Application of basic zinc carbonate in photocatalytic CO2 reduction

Abstract

The invention discloses an application of basic zinc carbonate in photocatalytic CO2 reduction. A product obtained by photocatalytic CO2 reduction is CO. According to the method, basic zinc carbonate is used, CO2 can be reduced into CO through photocatalytic reaction under the condition that no sacrificial agent or cocatalyst exists, reagents needed in the photocatalytic CO2 reduction process are saved, and the use condition is simple. The basic zinc carbonate is subjected to photocatalytic CO2 reduction reaction under a 300W high-voltage xenon lamp for 5 hours, the average generation rate of CO is 1.61 micromoles g <-1 > h <-1 >, and the basic zinc carbonate also shows good stability and repeatability in a circular reaction test.

Description

Technical Field

[0001] The invention belongs to the technical field of photocatalysis, and specifically relates to the photocatalytic reaction of basic zinc carbonate with CO 2 Restore the app. Background Art

[0002] The combustion of carbon dioxide-intensive fossil fuels causes CO 2 The large amount of emissions will 2 Conversion into high value-added chemicals is a way to reduce CO 2 method of emissions.

[0003] Photocatalytic CO 2 Reduction is the process of using photoelectrons to convert CO 2 Reduction to CO, CH 4 Artificial photosynthesis of high value-added products such as TiO 2 , ZnO, Fe 2 O 3 , gC 3 N 4 、WC、CeO 2 and BiVO 4 Traditional semiconductor photocatalysts have been widely used in the photocatalytic CO 2 However, these materials have great potential in photocatalytic CO reduction. 2 The reduction process requires a hole sacrificial agent, and some materials also require the use of a co-catalyst. The use of hole sacrificial agents and co-catalysts will result in additional energy consumption. Therefore, it is necessary to find a method for photocatalytic CO 2 New materials that do not require hole sacrificial agents and co-catalysts during reduction. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing a photocatalytic reaction of zinc carbonate with a photocatalytic reaction of CO 2 The application of the restoration is to solve at least one of the above technical problems.

[0005] In a first aspect of the present invention, basic zinc carbonate is provided in the photocatalytic CO 2 Applications of photocatalytic CO reduction 2 The product of reduction is CO.

[0006] The basic zinc carbonate of the present invention can convert CO into 2 Reduction to CO, saving photocatalytic CO 2 The reagents required for the reduction process are simple to use and also show that basic zinc carbonate has a photocatalytic effect on CO 2 High selectivity for CO in reduction.

[0007] In some embodiments, the molecular formula of basic zinc carbonate is Zn 5 (OH) 6 (CO 3 ) 2 .

[0008] In some embodiments, basic zinc carbonate is used to photocatalyze CO 2 The restoration method includes the following steps:

[0009] Disperse 20-40 mg of basic zinc carbonate in 300-500 μL of water to obtain a mixed solution, evenly apply the mixed solution on quartz glass, and then dry it at 50-70°C for 1-2 hours to obtain Zn loaded on quartz glass. 5 (OH) 6 (CO 3 ) 2 film;

[0010] After placing the quartz glass in a reactor filled with 10-15 mL of water, the reactor was evacuated to a pressure of 0.1 KPa, and 99.999% CO was introduced. 2 The pressure of the gas to the reactor is 80 KPa, which is repeated three times. The reactor is placed under a 300 W high-pressure xenon lamp for reaction for 1 to 10 hours.

[0011] In some embodiments, basic zinc carbonate is used to photocatalyze CO 2 The reduction method can be to disperse 30 mg of basic zinc carbonate in 400 μL of water to obtain a mixed solution, and evenly drop the mixed solution on a 3 cm × 3 cm quartz glass, and then dry it at 60 ° C for 1 hour to obtain Zn loaded on the quartz glass. 5 (OH) 6 (CO 3 ) 2 film;

[0012] After placing the quartz glass in a reactor filled with 10 mL of water, the reactor was evacuated to a pressure of 0.1 KPa, and 99.999% CO was introduced. 2 The pressure of the gas to the reactor was 80 KPa, which was repeated three times. The reactor was placed under a 300 W high-pressure xenon lamp for reaction for 5 h.

