Application of C / N-In2O3 / ZnIn2S4 double heterojunction in photocatalytic carboxylation of aromatic compounds and co2

Abstract

The application discloses application of C / N-In2O3 / ZnIn2S4 double heterojunction in photocatalytic carboxylation of aromatic compounds and CO2. 3+ A preparation method of the C / N-In2O3 / ZnIn2S4 catalyst is as follows: In-MOF precursors are constructed through a solvothermal reaction of ions and 2-amino terephthalic acid as an organic ligand; the In-MOF is calcined at high temperature under nitrogen to obtain hollow nanotube-shaped C / N-In2O3; ZnIn2S4 is decorated on the inner and outer surfaces of the hollow C / N-In2O3 by using a low-temperature hydrothermal method to obtain C / N-In2O3 / ZnIn2S4 rich in In-N sites and oxygen vacancies; and the C / N-In2O3 / ZnIn2S4 is used for photocatalytic carboxylation of aromatic compounds, a lignin model and carbon dioxide. In the C / N-In2O3 / ZnIn2S4, a receptor-donor compensation mechanism between the In-N sites and the oxygen vacancies improves light absorption capacity and maintains photocatalytic performance under long-wave visible light. The catalyst preparation method is simple, reaction conditions are mild, and the catalyst is easy to recycle.

Description

TECHNICAL FIELD

[0001] The present application relates to the application of C / N-In2O3 / ZnIn2S4 double heterojunction in the photocatalytic carboxylation of aromatic compounds and CO2. BACKGROUND

[0002] Due to the extensive exploitation of fossil fuels, the content of carbon dioxide in the air is gradually increasing, which will bring problems such as global warming, sea level rise and extreme weather. Developing effective technologies to capture, store and utilize carbon dioxide can alleviate these problems. In recent years, it has become an attractive proposal to use waste carbon dioxide to produce chemical products with increased value. CO2 can be converted into CO, HCOOH, HCHO, CH3OH and CH4, etc. through a series of heterogeneous photocatalytic processes. With the realization of CO2 photocatalytic continuous single electron reduction technology in recent years, it has become a new research hotspot of CO2 utilization to convert CO2 into high-value carboxyl products for the pharmaceutical and polymer industries. Aromatic compounds and their derivatives are ubiquitous in natural products, biologically active molecules and bulk chemicals, and are considered to be environmentally friendly reactants due to their stability and easy availability. Due to the thermodynamic barrier and low activity of CO2, it is still a difficult task to achieve photocatalytic CO2 carboxylation to produce value-added carboxylic acids through C-H activation and CO2 reduction without noble metal catalysts and sacrificial agents.

[0003] Biomass is the most easily available renewable organic source in the world; therefore, it has the potential to become a substitute for fossil energy in the preparation of materials, chemicals and fuels. Generally, lignin is considered to have abundant aromatic content. Scientists have explored various catalytic technologies for furan biomass. Selective cracking of lignin samples will help to develop the potential of lignin as an aromatic regenerative resource for the production of fuels and commercial chemicals. In addition to conversion into fuels, photocatalysis is also attractive for cracking and reducing lignin samples into valuable chemical substances. However, considering the high energy barrier of CO2 reduction, how to combine lignin utilization with CO2 recycling is still a challenging problem for sustainable development.

[0004] ZnIn2S4 is one of the most studied metal sulfides due to its narrow band gap and absence of toxic metal atoms. However, the severe charge recombination of photoinduced carriers in pristine ZnIn2S4 limits its widespread application in photocatalysis. Compared with pristine ZnIn2S4, C / N-In2O3 / ZnIn2S4 nanotubes with oxygen vacancies and In-N sites can increase the lifetime of photoinduced carriers, thus exhibiting excellent photocatalytic performance. In addition to defect engineering and morphology control, constructing a double heterojunction to inhibit carrier recombination, promote charge migration, and achieve strong redox ability is an attractive method. SUMMARY

[0005] The application discloses application of C / N-In2O3 / ZnIn2S4 double heterojunction in photocatalytic carboxylation of aromatic compounds and CO2, and is characterized in that: the C / N-In2O3 / ZnIn2S4 double heterojunction is used for photocatalyzing benzene ring sp 2 C-H activation to generate benzyl radicals and CO2 carboxylation to prepare dicarboxylic acids with increased value;

[0006] The preparation method of the C / N-In2O3 / ZnIn2S4 double heterojunction is as follows:

[0007] In-MOF: 120 mg of In (NO3)3·4.5H2O and 120 mg of 2-amino terephthalic acid are dissolved in 30 ml of DMF and stirred for 30 minutes, then the mixture is added to a polytetrafluoroethylene-lined autoclave, and reacted at 125°C for 6h, after cooling, In-MOF is obtained by centrifugation, water and ethanol washing, and vacuum drying for 5 hours;

