CN114433171B - Carbon dioxide reduction photocatalyst and preparation method and application thereof - Google Patents
Carbon dioxide reduction photocatalyst and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Chemical Kinetics & Catalysis (AREA)
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- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a second kindThe preparation method of the carbon oxide reduction photocatalyst and the application thereof comprises the following steps: dissolving bismuth salt and cesium salt in dimethyl sulfoxide, adding molecular sieve, mixing, grinding and soaking, and heating and maintaining for a certain period of time to form molecular sieve @ Cs 3 Bi 2 Br 9 A complex. Molecular sieve @ Cs prepared 3 Bi 2 Br 9 The photocatalyst has good photo-generated carrier separation and transfer efficiency, and can realize photo-catalytic reduction of CO when irradiated by light 2 CO is produced with a CO yield of 5.62-25.4. Mu. Mol g ‑1 h ‑1 Photocatalytic reduction of CO in the gas phase compared to pure cesium bismuth bromide 2 The performance of CO generation is improved by 2.97-13.4 times.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and in particular relates to a molecular sieve @ Cs 3 Bi 2 Br 9 Composite, preparation method and application thereof, and the composite can be applied to photocatalysis of CO in gas-solid phase 2 And (5) reduction.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
To mitigate global warming, much research effort is devoted to the conversion of CO by using renewable energy sources 2 Reduction produces high value chemicals. Wherein, the photo-catalytic CO 2 Reduction of CO that can be captured in the atmosphere 2 CO is taken as raw material 2 Conversion to CO, which is CO 2 Good routes for conversion and CO synthesis. However, the existing photocatalyst is mainly limited by low light conversion efficiency and cannot be well applied. The halide perovskite material is widely focused on due to the excellent optical performance, and is considered as a potential visible light photocatalytic material, however, the lead-based halide perovskite material prevents large-scale application due to high toxicity of lead, and has larger microscopic size due to the property of ionic crystals, and the larger microscopic size tends to bring smaller specific surface area, which is unfavorable for the adsorption of reactants on the surface of a catalyst, and meanwhile, fewer reaction sites and is unfavorable for the progress of photocatalytic reaction. Furthermore, it is unstable in the aqueous phase.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a molecular sieve @ Cs 3 Bi 2 Br 9 A compound and a preparation method and application thereof.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the present invention provides a molecular sieve @ Cs 3 Bi 2 Br 9 A method of preparing a composite comprising the steps of:
dissolving bismuth salt and cesium salt in organic solvent, adding molecular sieve, mixing, soaking, grinding to make molecular sieve powder and solution fully mixed, heating and heat-insulating for a set time to form molecular sieve @ Cs 3 Bi 2 Br 9 A complex.
In a second aspect, the present invention provides a molecular sieve @ Cs 3 Bi 2 Br 9 The compound is prepared by the preparation method.
In a third aspect, the molecular sieve @ Cs 3 Bi 2 Br 9 Complex in photocatalytic reduction of CO 2 Is used in the field of applications.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
the photocatalyst is synthesized by a method of chemical impregnation, grinding and heat preservation in an oven, and has the advantages of simple preparation method, mild reaction condition, low cost, large-scale preparation and no pollution, and has good application and industrialization values.
Molecular sieve @ Cs prepared 3 Bi 2 Br 9 The photocatalyst has good photo-generated carrier separation and transfer efficiency, and can realize photo-catalytic reduction of CO when irradiated by light 2 CO is produced with a CO yield of 5.62-25.4. Mu. Mol g -1 h -1 Photocatalytic reduction of CO in the gas phase compared to pure cesium bismuth bromide 2 The performance of CO generation is improved by 2.97-13.4 times.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 shows the different Cs prepared in Experimental example 1 3 Bi 2 Br 9 MCM-41 molecular sieve @ Cs in mass ratio 3 Bi 2 Br 9 XRD patterns of the photocatalyst, wherein a is a large-angle XRD pattern and b is a small-angle XRD pattern.
FIG. 2 shows the 50% by mass of Cs prepared in Experimental example 1 3 Bi 2 Br 9 Other molecular sieves @ Cs in proportion to the amount of the supported 3 Bi 2 Br 9 XRD patterns of the photocatalyst (including SBA-3, SBA-15 and MCM-48), wherein a, c and e are large-angle XRD patterns, and b, d and f are small-angle XRD patterns.
FIG. 3 shows the MCM-41 molecular sieve @ Cs prepared in Experimental example 1 3 Bi 2 Br 9 X-ray photoelectron spectroscopy (XPS) analysis of the photocatalyst, wherein a is XPS total spectrum; b is Cs 3d XPS spectrum; c is Bi 4f XPS spectrum; d is Br 3d XPS spectrum.
