in the examples, the experiments were carried out according to conventional methods in the art, techniques or conditions described in the literature, or product instructions. Reagents or instruments used without manufacturer specified were all purchased through regular channels.

[0037] Example 1

[0038] A method for preparing a molecular sieve-indium zinc sulfide heterogeneous material for photothermal driven CO2 cycloaddition, comprising the following steps:

[0039] First, weigh 0.1 g of TS-1 molecular sieve, add it to 40 mL of anhydrous ethanol, and stir for 1 h to obtain an ethanol solution in which TS-1 molecular sieve is dispersed;

[0040] Then, 0.136 g (1 mmol) ZnCl2, 0.5865 g (2 mmol) InCl3·4H2O, and 0.6012 g (8 mmol) TAA were weighed, mixed, and added to ethanol dispersed with TS-1 molecular sieves, and stirred for 30 min;

[0041] The obtained white emulsion was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave, which was heated in an oven at 160 °C for 12 h.

[0042] After the hydrothermal autoclave was cooled to room temperature, it was centrifugally washed with ethanol and deionized water and dried in an oven at 60° C. for 12 h. The obtained yellow powder was the molecular sieve-sulfur indium zinc heterogeneous material, named 20% TS-ZIS.

[0043] like Figure 1 Shown is the electron microscope (TEM) image of 20% TS-ZIS prepared in Example 1.

[0044] according to Figure 2 XRD pattern analysis shows that 20% TS-ZIS has the characteristic peaks of ZIS and TS-1, indicating that the preparation is successful.

[0045] Example 2

[0046] The 20% TS-ZIS material prepared in Example 1 was used as a photothermal catalyst, and tetrabutylammonium bromide (TBAB) was used as a co-catalyst to catalyze the CO2 cycloaddition reaction; the method comprises the following steps:

[0047] 30 mg of 20% TS-ZIS catalyst, 0.3 mmol of TBAB, and 20 mmol of styrene oxide were added to the reactor in sequence and sealed. The reactor was then purged with CO2 to ensure that there was no other gas in the reactor. After the CO2 gas entered the reactor, the reactor was continuously vented to maintain a CO2 atmosphere of 1.0 MPa.

[0048] The reactor was placed in an oil bath with a rotation speed of 20 rpm and a temperature of 80°C. The light source was visible light, and the distance between the light source and the reactor was controlled so that the light intensity was maintained at 300 mW / cm 2 After 4 hours of full spectrum irradiation, the reactor was placed in ice water to completely cool and release the gas.

[0049] After the reactor was opened, 30 ml of acetonitrile was used as a solvent, a quantitative amount of biphenyl was added as an internal standard, the resulting reaction solution was centrifuged, and the suspension was filtered using a 0.22 μl syringe filter.

[0050] Gas chromatography was used for quantitative and qualitative analysis to obtain the catalytic activity.

[0051] Yield (%) = (n SC / n SO )×100%;

[0052] Reaction rate (mmol·g -1 ·h -1 )=n SC / m catalyst / t;

[0053] Among them, N SO is the amount of styrene oxide (SO), n SC is the amount of styrene carbonate (SC), m catalyst is the mass of the catalyst used, and t is the reaction time.

[0054] Example 3

[0055] A method for preparing a molecular sieve-indium zinc sulfide heterogeneous material for photothermal driven CO2 cycloaddition, comprising the following steps:

[0056] First, weigh 0.021 g of TS-1 molecular sieve, add it to 40 mL of anhydrous ethanol, and stir for 0.5 h to obtain an ethanol solution in which TS-1 molecular sieve is dispersed;

[0057] Then, 0.136 g (1 mmol) ZnCl2, 0.5865 g (2 mmol) InCl3·4H2O, and 0.6012 g (8 mmol) TAA were weighed, mixed, and added to ethanol dispersed with TS-1 molecular sieves, and stirred for 20 min;

[0058] The obtained white emulsion was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave, which was heated in an oven at 140 °C for 10 h.

[0059] After the hydrothermal autoclave was cooled to room temperature, it was centrifugally washed with ethanol and deionized water and dried in an oven at 60° C. for 12 h. The obtained yellow powder was the molecular sieve-sulfur indium zinc heterogeneous material, named 5% TS-ZIS.