[0008] Hollow C / N-In2O3 nanotubes: In-MOF is placed in a crucible and heated to 500°C at a heating rate of 5°C / min in N2 and kept for 2 hours; -1

[0009] C / N-In2O3 / ZnIn2S4: ZnIn2S4 is modified on the inner and outer surfaces of hollow C / N-In2O3 by a low-temperature hydrothermal method, 4.5 mg of C / N-In2O3, 8 mL of dilute hydrochloric acid solution (pH=2.5), and 2 mL of glycerol are introduced into a 100 mL glass bottle, ultrasonic treatment is performed for 30 minutes, then stirring is continued for 30 minutes, then 0.0408 g of ZnCl2, 0.087 g of InCl3·4H2O, and 0.045 g of thioacetamide are sequentially added, and the mixture is kept at 80°C for 2 hours under stirring, and C / N-In2O3 / ZnIn2S4 (C / N-In2O3 / ZIS) is collected by centrifugation, ethanol washing, and vacuum drying;

[0010] ​The method for preparing value-added dicarboxylic acid by photocatalytic carboxylation of the aromatic compound and CO2 is: 10 mg of photocatalyst and 1 mmol of base additive Cs2CO3 are added to a 10 mL double-necked round-bottom flask, which is filled with CO2, then 0.1 mmol of the aromatic compound, 2 mL of H2O are added to the round-bottom flask, and then the reaction is stirred under irradiation of a blue LED lamp at a power of 0.75 W / cm2 for 24 h. 2 The reaction is stirred under irradiation of a blue LED lamp for 24 h, wherein the aromatic compound includes any one of benzoic acid, p-methoxybenzoic acid, benzyl alcohol, benzaldehyde, 3-chlorobenzaldehyde, chlorobenzene, bromobenzene, iodobenzene, and benzene; and wherein chlorobenzene, bromobenzene, iodobenzene, and benzene can be dicarboxylated.

[0011] The method for preparing isophthalic acid and salicylic acid by photocatalytic carboxylation of the lignin model substrate benzyl phenyl ether and CO2 is: 10 mg of photocatalyst and 1 mmol of base additive Cs2CO3 are added to a 10 mL double-necked round-bottom flask, which is filled with CO2, then 0.1 mmol of benzyl phenyl ether, 2 mL of H2O are added to the round-bottom flask, and then the reaction is stirred under irradiation of a blue LED lamp at a power of 0.75 W / cm2 for 24 h. 2 The reaction is stirred under irradiation of a blue LED lamp for 24 h.

[0012] The application of C / N-In2O3 / ZnIn2S4 double heterojunction in photocatalytic carboxylation of aromatic compounds and CO2 is characterized in that: the C-H bond activation of the aromatic compound and the photocatalytic carboxylation of CO2 to prepare value-added dicarboxylic acid are realized without a sacrificial agent.

[0013] The application of C / N-In2O3 / ZnIn2S4 double heterojunction in photocatalytic carboxylation of aromatic compounds and CO2 is characterized in that: the selective cleavage of the lignin model substrate benzyl phenyl ether and the photocatalytic carboxylation of CO2 to prepare value-added isophthalic acid and salicylic acid are realized without a sacrificial agent.

[0014] The application of C / N-In2O3 / ZnIn2S4 double heterojunction in photocatalytic carboxylation of aromatic compounds and CO2 is characterized in that: the acceptor-donor compensation mechanism between the In-N site and the oxygen vacancy improves the light absorption capacity and maintains the photocatalytic performance under long-wave visible light.

[0015] The application of C / N-In2O3 / ZnIn2S4 double heterojunction in photocatalytic carboxylation of aromatic compounds and CO2 is characterized in that: the conversion rate of the aromatic compound is as high as 90%-96%, and the selectivity of isophthalic acid is as high as 95%. The conversion rate of the lignin model substrate is as high as 97%, and the selectivity of isophthalic acid and salicylic acid is 93% and 47%, respectively. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 a-d are scanning electron microscopy (SEM) images of catalysts prepared in Example 1 : a) In-MOF, b) C / N-In203, c) C / N-In203 / ZnIn2S4 (abbreviated as: C / N-In203 / ZIS) bi-heterojunction, d) a magnified portion of C / N-In203 / ZIS bi-heterojunction. Figure 1 e-g are e) TEM image, f) high resolution transmission electron microscopy image, g) mapping image of catalysts prepared in Example 1.