FIG. 4 shows the MCM-41 molecular sieve @ Cs prepared in Experimental example 1 3 Bi 2 Br 9 High-angle annular dark field Scanning Transmission Electron Microscope (STEM) photo of photocatalyst, wherein small particles are Cs 3 Bi 2 Br 9 。
FIG. 5 shows the MCM-41 molecular sieve @ Cs prepared in Experimental example 1 3 Bi 2 Br 9 PhotocatalysisOptical testing of the agent. Wherein a is MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 B is MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 Is a sample color of (c).
FIG. 6 photocatalytic CO for the product of example 1 2 A reduction performance map; wherein a is MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 The CO yield of the photocatalyst under different test conditions changes with time in the 2h reaction time; b is a series of MCM-41 molecular sieves @ Cs 3 Bi 2 Br 9 CO gas production of the photocatalyst under the irradiation of visible light, c is 5 times of circulating photocatalysis experiments, and d is the use of 13 CO 2 MS diagram when gas source is used.
FIG. 7 shows the different molecular sieves @ Cs of the product of example 1 3 Bi 2 Br 9 Photocatalytic CO 2 Reduction performance diagram.
FIG. 8 is a graph of MCM-41 molecular sieves @ Cs in the product of example 1 3 Bi 2 Br 9 CO from the product of comparative example 1 2 -TPD spectrum.
FIG. 9 is a sample of the product MCM-41 molecular sieves @ Cs of example 1 3 Bi 2 Br 9 In the photocatalysis of CO 2 In situ infrared (FT-IR) spectrum during reduction and MCM-41 molecular sieves @ Cs 3 Bi 2 Br 9 And pure Cs 3 Bi 2 Br 9 PL and TRPL spectra of (a). Wherein a is MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 CO is introduced under dark condition 2 B is MCM-41 molecular sieve @ Cs after in-situ cell closure 3 Bi 2 Br 9 In-situ infrared spectrum under illumination condition, c is MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 And pure Cs 3 Bi 2 Br 9 Fluorescence emission spectrum of photocatalyst, d is MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 And pure Cs 3 Bi 2 Br 9 Steady state fluorescence spectrum of the photocatalyst.
FIG. 10 is a schematic diagram of the product MCM-41 molecular sieves @ Cs of example 1 3 Bi 2 Br 9 Schematic illustration during the preparation process.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As described in the background art, the prior art has the problems of toxicity, larger particle size and easy decomposition of water by using a single lead-containing halide perovskite, and the invention provides the following technical proposal for solving the problems.
In a first aspect, the present invention provides a molecular sieve @ Cs 3 Bi 2 Br 9 A method of preparing a composite comprising the steps of:
dissolving bismuth salt and cesium salt in organic solvent, adding molecular sieve, mixing, soaking, grinding to make molecular sieve powder and solution fully mixed, heating and heat-insulating for a set time to form molecular sieve @ Cs 3 Bi 2 Br 9 A complex.
Molecular sieves are used as substrate materials, and the pore channels can be used for limiting the growth of perovskite and increasing reaction sites. In addition, the molecular sieve can increase the specific surface area of the photocatalyst and increase CO 2 Promotes the separation and transfer of photogenerated carriers and reduces CO 2 The activation energy barrier of the reduction, thereby improving the photocatalytic performance.
In some embodiments, the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide. The corresponding bromide salt solution may be dissolved.
In some embodiments, the molecular sieve @ Cs 3 Bi 2 Br 9 In the complex, cs 3 Bi 2 Br 9 The loading of (2) is 10% to 60%, preferably 45% to 55%, more preferably 50%. Too much loading can result in reduced catalytic activity.
Preferably, the molar ratio of bismuth salt to cesium salt is 1.8-2.5:2.5 to 3.5, more preferably 2:3.
preferably, the bismuth salt is bismuth bromide (since the perovskite material is Cs 3 Bi 2 Br 9 The corresponding salt is a bromide of bismuth, namely bismuth bromide).
Preferably, the cesium salt is cesium bromide (since the perovskite material is Cs 3 Bi 2 Br 9 The corresponding salt is the bromide of cesium, i.e., cesium bromide).
In some embodiments, the milling time is 20-40 minutes. The particle size of the molecular sieve itself is not significantly changed during the milling process, which is only to allow the molecular sieve and the solution to be thoroughly mixed.
In some embodiments, the temperature of the heating and preserving heat is 150-160 ℃, and the temperature is too high and too low, which is not beneficial to the generation of perovskite particles, and the time of the heating and preserving heat is 10-14 hours; similarly, too long a soak time can affect the perovskite state. Preferably, the temperature of heating and heat preservation is 155 ℃, and the time of heating and heat preservation is 12 hours.