[0013] In some embodiments, Zn 5 (OH) 6 (CO 3 ) 2 It can be prepared by the following steps:

[0014] S1, Na 2 CO 3 Dissolve in deionized water and stir for 10 to 30 minutes to obtain Na2 CO 3 Solution;

[0015] S2, Zn(NO 3 ) 2 6H 2 O was dissolved in deionized water and stirred for 10 to 30 minutes to obtain Zn(NO 3 ) 2 6H 2 O in aqueous solution;

[0016] S3. Place Zn(NO 3 ) 2 6H 2 O solution is dropped into Na 2 CO 3 The solution was stirred for 5 to 7 hours and centrifuged. The precipitate obtained by centrifugation was washed with deionized water and anhydrous ethanol respectively and centrifuged 3 to 10 times to obtain a solid. The solid was then dried at 50 to 70 ° C for 10 to 12 hours to obtain Zn 5 (OH) 6 (CO 3 ) 2 ,

[0017] Among them, Na 2 CO 3 With Zn(NO 3 ) 2 6H 2 The molar ratio of O is (2.5~4):(1~2).

[0018] 5Zn was coprecipitated at room temperature 2+ +2CO 3 2- +6OH - →Zn 5 (OH) 6 (CO 3 ) 2 ↓Preparation of Zn 5 (OH) 6 (CO 3 ) 2 The preparation method is simple, the production cost is low, and the obtained Zn 5 (OH) 6 (CO 3 ) 2 It is a nanosheet structure.

[0019] In some embodiments, Na 2 CO 3 The solution can be prepared by mixing 0.3 to 1.3 g Na 2 CO 3Dissolve in 40-60 mL of deionized water and stir to obtain the product.

[0020] In some embodiments, Zn(NO 3 ) 2 6H 2 The preparation method of the aqueous solution of Zn(NO) can be as follows: 0.21-2.92 g Zn(NO 3 ) 2 6H 2 O is dissolved in 5-15 mL of deionized water and stirred to obtain the product.

[0021] In some embodiments, in step S1, the volume of deionized water may be 50 mL, and the stirring time may be 20 min.

[0022] In some embodiments, in step S2, the volume of deionized water may be 10 mL, and the stirring time may be 20 min.

[0023] In some embodiments, in step S3, the drying is vacuum drying, the drying temperature may be 60° C., and the drying time may be 12 h.

[0024] In some embodiments, in step S3, the volume of deionized water and anhydrous ethanol may be 10-20 mL. More preferably, the volume of deionized water and anhydrous ethanol may be 10 mL.

[0025] In some embodiments, in step S3, the centrifugal treatment method can be to use a centrifuge to centrifuge at a speed of 8000 to 10000 rpm for 3 to 5 minutes.

[0026] The beneficial effects of the present invention are:

[0027] The basic zinc carbonate of the present invention has hydroxide ions in its structure that can change the energy band structure and valence band oxidation potential of the zinc material, thereby improving the charge separation efficiency and rate, and converting CO into CO through a photocatalytic reaction without the need for a hole sacrificial agent and a co-catalyst. 2 reduction to CO, not only showing that basic zinc carbonate has a photocatalytic effect on CO 2 High selectivity for CO reduction, saving photocatalytic CO 2 The reagents required for the reduction process are simple to use. Zn 5 (OH) 6 (CO 3 ) 2 Photocatalytic CO generation under 300W high pressure xenon lamp 2 The average CO production rate was 1.61 μmol g –1 h –1 , and also showed good stability and repeatability in the 50h cyclic reaction test. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The Zn prepared in Example 1 of the present invention 5 (OH) 6 (CO 3 ) 2 XRD pattern of

[0029] Figure 2 The Zn prepared in Example 1 of the present invention 5 (OH) 6 (CO 3 ) 2 XPS analysis fitting results; Figure 2 (a) Zn 5 (OH) 6 (CO 3 ) 2 The full XPS spectrum, Figure 2 (b) is the O 1s XPS graph, Figure 2 (c) is the Zn 2p XPS graph, Figure 2 (d) is the C 1s XPS pattern;