[0017] Figure 2 is a scanning electron microscopy (SEM) image of catalyst ZnIn2S4 (ZIS) prepared in Example 1.

[0018] Figure 3 is powder X-ray diffraction (XRD) patterns of catalysts ZnIn2S4 (ZIS), C / N-In203 / ZnIn2S4 (C / N-In203 / ZIS), C / N-In203 and In203 prepared in Example 1.

[0019] Figure 4 is X-ray photoelectron spectroscopy (XPS) of catalysts ZnIn2S4 (ZIS), C / N-In203, C / N-In203 / ZnIn2S4 (C / N-In203 / ZIS) prepared in Example 1 : (a) full spectrum, (b) C 1s, (c) N 1s, (d) O 1s, (e) In 3d, (f) S 2p, (g) Zn 2p. (h) Electron paramagnetic resonance (EPR) images of C / N-In203 / ZIS and C / N-In203. DETAILED DESCRIPTION

[0020] The application will be described in detail below with reference to specific examples.

[0021] Example 1 :

[0022] Preparation of ZnIn2S4 (abbreviated as: ZIS) photocatalyst: 68 mg ZnCl2and 293 mg InCl3·4H2O were dissolved in 25 mL deionized water and 5 mL ethylene glycol. After stirring vigorously at room temperature for 30 minutes, 150 mg of thioacetamide (TAA) was added to the solution. After stirring for another 30 minutes, the solution was transferred to a 100-milliliter Teflon-lined stainless steel hydrothermal autoclave, which was kept in an oven at 120 °C for 12 hours. After natural cooling, the product was collected by centrifugation, washed with ethanol and distilled water twice, and dried in vacuum for 6 h for standby use.

[0023] Preparation of In2O3: 60 mg of In(N03)3.xH20 and 60 mg of terephthalic acid were dissolved in 40 mL of DMF and stirred for 20 minutes. Then, the resulting solution was placed in an oil bath at 120 °C and stirred for 30 minutes. After cooling the temperature to room temperature, the white precipitate was filtered, washed with ethanol three times and dried under vacuum to obtain MIL-68(In). The obtained MIL-68(In) was heated in air at a heating rate of 5 °C min -1 -1 to 120 °C for 2 hours and then at a temperature of 500 °C for 2 hours to obtain In203.

[0024] Preparation of modified C / N-In203 / ZnIn2S4bifheterojunction:

[0025] In-MOF: 120 mg of In(N03)3.4.5H20 and 120 mg of 2-amino terephthalic acid were dissolved in 30 ml of DMF, after stirring for 30 minutes, the mixture was added to a polytetrafluoroethylene lined autoclave, heated at 125 °C for 6 hours. After cooling, In-MOF was obtained by centrifugation, water and ethanol washing and vacuum drying for 5 hours.

[0026] C / N-In203: To synthesize hollow C / N-In203nanotubes, In-MOF was placed in a crucible and heated to 500 °C at a heating rate of 5 °C min -1 -1 under N2and kept for 2 hours.

[0027] C / N-In203 / ZnIn2S4(abbr: C / N-In203 / ZIS): ZnIn2S4(ZIS) was modified on the inner and outer surfaces of hollow C / N-In203using a low-temperature hydrothermal method. 4.5 mg of C / N-In203, 8 mL of dilute hydrochloric acid solution (pH = 2.5), 2 mL of glycerol were introduced into a 100 mL glass bottle, and ultrasonic treatment was carried out for 30 minutes, followed by stirring for 30 minutes. Then 0.0408 g of ZnCl2, 0.087 g of InCl3.4H20 and 0.045 g of thioacetamide (TAA) were added in turn. The mixture was kept at 80 °C for 2 hours under stirring. C / N-In203 / ZnIn2S4was collected by centrifugation, ethanol washing and vacuum drying.

[0028] For the catalytic materials prepared in this embodiment, scanning electron microscopy (SEM) was used to obtain the morphology of the materials, Figure 1 a shows that In-MOF has a solid hexagonal prism morphology, and the surface is smooth and seamless. After calcination, C / N-In203with a hollow hexagonal prism structure was obtained, and the diameter of the tube was about 1.1 pm Figure 1 b). In Figure 2In the original ZnIn2S4, the structure is typical of nanoflower-shaped microspheres. C / N-In2O3 / ZIS double heterojunctions prepared by a simple hydrothermal process, such as... Figure 1 As shown in c and 1d, thin layers of ZIS were successfully grown on the inner and outer sides of C / N-In2O3 nanotubes. Figure 1 The TEM images in e further confirm the successful formation of the hollow tubular structure and the double heterojunction. For example... Figure 1 The HRTEM image shown in f indicates that the lattice spacings of 0.32 and 0.41 nm correspond to the (102) crystal plane of ZIS and the (211) crystal plane of In2O3, respectively. The elemental spectrum of C / N-In2O3 / ZIS nanotubes confirms the good distribution of C, N, O, In, S, and Zn elements.