[0060] according to Figure 2 The XRD pattern analysis showed that 5% TS-ZIS had the characteristic peaks of ZIS and TS-1, indicating that the preparation was successful.

[0061] Example 4

[0062] A method for preparing a molecular sieve-indium zinc sulfide heterogeneous material for photothermal driven CO2 cycloaddition, comprising the following steps:

[0063] First, weigh 0.044 g of TS-1 molecular sieve, add it to 40 mL of anhydrous ethanol, and stir for 1.5 h to obtain an ethanol solution in which TS-1 molecular sieve is dispersed;

[0064] Then, 0.136 g (1 mmol) ZnCl2, 0.5865 g (2 mmol) InCl3·4H2O, and 0.6012 g (8 mmol) TAA were weighed, mixed, and added to ethanol dispersed with TS-1 molecular sieves, and stirred for 40 min;

[0065] The obtained white emulsion was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave, which was heated in an oven at 180 °C for 14 h.

[0066] After the hydrothermal autoclave was cooled to room temperature, it was centrifugally washed with ethanol and deionized water and dried in an oven at 60° C. for 12 h. The obtained yellow powder was the molecular sieve-sulfur indium zinc heterogeneous material, named 10% TS-ZIS.

[0067] according to Figure 2 XRD pattern analysis shows that 10% TS-ZIS has the characteristic peaks of ZIS and TS-1, indicating that the preparation is successful.

[0068] Example 5

[0069] A method for preparing a molecular sieve-indium zinc sulfide heterogeneous material for photothermal driven CO2 cycloaddition, comprising the following steps:

[0070] First, weigh 0.171 g of TS-1 molecular sieve, add it to 40 mL of anhydrous ethanol, and stir for 1 h to obtain an ethanol solution in which TS-1 molecular sieve is dispersed;

[0071] Then, 0.136 g (1 mmol) ZnCl2, 0.5865 g (2 mmol) InCl3·4H2O, and 0.6012 g (8 mmol) TAA were weighed, mixed, and added to ethanol dispersed with TS-1 molecular sieves, and stirred for 30 min;

[0072] The obtained white emulsion was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave, which was heated in an oven at 160 °C for 12 h.

[0073] After the hydrothermal autoclave was cooled to room temperature, it was centrifugally washed with ethanol and deionized water and dried in an oven at 60° C. for 12 h. The obtained yellow powder was the molecular sieve-sulfur indium zinc heterogeneous material, named 30% TS-ZIS.

[0074] according to Figure 2XRD pattern analysis shows that 30% TS-ZIS has the characteristic peaks of ZIS and TS-1, indicating that the preparation is successful.

[0075] Test Example 1

[0076] ZIS, molecular sieve TS-1, and TS-ZIS catalyst materials with different TS-1 molecular sieve qualities prepared in Examples 1 and 3-5 above were subjected to CO2 cycloaddition catalytic reactions respectively.

[0077] The specific steps are as follows:

[0078] Catalysts (ZIS, 5% TS-ZIS, 10% TS-ZIS, 20% TS-ZIS, 30% TS-ZIS, and TS-1, respectively), 0.3 mmol TBAB, and 20 mmol styrene oxide were added to the reactor and sealed. The reactor was then purged with CO2 to ensure that no other gases were present in the reactor. After the CO2 gas entered the reactor, the reactor was continuously vented to maintain a CO2 atmosphere of 1.0 MPa.

[0079] The reactor was placed in an oil bath with a rotation speed of 20 rpm and a temperature of 80°C. The light source was visible light, and the distance between the light source and the reactor was controlled so that the light intensity was maintained at 300 mW / cm 2 After 4 hours of full spectrum irradiation, the reactor was placed in ice water to completely cool and release the gas.

[0080] After the reactor was opened, 30 ml of acetonitrile was used as the solvent, and a quantitative amount of biphenyl was added as the internal standard. The resulting reaction solution was centrifuged and the suspension was filtered using a 0.22 μl syringe filter. Gas chromatography was used for quantitative and qualitative analysis to obtain the yield of the photothermal catalytic CO2 cycloaddition reaction of TS-ZIS catalysts with different mass ratios. The results are shown in Figure 2. Figure 3 shown.