[0030] Figure 3 (a) is the Zn prepared in Example 1 of the present invention 5 (OH) 6 (CO 3 ) 2 SEM images of Figure 3 (b) Figure 3 (a) is an enlarged view of Figure 3 (c) Zn prepared in Example 1 of the present invention 5 (OH) 6 (CO 3 ) 2 TEM images of

[0031] Figure 4 (a) is the Zn prepared in Example 1 5 (OH) 6 (CO 3 ) 2 UV-diffuse reflectance spectrum; Figure 4 (b) Figure 4 (a) is an enlarged view; Figure 4 (c) is the Zn prepared in Example 1 5 (OH) 6 (CO 3 ) 2 Bandgap diagram of Figure 4 (d) is the Zn prepared in Example 1 5 (OH) 6(CO 3 ) 2 of Motshotkey;

[0032] Figure 4 (e) is the Zn prepared in Example 1 5 (OH) 6 (CO 3 ) 2 The energy band calculation results of Figure 4 (f) is the Zn prepared in Example 1 5 (OH) 6 (CO 3 ) 2 Photoluminescence spectrum of

[0033] Figure 5 The photocatalytic CO 2 Restore test results. Figure 5 (a) Zn 5 (OH) 6 (CO 3 ) 2 The result of the photocatalytic reaction in 0-5h. Figure 5 (b) is a comparison chart of CO production under different conditions. Figure 5 (c) is the CO evolution-time diagram. DETAILED DESCRIPTION

[0034] The present invention is further described in detail below in conjunction with the accompanying drawings, but the embodiments of the present invention are not limited thereto. The raw materials and reagents involved in the following examples can all be obtained from commercial channels.

[0035] Example 1

[0036] This embodiment provides Zn 5 (OH) 6 (CO 3 ) 2 The preparation method comprises the following steps:

[0037] Weigh 1.272gNa 2 CO 3 (0.012 mol) was added into 50 mL of deionized water and stirred with a magnetic stirrer for 20 min to obtain Na 2 CO 3 solution; then weigh 2.38gZn(NO 3 ) 2 6H 2 O (0.008 mol) was added into 10 mL of deionized water and stirred with a magnetic stirrer for 20 min to obtain Zn(NO 3 ) 2 6H2 O aqueous solution; then Zn(NO 3 ) 2 6H 2 O solution is dropped into Na 2 CO 3 The solution was stirred at room temperature for 6 h, and centrifuged at 9000 rpm for 3 min. The precipitate obtained by centrifugation was washed with 10 mL of anhydrous ethanol and 10 mL of deionized water, respectively, and centrifuged 3 times, each time for 3 min. The solid obtained after centrifugation was placed in a vacuum oven at 60 ° C and dried for 12 h to obtain a white sample.

[0038] The white sample obtained in Example 1 was subjected to XRD analysis, and the results were as follows: Figure 1 As shown. Figure 1 It can be seen that the diffraction peaks at 13.05, 16.42, 22.16, 24.24, 28.28, 31.29, 32.91, 34.88, 36.18, 38.35, 40.56, 43.69, 47.31, 50.75, 54.04, 58.04, 59.53, 63.64, 66.64, 68.09, and 73.20 can be indexed to Zn 5 (OH) 6 (CO 3 ) 2 (PDF#No.72-1100) of (200), (001), (111), (310), (020), (220), (021), (221), (112), (511), (402), (421), (222), (003), (800), (332), (223), (622), (731), (532), (640). The crystal planes of the two samples match well, indicating that the white sample is Zn 5 (OH) 6 (CO 3 ) 2 , verify that Zn in Example 1 5 (OH) 6 (CO 3 ) 2 Preparation was successful.