[0029] The phase composition of the catalytic material prepared in this embodiment was determined by X-ray diffraction (XRD) to be In2O3, C / N-In2O3, C / N-In2O3 / ZIS, and ZnIn2S4. Figure 3 In2O3 and C / N-In2O3 exhibit characteristic peaks at 21.5°, 30.6°, 35.5°, and 51.0°, corresponding to the (211), (222), (400), (440), and (622) crystal planes of In2O3 (JCPDS No. 06–0416). ZnIn2S4 shows signals near 21.4°, 27.3°, and 47.0°, attributable to the (006), (102), and (110) crystal planes (JCPDS No. 65-2023). The composite material C / N-In2O3 / ZIS displays characteristic peaks of C / N-In2O3 and ZIS, demonstrating the successful synthesis of the double heterojunction.

[0030] The chemical state and surface atomic composition of ZnIn2S4, C / N-In2O3 and C / N-In2O3 / ZIS were analyzed by X-ray photoelectron spectroscopy (XPS). Figure 4 a shows the full spectrum of all materials, confirming the presence of C, N, O, In, S and Zn elements in the C / N-In2O3 / ZIS double heterojunction. Figure 4 b shows the high-resolution XPS spectrum of C 1s, where the peaks at 284.6, 285.8, and 288.0 eV correspond to C=C / CC, CN, and C=O bonds, respectively. Figure 4 In c, the XPS spectrum of N 1s shows three peaks at 397.6, 398.6, and 400.2 eV, which can be attributed to In-N, lattice N, and CN bonds, respectively. The XPS of C 1s and N 1s demonstrates that N is substituted and doped into the In2O3 nanotubes, forming In-N sites. Figure 4Figure d shows the XPS spectrum of O 1s, where the peaks at 529.8, 531.6, and 533.0 eV represent lattice oxygen (OL), oxygen vacancy (Ov), and OH bonds, respectively. Figure 4 As shown in Figure e, the XPS spectrum of In 3d was fitted with peaks around 444.8 eV and 452.5 eV, respectively, representing the peaks of In 3d. 2 / 3 and In 3d 5 / 2 The In 3d peaks of C / N-In₂O₃ shift towards lower binding energies (444.4 eV and 452 eV), which is related to the generation of oxygen vacancies during calcination. After recombination with ZIS, the In 3d peaks of C / N-In₂O₃ / ZIS are 444.8 eV and 452.5 eV, respectively, which should be explained by the fact that the oxygen-vacancy-rich In₂O₃ is well covered by the outer ZIS layer. Figure 4 f and 4g show the XPS spectra of S 2p and Zn 2p in ZnIn2S4 and C / N-In2O3 / ZIS, with peaks at 161.6 eV and 162.8 eV, respectively, for S 2p. 3 / 2 and S 2p 1 / 2 The peaks at 1021.5 eV and 1044.5 eV are Zn2p. 3 / 2 and Zn 2p 1 / 2 To further confirm the existence of oxygen vacancies, in Figure 4 EPR tests were performed in h. The strong EPR signal of C / N-In2O3 at g=2.004 can be interpreted as the formation of oxygen vacancies during calcination. In addition, the EPR signal of oxygen vacancies in C / N-In2O3 / ZIS did not change significantly after the formation of the heterojunction.

[0031] Implementation Case 2 (Reaction Reference Table 1, Item 1)

[0032] Add ZnIn2S4 (10 mg) and Cs2CO3 (1 mmol) to a 10 ml double-necked round-bottom flask, fill the flask with CO2, and then add benzoic acid (0.1 mmol) and 2 ml H2O. Then, while stirring, add 0.15 W cm⁻¹ water. -2 Blue LEDs (λ = 460 nm) were used for irradiation at room temperature for 24 h. The conversion rate of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion rate of benzoic acid was 39%, and the selectivity of isophthalic acid was 93%.

[0033] Implementation Case 3 (Reaction Reference Table 1, Item 2)

[0034] ZnIn2S4(10 mg) and Cs2CO3(1 mmol) were added to a 10 ml two necked round bottom flask and filled with N2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then the reaction was stirred for 24 h at room temperature under visible light irradiation. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 6% and the selectivity of isophthalic acid was 98%. -2 The blue LED (λ = 460 nm) was irradiated for 24 h at room temperature. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. No conversion of benzoic acid was detected.