[0081] from Figure 3 As can be seen, the 20% TS-ZIS catalyst has the strongest catalytic performance, followed by the 10% TS-ZIS catalyst, the 5% TS-ZIS catalyst, and the 30% TS-ZIS catalyst. Comparing the yields of the catalytic reactions reveals that the molecular sieve-sulfur indium zinc heterogeneous material TS-ZIS prepared in this invention outperforms both ZIS and TS-1 in catalytic performance.

[0082] Test Example 2

[0083] 20% TS-ZIS catalyst, 0.3 mmol TBAB, and 20 mmol styrene oxide were added to the reactor and sealed. The reactor was then purged with CO2 to ensure that there was no other gas in the reactor. After the CO2 gas entered the reactor, the reactor was continuously vented to maintain a CO2 atmosphere of 1.0 MPa.

[0084] The reactor was placed in an oil bath with a rotation speed of 20 rpm and a temperature of 80°C. The light source was visible light, and the distance between the light source and the reactor was controlled so that the light intensity was maintained at 300 mW / cm 2 After 4 hours of full spectrum irradiation, the reactor was placed in ice water to completely cool and release the gas.

[0085] After the reactor was opened, 30 ml of acetonitrile was used as a solvent, a quantitative amount of biphenyl was added as an internal standard, and the obtained reaction solution was centrifuged. The solid after centrifugation was washed three times with ethanol and water respectively and used as the catalyst for the first cycle experiment.

[0086] The first cycle catalyst, 0.3 mmol TBAB, and 20 mmol styrene oxide were added to the reactor and sealed. The above experimental procedures were repeated to obtain the catalyst for the second cycle experiment. The suspension after centrifugation was filtered through a 0.22 μL syringe filter, and the yield of the first cycle was determined by gas chromatography.

[0087] Repeat the above steps five times for the catalyst after each cycle to obtain the cycle yield graph of five cycles, as shown in Figure 4 As shown. Figure 4 It can be concluded that the catalytic performance remains above 80% after multiple cycles, proving that 20% TS-ZIS has cyclic stability.

[0088] Test Example 3

[0089] The 20% TS-ZIS catalyst prepared in Example 1 was used to catalyze different epoxy substrates. The specific steps of the cycloaddition reaction were as follows:

[0090] 20% TS-ZIS catalyst, 0.3 mmol TBAB, and 20 mmol epoxides (epichlorohydrin, epibromohydrin, 1,2-epoxyhexane, 1,2-epoxybutylene, and styrene oxide) were added to the reactor and sealed. The reactor was then purged with CO2 to ensure that there were no other gases in the reactor. After the CO2 gas entered the reactor, the reactor was continuously vented to maintain a CO2 atmosphere of 1.0 MPa.

[0091] The reactor was placed in an oil bath with a rotation speed of 20 rpm and a temperature of 80°C. The light source was visible light, and the distance between the light source and the reactor was controlled so that the light intensity was maintained at 300 mW / cm 2After 4 hours of full spectrum irradiation, the reactor was placed in ice water to completely cool and release the gas.

[0092] After the reactor was opened, 30 ml of acetonitrile was used as the solvent, and a quantitative amount of biphenyl was added as the internal standard. The resulting reaction solution was centrifuged and the suspension was filtered using a 0.22 μl syringe filter. Gas chromatography was used for quantitative and qualitative analysis to obtain the yields of different epoxides in the photothermal catalytic CO2 cycloaddition reaction with 20% TS-ZIS catalyst, as shown in Figure 2. Figure 5 shown.

[0093] from Figure 5 It can be concluded that the 20% TS-ZIS catalyst can still exert good catalytic performance when facing different epoxy substrates, which confirms the excellent applicability of 20% TS-ZIS.

[0094] Test Example 4

[0095] 20% TS-ZIS catalyst, 0.3 mmol TBAB, and different molar amounts of SO (5 mmol or 20 mmol, respectively) were added to the reactor and sealed. The reactor was then purged with industrial flue gas (air containing 10% CO2) to ensure that there was no other gas in the reactor. After the gas entered the reactor, the reactor was continuously vented to maintain an atmosphere of 1.0 MPa.