[0039] For Zn in Example 1 5 (OH) 6 (CO 3 ) 2 X-ray photoelectron spectroscopy (XPS) analysis was performed and the obtained XPS peaks were fitted. The results are as follows Figure 2 As shown, Figure 2 (a) Zn 5 (OH) 6 (CO3 ) 2 The full XPS spectrum, Figure 2 (b) is the O 1s XPS graph, Figure 2 (c) is the Zn 2p XPS graph, Figure 2 (d) is the C 1s XPS spectrum. Figure 2 (b) It can be seen that the peaks at 530.6 eV and 535.4 eV correspond to the core energy level O1s, and the first peak is related to Zn 5 (OH) 6 (CO 3 ) 2 The second peak is attributed to the oxygen vacancy in the structure, and the second peak is attributed to the oxygen of the hydroxyl anion. Figure 2 (c) It can be seen that in the core energy level Zn 2p, the peaks at 1020.9, 1025.2, and 1041.1 eV are consistent with Zn(OH) 2 Zn 2p 1 / 2 The peaks at 1022.9 eV and 1046.4 eV are related to Zn 2p 1 / 2 The peak at 1044.1 eV is related to the ·OH group attached to the Zn ion. 3 Related. From Figure 2 (d) It can be seen that in the C1s core energy level, OCC, CO, COC and CC characteristic peaks appear at the binding energies of 289.6 eV, 286.3 eV and 284.8 eV, among which the peaks of 284.8 eV and 286.3 eV belong to hydrocarbons and carbon oxygen pollutants, respectively, and the peak of 289.6 eV belongs to C in carbonate, which indicates that Zn 5 (OH) 6 (CO 3 ) 2 Highly carbonized, and confirmed that Zn 5 (OH) 6 (CO 3 ) 2 There are free and anchored carbonates between the layered structures.

[0040] The Zn prepared in Example 1 was observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). 5 (OH) 6 (CO 3 ) 2 The morphology was characterized and the results were as follows Figure 3 (a) to (c) are shown. Figure 3 It can be seen that the Zn prepared in Example 1 5 (OH) 6 (CO 3 ) 2 It is a nanosheet structure.

[0041] To study Zn 5 (OH) 6 (CO 3 ) 2 Optical band gap properties, for Zn 5 (OH) 6 (CO 3 ) 2 UV-Vis DRS, band gap (Tauc), Mott-Schottky (MS) and photoluminescence (PL) spectra were analyzed. Figure 4 As shown in (a) to (f).

[0042] from Figure 4 (a) The UV-diffuse reflectance spectrum shows that Zn 5 (OH) 6 (CO 3 ) 2 There is a high absorption edge between 200-250nm and a low absorption edge between 250-375nm. The characteristics of the low absorption edge are Figure 4 It can also be clearly observed in (b) that the high absorption edge (200-250nm) is characteristic of the band gap energy (5.1eV) of basic zinc carbonate, while the low absorption edge (250-375nm) indicates that Smithsonite (ZnCO 3 ) are present in trace amounts, respectively, and are attributed to Zn 5 (OH) 6 (CO 3 ) 2 In CO 3 2- n-π* and π-π* electronic transitions in Zn 5 (OH) 6 (CO 3 ) 2 CT transition of Zn-O in Figure 4 (c) It can be seen that Zn 5 (OH) 6 (CO 3 ) 2 The optical band gap is 3.5 eV.