In the heating and heat preserving process, the precursor liquid is converted into lead-free perovskite cesium bismuth bromine (Cs) 3 Bi 2 Br 9 )。
In a second aspect, the present invention provides a molecular sieve @ Cs 3 Bi 2 Br 9 The compound is prepared by the preparation method.
In a third aspect, the molecular sieve @ Cs 3 Bi 2 Br 9 Complex in photocatalytic reduction of CO 2 Is used in the field of applications.
In order to enable those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below with reference to specific examples and comparative examples.
The test materials used in the examples below are all conventional in the art and are commercially available.
Example 1
A visible light photocatalyst for photocatalytic carbon dioxide reduction and a preparation method thereof comprise the following steps:
(1) With the aid of ultrasound, a certain amount of bismuth bromide (BiBr 3 ) And a certain amount of cesium bromide (CsBr) was dissolved in 500 μl of dimethyl sulfoxide.
(2) The resulting solution was added to a mortar containing 250mg of MCM-41 molecular sieve powder and ground for 30min.
(3) Placing the ground mortar into an oven, and preserving the temperature for 12 hours at 155 ℃ to obtain the MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 A photocatalyst. Can be used for photocatalytic CO 2 And (3) reduction reaction.
(4) By varying the bismuth bromide (BiBr) 3 ) And cesium bromide (CsBr), i.e., 12mg cesium bromide and 16.8mg bismuth bromide are dissolved in 500 microliters dimethyl sulfoxide, and after being fully ground and mixed with 250mg MCM-41 molecular sieve powder, the mixture is heat-preserved for 12 hours at 155 ℃ to obtain the MCM-41 molecular sieve@Cs with the mass fraction of 10 percent 3 Bi 2 Br 9 ；
24mg of cesium bromide and 33.6mg of bismuth bromide are dissolved in 500 microliters of dimethyl sulfoxide, and after being fully ground and mixed with 250mg of MCM-41 molecular sieve powder, the mixture is preserved for 12 hours at 155 ℃ to obtain the MCM-41 molecular sieve @ Cs with the mass fraction of 20 percent 3 Bi 2 Br 9 ；
And the like, the MCM-41 molecular sieve @ Cs with different mass fractions can be obtained 3 Bi 2 Br 9 。
The same method is adopted to change the MCM-41 molecular sieve into SBA-3, SBA-15 and MCM-48 molecular sieves, and a series of molecular sieves @ Cs can be synthesized 3 Bi 2 Br 9 The photocatalyst, taking SBA-3 molecular sieve as an example, is prepared by dissolving 60mg cesium bromide and 84mg bismuth bromide in 500 microliters dimethyl sulfoxide, grinding and mixing with 250mg SBA-3 molecular sieve powder, and then preserving the temperature at 155 ℃ for 12 hours to obtain SBA-3 molecular sieve @ Cs with the mass fraction of 50% 3 Bi 2 Br 9 。
Photocatalytic CO 2 Reduction test
1. The test method comprises the following steps:
the photocatalytic CO was carried out at atmospheric pressure using a self-made cylindrical quartz reactor (volume 45 mL) 2 And (5) reduction experiment. Before the photoreaction, 5mg of the photocatalyst was uniformly dispersed into a round cap having a diameter of 2.5cm, and the original form containing the photocatalyst was put into a reactor. 500 microliters of water was dropped outside the round cap and the reactor was covered with quartzAnd (5) sealing. Before the reaction, the flow rate was 10mL min -1 High purity CO of (C) 2 The air in the reactor was discharged. The reactor is connected with circulating cooling water, so that the reaction is kept at 20 ℃ and the change of the yield caused by overhigh temperature is avoided. Using a 300W xenon lamp equipped with a visible light filter as a light source, 0.5mL of gas was withdrawn from the reactor with a sampling needle after 2 hours of illumination, and analyzed by an on-line gas chromatograph equipped with a Flame Ionization Detector (FID).
2. Test results:
CBB in each figure refers to Cs 3 Bi 2 Br 9 。
Example 1 product MCM-41 molecular sieves @ Cs 3 Bi 2 Br 9 The XRD pattern of the photocatalyst is shown in FIG. 1, and it can be seen that in the composite material, MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 The shape and position of characteristic peaks and Cs 3 Bi 2 Br 9 The XRD spectrum of the standard card matches well. In addition, the low angle XRD pattern indicates that the process of growing perovskite in a limited domain does not change the structure of the MCM-41 molecular sieve.