[0035] Example 4 (reaction refers to Table 1, entry 3)

[0036] ZnIn2S4(10 mg) and Cs2CO3(1 mmol) were added to a 10 ml two necked round bottom flask and filled with CO2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then the reaction was stirred for 24 h at room temperature without visible light irradiation. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. No conversion of benzoic acid was detected.

[0037] Example 5 (reaction refers to Table 1, entry 4)

[0038] Cs2CO3(1 mmol) was added to a 10 ml two necked round bottom flask and filled with CO2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then the reaction was stirred for 24 h at room temperature under visible light irradiation of 0.15 W cm-2. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. No conversion of benzoic acid was detected. -2 The blue LED (λ = 460 nm) was irradiated for 24 h at room temperature. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. No conversion of benzoic acid was detected.

[0039]

[0040] Example 6 (reaction refers to Table 1, entry 5)

[0041] ZnIn2S4(10 mg) was added to a 10 ml two necked round bottom flask and filled with CO2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then the reaction was stirred for 24 h at room temperature under visible light irradiation of 0.15 W cm-2. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. No conversion of benzoic acid was detected. -2 The blue LED (λ = 460 nm) was irradiated for 24 h at room temperature. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. No conversion of benzoic acid was detected.

[0042] Example 7 (reaction refers to Table 1, entry 6)

[0043] ZnIn2S4(10 mg) and Cs2CO3(1 mmol) were added to a 10 ml two necked round bottom flask and filled with CO2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 55% and the selectivity of isophthalic acid was 95%. -2 ZnIn2S4(10 mg) and Cs2CO3(1 mmol) were added to a 10 ml two necked round bottom flask and filled with CO2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 55% and the selectivity of isophthalic acid was 95%.

[0044] Example 8 (reaction refers to Table 1, entry 7)

[0045] ZnIn2S4(10 mg) and K3PO4(1 mmol) were added to a 10 ml two necked round bottom flask and filled with CO2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 61% and the selectivity of isophthalic acid was 62%. -2 ZnIn2S4(10 mg) and K3PO4(1 mmol) were added to a 10 ml two necked round bottom flask and filled with CO2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 61% and the selectivity of isophthalic acid was 62%.

[0046] Example 9 (reaction refers to Table 1, entry 8)

[0047] ZnIn2S4(10 mg) and Na2CO3(1 mmol) were added to a 10 ml two necked round bottom flask and filled with CO2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 19% and the selectivity of isophthalic acid was 94%. -2 ZnIn2S4(10 mg) and Na2CO3(1 mmol) were added to a 10 ml two necked round bottom flask and filled with CO2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 19% and the selectivity of isophthalic acid was 94%.

[0048] Example 10 (reaction refers to Table 1, entry 9)

[0049] ZnIn2S4(10 mg) and K2CO3(1 mmol) were added to a 10 ml two necked round bottom flask and filled with CO2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 32% and the selectivity of isophthalic acid was 95%. -2 ZnIn2S4(10 mg) and K2CO3(1 mmol) were added to a 10 ml two necked round bottom flask and filled with CO2, then benzoic acid (0.1 mmol) and 2 ml H2O were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 32% and the selectivity of isophthalic acid was 95%.

[0050] Case 11 (reaction according to Table 1, entry 10)

[0051] C / N-In203(10 mg) and Cs2C03(1 mmol) were added to a 10 ml two-necked round bottom flask and filled with C02, then benzoic acid (0.1 mmol) and 2 ml H20 were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 25% and the selectivity of isophthalic acid was 93%. -2 C / N-In203(10 mg) and Cs2C03(1 mmol) were added to a 10 ml two-necked round bottom flask and filled with C02, then benzoic acid (0.1 mmol) and 2 ml H20 were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 25% and the selectivity of isophthalic acid was 93%.

[0052] Case 12 (reaction according to Table 1, entry 11)

[0053] C / N-In203(10 mg) and Cs2C03(1 mmol) were added to a 10 ml two-necked round bottom flask and filled with C02, then benzoic acid (0.1 mmol) and 2 ml H20 were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 25% and the selectivity of isophthalic acid was 93%. -2 C / N-In203(10 mg) and Cs2C03(1 mmol) were added to a 10 ml two-necked round bottom flask and filled with C02, then benzoic acid (0.1 mmol) and 2 ml H20 were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 25% and the selectivity of isophthalic acid was 93%.