[0043] Mott-Schottky analysis was used to further verify the Zn 5 (OH) 6 (CO 3 ) 2 The accurate conduction band energy (ECB) and valence band energy (EVB) of Figure 4 (d). Figure 4(d) It can be seen that Zn 5 (OH) 6 (CO 3 ) 2 It has the characteristics of an n-type semiconductor with a positive slope. Figure 4 (d) Zn 5 (OH) 6 (CO 3 ) 2 The flat band potential (Efb) is -0.55 eV (vs. RHE) and the conduction band minimum (CBM). And according to Figure 4 (a) Obtain the estimated Eg value of UV-visible absorption and perform energy band calculation according to Figure 4 The result of (e) can determine Zn 5 (OH) 6 (CO 3 ) 2 The maximum value (VBM) position of the valence band is about -0.2 V more negative than Efb. 5 (OH) 6 (CO 3 ) 2 The ECB is higher than many CO 2 The reduction potential required for the reduction product is more negative, so Zn 5 (OH) 6 (CO 3 ) 2 The ECB is located in CO 2 / CO reduction potential is above that of Zn 5 (OH) 6 (CO 3 ) 2 For photocatalytic CO 2 Reduction to CO is thermodynamically feasible. Zn 5 (OH) 6 (CO 3 ) 2 The oxidation potential of Zn is 4.35 eV. Generally speaking, the higher the oxidation potential, the stronger the oxidation ability of the generated holes, which is also conducive to the formation of ·OH. 5 (OH) 6 (CO 3 ) 2 The EVB is located at H 2 O / H 2 O 2 The oxidation potential of Zn 5 (OH) 6 (CO 3 ) 2 For H 2 O is photooxidized to H 2 O2 It is thermodynamically feasible. The above results show that Zn 5 (OH) 6 (CO 3 ) 2 The photocatalytic redox reaction is thermodynamically feasible and has the potential to convert CO 2 Potential for reduction to CO.

[0044] The carrier dynamics of semiconductors are closely related to their photocatalytic performance. 5 (OH) 6 (CO 3 ) 2 The carrier dynamics of Zn 5 (OH) 6 (CO 3 ) 2 The steady-state photoluminescence spectrum (PL) analysis was performed, and the results were as follows Figure 4 (f). Figure 4 (f) It can be seen that Zn 5 (OH) 6 (CO 3 ) 2 Under 295 nm light excitation, the fluorescence emission peak appears at about 360 nm.

[0045] Example 2

[0046] This embodiment provides Zn 5 (OH) 6 (CO 3 ) 2 The preparation method comprises the following steps:

[0047] Weigh 0.318gNa 2 CO 3 (0.003 mol) was added into 50 mL of deionized water and stirred with a magnetic stirrer for 20 min to obtain Na 2 CO 3 solution; then weigh 0.595g Zn(NO 3 ) 2 6H 2 O (0.002 mol) was added into 10 mL of deionized water and stirred with a magnetic stirrer for 20 min to obtain Zn(NO 3 ) 2 6H 2 O aqueous solution; then Zn(NO 3 ) 2 6H 2 O solution is dropped into Na 2 CO 3The solution was stirred at room temperature for 6 hours, centrifuged at 9000 rpm for 3 minutes, and the precipitate obtained by centrifugation was washed with 10 mL of anhydrous ethanol and 10 mL of deionized water respectively and centrifuged 3 times, each time for 3 minutes, and then the solid obtained after centrifugation was placed in a 60°C vacuum oven and dried for 12 hours to obtain a white sample. The white sample was subjected to XPS analysis and SEM characterization, and the results were respectively Figure 1 and Figure 3 The results are the same, indicating that Zn 5 (OH) 6 (CO 3 ) 2 Successful preparation.

[0048] Example 3

[0049] This embodiment provides Zn 5 (OH) 6 (CO 3 ) 2 The preparation method comprises the following steps:

[0050] 0.3 g Na 2 CO 3 Add 40 mL of deionized water and stir with a magnetic stirrer for 10 min to obtain Na 2 CO 3 solution; then weigh 0.2104gZn(NO 3 ) 2 6H 2 O was added into 5 mL of deionized water and stirred with a magnetic stirrer for 10 min to obtain Zn(NO 3 ) 2 6H 2 O aqueous solution; then Zn(NO 3 ) 2 6H 2 O solution is dropped into Na 2 CO 3 The solution was stirred at room temperature for 5 hours, centrifuged at 9000 rpm for 3 minutes, and the precipitate obtained by centrifugation was washed with 10 mL of anhydrous ethanol and 10 mL of deionized water respectively and centrifuged 3 times, each time for 3 minutes, and then the solid obtained after centrifugation was placed in a 50°C vacuum oven and dried for 10 hours to obtain a white sample. The white sample was subjected to XPS analysis and SEM characterization, and the results were respectively Figure 1 and Figure 3 The results are the same, indicating that Zn 5 (OH) 6 (CO 3 ) 2 Successful preparation.