Example 1 product other molecular sieves @ Cs 3 Bi 2 Br 9 XRD patterns of the photocatalyst are shown in FIG. 2, and it can be seen that SBA-3, SBA-15 and MCM-48 molecular sieves limit-grown Cs 3 Bi 2 Br 9 The characteristic peak positions of the nano particles are equal to Cs 3 Bi 2 Br 9 The XRD spectrum of the standard card matches well. The small angle XRD pattern also illustrates that the process of confinement growth does not alter the structure of the molecular sieve.
Example 1 product MCM-41 molecular sieves @ Cs 3 Bi 2 Br 9 The XPS spectrum of the photocatalyst is shown in FIG. 3. XPS characterization further investigated the chemical state and the sample composition. The binding energy positions of the peaks of the elements are consistent with those in the literature, and the result of the binding with XRD shows that the sample photocatalyst is successfully synthesized.
Example 1 product MCM-41 molecular sieves @ Cs 3 Bi 2 Br 9 A high angle annular dark field Scanning Transmission Electron Microscope (STEM) photograph of the photocatalyst is shown in FIG. 4. Wherein the small particles are lead-free perovskite Cs 3 Bi 2 Br 9 。
Product MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 Optical testing of the photocatalyst is shown in FIG. 5, and it can be seen that the photocatalyst compares to pure Cs 3 Bi 2 Br 9 MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 The absorption edge of the photocatalyst shows blue shift, and as the load ratio increases, the light absorption gradually increases, which is caused by quantum size effect. Proved Cs 3 Bi 2 Br 9 The finite field is grown in the MCM-41 molecular sieve, and the photo of the sample is shown in figure 5, so that the color depth of the sample is deepened continuously.
Example 1 product MCM-41 molecular sieves @ Cs 3 Bi 2 Br 9 Photocatalytic CO of photocatalyst 2 As shown in FIG. 6, the comparative experiment shows that the CO generation is driven by the photocatalytic reaction (FIG. 6 a), MCM-41 molecular sieves @ Cs are irradiated with visible light 3 Bi 2 Br 9 CO of photocatalyst 2 Reduction power compared to initial Cs 3 Bi 2 Br 9 Has great improvement on Cs 3 Bi 2 Br 9 The performance is best when the mass fraction of the property is 50%, and the CO production rate is 17.24 mu mol g -1 h -1 Is the initial Cs 3 Bi 2 Br 9 9 times (fig. 6 b). Stability can be used to characterize the practical application potential of the photocatalyst, and after 5 cycling stability experiments (fig. 6 c), the activity of the photocatalyst is hardly reduced, indicating that the photocatalyst is stable during the hydrolysis experiment. Isotope testing further verifies that the carbon source in the CO in the product comes from CO 2 (FIG. 6 d).
Different molecular sieves @ Cs 3 Bi 2 Br 9 Photocatalytic CO of photocatalyst 2 The performance of the reduction is shown in FIG. 7, where SBA-3, SBA-15 and MCM-48 molecular sieves limit Cs growth 3 Bi 2 Br 9 All are against CO 2 The reduction performance is improved to a certain extent, and the method is proved to have certain universality.
Example 1 product MCM-41 molecular sieves @ Cs 3 Bi 2 Br 9 Photocatalyst comparative Cs 3 Bi 2 Br 9 CO of (c) 2 The TPD spectrum is shown in fig. 8. The active sites of photocatalytic CO2 reduction can be assessed by the total area under each desorption peak curve. MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 The peak area of the photocatalyst is larger than Cs 3 Bi 2 Br 9 Proved by MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 Can obviously improve CO 2 Is used for the adsorption capacity of the catalyst. This facilitates photocatalytic CO 2 And (5) a reduction process. At the same time, MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 The desorption temperature of the photocatalyst moves to the high temperature direction, which indicates CO 2 Molecular and MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 The photocatalyst is more strongly bound. Due to this strong interaction, the photocatalytic CO 2 The activation energy barrier for reduction is reduced.