[0054] Case 13 (reaction according to Table 1, entry 12)

[0055] C / N-In203(10 mg) and Cs2C03(1 mmol) were added to a 10 ml two-necked round bottom flask and filled with C02, then benzoic acid (0.1 mmol) and 2 ml H20 were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 25% and the selectivity of isophthalic acid was 93%. -2 C / N-In203(10 mg) and Cs2C03(1 mmol) were added to a 10 ml two-necked round bottom flask and filled with C02, then benzoic acid (0.1 mmol) and 2 ml H20 were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 25% and the selectivity of isophthalic acid was 93%.

[0056] Case 14 (reaction according to Table 1, entry 13)

[0057] C / N-In203(10 mg) and Cs2C03(1 mmol) were added to a 10 ml two-necked round bottom flask and filled with C02, then benzoic acid (0.1 mmol) and 2 ml H20 were added to the round bottom flask. Then 0.75 W cm-2 blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion of benzoic acid was 25% and the selectivity of isophthalic acid was 93%. -2A green LED (λ = 517 nm) was used for irradiation at room temperature for 24 h. The conversion rate of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion rate of benzoic acid was 90%, and the selectivity of isophthalic acid was 94%. This indicates that the acceptor-donor compensation mechanism between the In-N site and the oxygen vacancy enhances the light absorption capacity and maintains the photocatalytic performance under long-wavelength visible light.

[0058] Implementation Case 15 (Reaction Reference Table 1, Item 14)

[0059] C / N-In₂O₃ / ZIS (10 mg) and Cs₂CO₃ (1 mmol) were added to a 10 ml double-necked round-bottom flask, which was then filled with CO₂. Benzoic acid (0.1 mmol) and 2 ml H₂O were then added to the flask with stirring and 0.75 W / cm²⁻¹. -2 A yellow LED (λ = 590 nm) was used for irradiation at room temperature for 24 h. The conversion rate of benzoic acid and the selectivity of isophthalic acid were analyzed by HPLC. The conversion rate of benzoic acid was 91%, and the selectivity of isophthalic acid was 95%. This indicates that the acceptor-donor compensation mechanism between the In-N site and the oxygen vacancy enhances the light absorption capacity and maintains the photocatalytic performance under long-wavelength visible light.

[0060] Implementation Case 16 (Reaction Reference Table 2, Item 2)

[0061] C / N-In₂O₃ / ZIS (10 mg) and Cs₂CO₃ (1 mmol) were added to a 10 mL double-necked round-bottom flask, which was then filled with CO₂. Next, p-methoxybenzoic acid (0.1 mmol) and 2 mL of H₂O were added to the flask. The mixture was then stirred and heated with 0.75 W / cm² water. -2 Blue LEDs (λ = 460 nm) were used for irradiation at room temperature for 24 h. The conversion rate of p-methoxybenzoic acid and the selectivity of 4-methoxyisophthalic acid were analyzed by HPLC. The conversion rate of p-methoxybenzoic acid was 95%, and the selectivity of 4-methoxyisophthalic acid was 90%.

[0062] Implementation Case 18 (Reaction Reference Table 2, Item 3)

[0063] C / N-In₂O₃ / ZIS (10 mg) and Cs₂CO₃ (1 mmol) were added to a 10 mL double-necked round-bottom flask, which was then filled with CO₂. Benzyl alcohol (0.1 mmol) and 2 mL of H₂O were then added to the flask with stirring and 0.75 W / cm⁻¹. -2Blue LED (λ = 460 nm) irradiated the vehicle at room temperature for 24 h. The conversion rate of benzyl alcohol and the selectivity for isophthalic acid were analyzed by HPLC. The conversion rate of benzyl alcohol was 95%, and the selectivity for isophthalic acid was 91%.

[0064] Implementation Case 19 (Reaction Reference Table 2, Item 4)

[0065] C / N-In₂O₃ / ZIS (10 mg) and Cs₂CO₃ (1 mmol) were added to a 10 ml double-necked round-bottom flask, which was then filled with CO₂. Benzaldehyde (0.1 mmol) and 2 ml of H₂O were then added to the flask with stirring and 0.75 W / cm⁻¹. -2 Blue LEDs (λ = 460 nm) were used for irradiation at room temperature for 24 h. The conversion rate of benzaldehyde and the selectivity for isophthalic acid were analyzed by HPLC. The conversion rate of benzaldehyde was 97%, and the selectivity for isophthalic acid was 95%.

[0066] Implementation Case 20 (Reaction Reference Table 2, Item 5)

[0067] Add C / N-In₂O₃ / ZIS (10 mg) and Cs₂CO₃ (1 mmol) to a 10 ml double-necked round-bottom flask, fill the flask with CO₂, then add 3-chlorobenzaldehyde (0.1 mmol) and 2 ml H₂O. Then, while stirring, add 0.75 W / cm³ of water. -2 Blue LED (λ = 460 nm) irradiated the sample for 24 h at room temperature. The conversion rate of 3-chlorobenzaldehyde and the selectivity of isophthalic acid were analyzed by HPLC. The conversion rate of 3-chlorobenzaldehyde was 94%, and the selectivity of isophthalic acid was 90%.