[0051] Example 4

[0052] This embodiment provides Zn 5 (OH) 6 (CO 3 ) 2 The preparation method comprises the following steps:

[0053] Weigh 1.3gNa 2 CO 3 Add 70 mL of deionized water and stir with a magnetic stirrer for 30 min to obtain Na 2 CO 3 solution; then weigh 2.9187g Zn(NO 3 ) 2 6H 2 O was added into 15 mL of deionized water and stirred with a magnetic stirrer for 300 min to obtain Zn(NO 3 ) 2 6H 2 O aqueous solution; then Zn(NO 3 ) 2 6H 2 O solution is dropped into Na 2 CO 3 The solution was stirred at room temperature for 7 hours, centrifuged at 9000 rpm for 3 minutes, and the precipitate obtained by centrifugation was washed with 10 mL of anhydrous ethanol and 10 mL of deionized water respectively and centrifuged 3 times, each time for 3 minutes, and then the solid obtained after centrifugation was placed in a 70°C vacuum oven and dried for 12 hours to obtain a white sample. The white sample was subjected to XPS analysis and SEM characterization, and the results were respectively Figure 1 and Figure 3 The results are the same, indicating that Zn 5 (OH) 6 (CO 3 ) 2 Successful preparation.

[0054] Experimental Example 1

[0055] This experimental example is based on the Zn prepared in Example 1. 5 (OH) 6 (CO 3 ) 2 Photocatalytic CO 2 Reduction test, photocatalytic CO 2 The reduction reaction was carried out in a gas-solid heterogeneous reaction mode.

[0056] 30mgZn 5 (OH) 6 (CO 3 )2 Dispersed in 400 μL HO 2 O, and then evenly drop the mixed solution on a 3cm×3cm piece of quartz glass, and then vacuum dry it at 60℃ for 1h to prepare Zn 5 (OH) 6 (CO 3 ) 2 Photocatalyst film. Hold the quartz glass with a holder and place it in a 2 Photocatalytic CO 2 Restore test, the result is as follows Figure 5 As shown in (a) to (c).

[0057] Photocatalytic CO 2 The reduction test process is to test in the Labsolar-6A photochemical reaction system of Beijing Bofeilai Technology Co., Ltd. The gas products generated during the test are detected online by the GC8860 gas chromatograph of Agilent Technologies Co., Ltd., USA, which is equipped with a HayeSep Q chromatographic column (8ft×0.125in.×2mm) and MolSieve 5A molecular sieve (8ft×0.125in.×2mm). The chromatographic column is connected to a thermal conductivity (TCD) detector and a hydrogen flame ionization (FID) detector to ensure the detection of all products. First, the entire system is evacuated to 0.1KPa with a vacuum pump to remove air, and then 99.999% high-purity CO is introduced. 2 After three cycles, the system pressure was controlled to 80 KPa, and finally the reaction system was placed under a 300 W high pressure xenon lamp (PLS SXE300UV) for photocatalytic CO 2 For the reduction reaction, turn on the high-pressure xenon lamp and start long-term illumination. The system will automatically take a sample once an hour and pass it into the gas chromatograph for online detection. After the reaction is completed, a standard curve is made using standard gas, and the gas production generated by the reaction is calculated using the external standard method.

[0058] The results show that the Zn 5 (OH) 6 (CO 3 ) 2 In the filled CO 2 and H 2 In the photocatalytic reaction system of O, CO 2 It was reduced to CO and no other gaseous products were detected. Figure 5 (a) It can be seen that Zn 5 (OH) 6 (CO 3 ) 2During the 5 h photoreaction, the CO production gradually increased, with an average CO production rate of 1.61 μmol g –1 h –1 . No Zn 5 (OH) 6 (CO 3 ) 2 and a blank test without light, the results are as follows Figure 5 As shown in (b), it can be seen that in the absence of catalyst and light, only a negligible amount of CO can be detected after 5 h of reaction, indicating that the production of CO is only induced by Zn 5 (OH) 6 (CO 3 ) 2 Produced under light irradiation. Evaluation of Zn by cycle test 5 (OH) 6 (CO 3 ) 2 The long-term stability of CO release varies with time. Figure 5 As shown in (c), it can be seen that during the 10 cycles, the production of CO gradually increased, indicating that Zn 5 (OH) 6 (CO 3 ) 2 It has good stability and repeatability. The average CO generation rate was 3.22 μmol g in a continuous 50-hour cycle test under a 300W high-pressure xenon lamp. –1 h –1 .