[0096] The reactor was placed in an oil bath with a rotation speed of 20 rpm and a temperature of 80°C. The light source was visible light, and the distance between the light source and the reactor was controlled so that the light intensity was maintained at 300 mW / cm 2 ;

[0097] When the molar amount of SO was 20 mmol, the full-spectrum irradiation reaction time was set to 4 h and 6 h, respectively;

[0098] When the molar amount of SO was 5 mmol, the full-spectrum irradiation reaction time was set to 4 h and 6 h, respectively;

[0099] After the reaction was completed, the reactor was placed in ice water to completely cool and release the gas.

[0100] After the reactor was opened, 30 ml of acetonitrile was used as a solvent, a quantitative amount of biphenyl was added as an internal standard, the resulting reaction solution was centrifuged, and the suspension was filtered using a 0.22 μl syringe filter.

[0101] Quantitative and qualitative analysis using gas chromatography revealed that when 20 mmol of SO was catalyzed by 20% TS-ZIS, the yield after a full-spectrum irradiation reaction time of 4 hours was 34.90%. Extending the reaction time to 6 hours increased the yield to 35.58%. This is because the 10% CO₂-containing industrial flue gas is completely absorbed by the 20 mmol of SO. Therefore, while maintaining a constant pressure, the amount of SO needed to be reduced to observe the catalytic performance of 20% TS-ZIS.

[0102] Therefore, when 20% TS-ZIS was used to catalyze 5 mmol SO, the yield was 64.94% after 4 h of full spectrum irradiation reaction time. When the reaction time was extended to 6 h, the yield was 89.58%.

[0103] The results are as follows Figure 6 As shown, 20% TS-ZIS was demonstrated to convert epoxides into high-value chemicals using industrial flue gas, demonstrating the potential of this catalyst for industrial catalysis.

[0104] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art may still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein with equivalents. Any modifications, equivalent replacements, and modifications made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing a molecular sieve-indium zinc sulfide heterogeneous material for photothermal driven CO2 cycloaddition, characterized in that: The following steps are involved: (1) Add a certain amount of TS-1 molecular sieve to anhydrous ethanol and stir for 0.5 to 1.5 hours; (2) Anhydrous zinc chloride, indium trichloride tetrahydrate, and thioacetamide were weighed in a molar ratio of 1:2:(6-10), mixed, and added to ethanol dispersed with TS-1 molecular sieves, and stirred for 20-40 minutes; (3) heating the mixture at 140-180° C. for 10-14 h, cooling the mixture to room temperature, centrifuging, washing, and drying the mixture to obtain a molecular sieve-sulfur indium zinc heterogeneous material TS-ZIS.

2. The preparation method according to claim 1, characterized in that The molar ratio of the anhydrous zinc chloride, indium trichloride tetrahydrate and thioacetamide is 1:2:

8.

3. The preparation method according to claim 1, characterized in that The mass ratio of the molecular sieve to the sulfur indium zinc in preparing the molecular sieve-sulfur indium zinc heterogeneous material is 1: (3-20).

4. The preparation method according to claim 3, characterized in that The mass ratio of the TS-1 molecular sieve to zinc indium sulfide ZIS is TS-1:ZIS=1:

5.

5. The preparation method according to claim 1, characterized in that The TS-1 molecular sieve can be replaced by MCM-41 molecular sieve or SBA-15 molecular sieve.

6. Use of a molecular sieve-sulfur indium zinc heterogeneous material prepared according to the preparation method according to any one of claims 1 to 5 in driving CO2 cycloaddition.

7. The use according to claim 6, characterized in that The molecular sieve-sulfur indium zinc heterogeneous material TS-ZIS is used as a photothermal catalyst to drive the CO2 cycloaddition reaction at 60-90°C and normal pressure.

8. The use according to claim 7, characterized in that The application method includes the following steps: In a 1.0 MPa CO2 atmosphere, TS-ZIS catalyst, tetrabutylammonium bromide as a co-catalyst, and epoxide were added. The reaction temperature was set to 80 °C, the speed was set to 20 rpm, and the light intensity was set to 300-600 mW / cm 2 The cycloaddition reaction was carried out under visible light irradiation, and the reaction time was 3.5 to 4.5 hours; The epoxides include epichlorohydrin, epibromohydrin, 1,2-epoxyhexane, 1,2-epoxybutylene, and styrene oxide.

9. The use according to claim 8, characterized in that The CO2 atmosphere can be replaced by industrial flue gas containing 10% CO2.

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