[0068] Implementation Case 21 (Reaction Reference Table 2, Item 6)

[0069] C / N-In₂O₃ / ZIS (10 mg) and Cs₂CO₃ (1 mmol) were added to a 10 ml double-necked round-bottom flask, which was then filled with CO₂. Chlorobenzene (0.1 mmol) and 2 ml of H₂O were then added to the flask with stirring and 0.75 W / cm²⁻¹. -2 Blue LED (λ = 460 nm) irradiated the sample for 24 h at room temperature. The conversion rate of chlorobenzene and the selectivity of isophthalic acid were analyzed by HPLC. The conversion rate of chlorobenzene was 93%, and the selectivity of isophthalic acid was 92%.

[0070]

[0071] Implementation Case 22 (Reaction Reference Table 2, Item 7)

[0072] C / N-In₂O₃ / ZIS (10 mg) and Cs₂CO₃ (1 mmol) were added to a 10 mL double-necked round-bottom flask, which was then filled with CO₂. Bromobenzene (0.1 mmol) and 2 mL of H₂O were then added to the flask with stirring and 0.75 W / cm²⁻¹. -2 Blue LEDs (λ = 460 nm) were used for irradiation at room temperature for 24 h. The conversion rate of bromobenzene and the selectivity of isophthalic acid were analyzed by HPLC. The conversion rate of bromobenzene was 92%, and the selectivity of isophthalic acid was 91%.

[0073] Implementation Case 23 (Reaction Reference Table 2, Item 8)

[0074] Add C / N-In₂O₃ / ZIS (10 mg) and Cs₂CO₃ (1 mmol) to a 10 ml double-necked round-bottom flask, fill the flask with CO₂, and then add iodobenzene (0.1 mmol) and 2 ml H₂O. Then, while stirring, add 0.75 W / cm³ of water. -2 Blue LEDs (λ = 460 nm) were used for irradiation at room temperature for 24 h. The conversion rate of iodobenzene and the selectivity of isophthalic acid were analyzed by HPLC. The conversion rate of iodobenzene was 90%, and the selectivity of isophthalic acid was 88%.

[0075] Implementation Case 24 (Reaction Reference Table 2, Item 9)

[0076] C / N-In₂O₃ / ZIS (10 mg) and Cs₂CO₃ (1 mmol) were added to a 10 mL double-necked round-bottom flask, which was then filled with CO₂. Benzene (0.1 mmol) and 2 mL of H₂O were then added to the flask with stirring and 0.75 W / cm²⁻¹. -2 Blue LEDs (λ = 460 nm) were used for irradiation at room temperature for 24 h. The conversion rate of benzene and the selectivity for isophthalic acid were analyzed by HPLC. The conversion rate of benzene was 96%, and the selectivity for isophthalic acid was 90%.

[0077] Implementation Case 25 (Reaction Reference Table 2, Item 10)

[0078] C / N-In₂O₃ / ZIS (10 mg) and Cs₂CO₃ (1 mmol) were added to a 10 ml double-necked round-bottom flask, which was then filled with CO₂. Benzylphenyl ether (0.1 mmol) and 2 ml H₂O were then added to the flask with stirring and 0.75 W / cm⁻¹. -2A blue LED (λ = 460 nm) was irradiated at room temperature for 24 h. The conversion of benzyl phenyl ether and the selectivity of isophthalic acid, salicylic acid were analyzed by HPLC. The conversion of benzyl phenyl ether was 97%, and the selectivity of isophthalic acid, salicylic acid was 93%, 47%, respectively.