[0059] The above are only some embodiments of the present invention. For those skilled in the art, several modifications and improvements can be made without departing from the creative concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. Application of basic zinc carbonate in photocatalytic CO2 reduction, wherein the product of the photocatalytic CO2 reduction is CO.

2. The use according to claim 1, characterized in that: The molecular formula of the basic zinc carbonate is Zn5(OH)6(CO3)2.

3. The use according to claim 2, characterized in that: The method for using basic zinc carbonate for photocatalytic CO2 reduction comprises the following steps: Disperse 20-40 mg of basic zinc carbonate in 300-500 μL of water to obtain a mixed solution, evenly drop the mixed solution on quartz glass, and then dry it at 50-70° C. for 1-2 hours to obtain a Zn5(OH)6(CO3)2 film supported on the quartz glass; After placing the quartz glass in a reactor filled with 10-15 mL of water, evacuate the reactor to a pressure of 0.1 KPa, introduce 99.999% CO2 gas by volume to a pressure of 80 KPa, repeat 3 times, and place the reactor under a 300 W high-pressure xenon lamp to react for 1-10 hours.

4. The use according to claim 3, characterized in that: The method for using basic zinc carbonate for photocatalytic CO2 reduction comprises the following steps: 30 mg of basic zinc carbonate was dispersed in 400 μL of water to obtain a mixed solution, which was evenly dropped on quartz glass and then dried at 60°C for 1 h to obtain a Zn5(OH)6(CO3)2 film supported on quartz glass; After placing the quartz glass in a reactor filled with 10 mL of water, the reactor was evacuated to a pressure of 0.1 KPa, and CO2 gas with a volume fraction of 99.999% was introduced to a pressure of 80 KPa. This was repeated three times, and the reactor was placed under a 300 W high-pressure xenon lamp for reaction for 5 hours.

5. The use according to claim 2, characterized in that: The preparation method of Zn5(OH)6(CO3)2 comprises the following steps: S1. Dissolve Na2CO3 in deionized water and stir for 10 to 30 minutes to obtain a Na2CO3 solution; S2. Dissolve Zn(NO3)2·6H2O in deionized water and stir for 10 to 30 minutes to obtain an aqueous solution of Zn(NO3)2·6H2O; S3, drop the aqueous solution of Zn(NO3)2·6H2O into the Na2CO3 solution, stir for 5-7h, centrifuge, wash the precipitate obtained by centrifugation with 10-20mL deionized water and anhydrous ethanol respectively, centrifuge for 3-10 times to obtain a solid, and then dry the solid at 50-70°C for 10-12h to obtain; Among them, the molar ratio of Na2CO3 to Zn(NO3)2·6H2O is (2.5~4):(1~2).

6. The use according to claim 5, characterized in that: The preparation method of the Na2CO3 solution is as follows: dissolve 0.3-1.3g Na2CO3 in 40-60mL deionized water and stir for 10-30min; the preparation method of the Zn(NO3)2·6H2O aqueous solution is as follows: dissolve 0.21-2.92g Zn(NO3)2·6H2O in 5-15mL deionized water and stir for 10-30min.

7. The use according to claim 5, characterized in that: In step S1, the volume of deionized water is 50 mL, and the stirring time is 20 min; in step S2, the volume of deionized water is 10 mL, and the stirring time is 20 min; in step S3, the drying temperature is 60° C., the drying time is 12 h, and the volume of deionized water and anhydrous ethanol is 10 mL.

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