Example 1 product MCM-41 molecular sieves @ Cs 3 Bi 2 Br 9 Photocatalytic CO 2 In situ infrared (FT-IR) spectrum in reduction process, MCM-41 molecular sieve @ Cs 3 Bi 2 Br 9 And pure Cs 3 Bi 2 Br 9 PL and TRPL spectra PL spectra and TRPL spectra of (c) are shown in fig. 9. It can be seen that the CO2 adsorbing species in the CO2 adsorption process mainly comprise bidentate carbonates (b-CO 3 2- ) And bicarbonate (HCO) 3 - ) (FIG. 9 a). In the photocatalysis process, the main intermediate is monodentate carbonate m-CO 3 2- And formate (×cooh) (fig. 9 b). As shown in FIG. 9c, MCM-41 molecular sieves @ Cs 3 Bi 2 Br 9 PL emission peak intensity and Cs of photocatalyst 3 Bi 2 Br 9 The decrease in the ratio is significant, indicating a decrease in the recombination rate of photogenerated electrons and holes. In FIG. 6d, a Time Resolved Photoluminescence (TRPL) spectrum was studied, and a three exponential function was used to fit the decay curve, MCM-41 molecular sieves @ Cs 3 Bi 2 Br 9 τ is 5.274ns, compared with Cs 3 Bi 2 Br 9 (2.038 ns) there is a significant increase in average PL lifetime, an increase in average PL lifetime implying molecular sieve limited domain Cs 3 Bi 2 Br 9 Has longer carrier life and is favorable for the photocatalytic reaction.
Example 1 product MCM-41 molecular sieves @ Cs 3 Bi 2 Br 9 A schematic of the synthesis of the photocatalyst is shown in FIG. 10.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. Molecular sieve @ Cs 3 Bi 2 Br 9 Complex in photocatalytic reduction of CO 2 Is characterized in that:
the molecular sieve @ Cs 3 Bi 2 Br 9 The preparation method of the compound comprises the following steps:
dissolving bismuth salt and cesium salt in organic solvent, adding molecular sieve, mixing, soaking, grinding to make molecular sieve powder and solution fully mixed, heating and heat-insulating for a set time to form molecular sieve @ Cs 3 Bi 2 Br 9 A complex; the temperature of heating and heat preservation is 150-160 ℃, and the time of heating and heat preservation is 10-14h; the molecular sieve @ Cs 3 Bi 2 Br 9 In the complex, cs 3 Bi 2 Br 9 The loading of (2) is 45% -55%; the molecular sieve is SBA-3;
the photocatalytic reduction of CO 2 The test steps of (a) are as follows:
a self-made cylindrical quartz reactor with the volume of 45mL is used for photocatalysis of CO under normal pressure 2 Reduction experiments 5mg of molecular sieves @ Cs prior to photoreaction 3 Bi 2 Br 9 The composite was uniformly dispersed in a round cap having a diameter of 2.5cm and was charged with molecular sieves @ Cs 3 Bi 2 Br 9 Putting the round cap of the compound into a reactor; dropping 500 microliters of water outside the round cap, and sealing the reactor with a quartz cover; before the reaction, the flow rate was 10mL min -1 High purity CO of (C) 2 Discharging the air in the reactor; reactor and method for producing sameThe circulating cooling water is connected, so that the reaction is kept at 20 ℃, and the change of the yield caused by overhigh temperature is avoided; using a 300W xenon lamp equipped with a visible light filter as a light source, 0.5mL of gas was extracted from the reactor with a sampling needle after 2 hours of illumination, and analyzed by an on-line gas chromatograph equipped with a flame ionization detector.
2. The molecular sieve @ Cs according to claim 1 3 Bi 2 Br 9 Complex in photocatalytic reduction of CO 2 Is characterized in that: the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide.
3. The molecular sieve @ Cs according to claim 1 3 Bi 2 Br 9 Complex in photocatalytic reduction of CO 2 Is characterized in that: cs (cells) 3 Bi 2 Br 9 Is 50%.
4. The molecular sieve @ Cs according to claim 1 3 Bi 2 Br 9 Complex in photocatalytic reduction of CO 2 Is characterized in that: the molar ratio of bismuth salt to cesium salt is 1.8-2.5:2.5-3.5.
5. The molecular sieve @ Cs according to claim 1 3 Bi 2 Br 9 Complex in photocatalytic reduction of CO 2 Is characterized in that: the molar ratio of bismuth salt to cesium salt is 2:3.
6. the molecular sieve @ Cs according to claim 5 3 Bi 2 Br 9 Complex in photocatalytic reduction of CO 2 Is characterized in that: the bismuth salt is bismuth bromide.
7. The molecular sieve @ Cs according to claim 5 3 Bi 2 Br 9 Complex in photocatalytic reduction of CO 2 Is characterized in that: the cesium salt is cesium bromide.
8. The molecular sieve @ Cs according to claim 1 3 Bi 2 Br 9 Complex in photocatalytic reduction of CO 2 Is characterized in that: the grinding time is 20-40min.
9. The molecular sieve @ Cs according to claim 1 3 Bi 2 Br 9 Complex in photocatalytic reduction of CO 2 Is characterized in that: the temperature of heating and heat preservation is 155 ℃, and the time of heating and heat preservation is 12 hours.
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