Claims

1. Application of C / N-In2O3 / ZnIn2S4 double heterojunction in photocatalytic carboxylation of aromatic compounds and CO2, characterized in that: Photocatalytic sp2 2 C-H activation to produce benzyl radicals and CO2 carboxylation to produce value-added dicarboxylic acids; The preparation method of the C / N-In2O3 / ZnIn2S4 double heterojunction is: Preparation of In-MOF: 120 mg of In(NO3)3.4.5H2O and 120 mg of 2-amino terephthalic acid were dissolved in 30 mL of DMF and stirred for 30 minutes, and then the mixture was added to a polytetrafluoroethylene-lined autoclave and reacted at 125 DEG C for 6 hours. After cooling, In-MOF was obtained by centrifugation, water and ethanol washing, and vacuum drying for 5 hours; Preparation of hollow C / N-In2O3nanotubes: In-MOF was put into a crucible and heated to 500 °C at a heating rate of 5 °C min -1 for 2 hours in N2; Preparation of C / N-In2O3 / ZnIn2S4: ZnIn2S4 was modified on the inner and outer surfaces of hollow C / N-In2O3 by low-temperature hydrothermal method. 4.5 mg of C / N-In2O3, 8 mL of dilute hydrochloric acid solution with pH = 2.5, and 2 mL of glycerol were introduced into a 100 mL glass bottle, and then ultrasonic treatment was carried out for 30 minutes, followed by stirring for 30 minutes. Then 0.0408 g of ZnCl2, 0.087 g of InCl3.4H2O and 0.045 g of thioacetamide were added in sequence, and the mixture was kept at 80 DEG C under stirring for 2 hours. C / N-In2O3 / ZnIn2S4 double heterojunction was collected by centrifugation, ethanol washing and vacuum drying; A method for preparing value-added dicarboxylic acid by photocatalytic carboxylation of aromatic compounds and CO2 is as follows: 10 mg of C / N-In2O3 / ZnIn2S4 double heterojunction and 1 mmol of alkali additive Cs2CO3 are added to a 10 mL double-necked round-bottom flask, and the flask is filled with CO2, then 0.1 mmol of an aromatic compound, 2 mL of H2O, and then 0.75 W / cm 2 The reaction is stirred under the irradiation of a blue LED lamp for 24 h, wherein the aromatic compound includes any one of benzoic acid, p-methoxybenzoic acid, benzyl alcohol, benzaldehyde, 3-chlorobenzaldehyde, chlorobenzene, bromobenzene, iodobenzene, and benzene; wherein chlorobenzene, bromobenzene, iodobenzene, and benzene can be dicarboxylated.

2. Use according to claim 1, characterized in that: The selective cleavage of lignin model substrate benzyl phenyl ether and photocatalytic carboxylation with CO2 to prepare value-added isophthalic acid and salicylic acid were realized without sacrificial agent.

3. Application of C / N-In2O3 / ZnIn2S4 double heterojunction in photocatalytic carboxylation of aromatic compounds and CO2, characterized by: through C / N-In2O3 / ZnIn2S4 double heterojunction photocatalysis, the benzene ring sp 2 C-H activation to generate benzyl radicals and CO2 carboxylation to prepare dicarboxylic acids with increased value; The preparation method of the C / N-In2O3 / ZnIn2S4 double heterojunction is: Preparation of In-MOF: 120 mg of In(NO3)3.4.5H2O and 120 mg of 2-amino terephthalic acid were dissolved in 30 mL of DMF and stirred for 30 minutes, and then the mixture was added to a polytetrafluoroethylene-lined autoclave and reacted at 125 DEG C for 6 hours. After cooling, In-MOF was obtained by centrifugation, water and ethanol washing, and vacuum drying for 5 hours; Preparation of hollow C / N-In2O3nanotubes: In-MOF was put into a crucible and heated to 500 °C at a heating rate of 5 °C min -1 under N2and kept for 2 hours; Preparation of C / N-In2O3 / ZnIn2S4: ZnIn2S4 was modified on the inner and outer surfaces of hollow C / N-In2O3 by low-temperature hydrothermal method. 4.5 mg of C / N-In2O3, 8 mL of dilute hydrochloric acid solution with pH = 2.5, and 2 mL of glycerol were introduced into a 100 mL glass bottle, and then ultrasonic treatment was carried out for 30 minutes, followed by stirring for 30 minutes. Then 0.0408 g of ZnCl2, 0.087 g of InCl3.4H2O and 0.045 g of thioacetamide were added in sequence, and the mixture was kept at 80 DEG C under stirring for 2 hours. C / N-In2O3 / ZnIn2S4 double heterojunction was collected by centrifugation, ethanol washing and vacuum drying; The method for photocatalytic preparation of isophthalic acid and salicylic acid from lignin model substrate benzyl phenyl ether and CO2 is: 10 mg of C / N-In2O3 / ZnIn2S4 double heterojunction and 1 mmol of base additive Cs2CO3 are added to a 10 mL double-neck round-bottom flask, and the flask is filled with CO2, then 0.1 mmol of benzyl phenyl ether, 2 mL of H2O, and 0.75 W / cm 2 The reaction is stirred under the irradiation of a blue LED lamp for 24 h.

4. Use according to claim 3, characterized in that: The selective cleavage of lignin model substrate benzyl phenyl ether and photocatalytic carboxylation with CO2 to prepare value-added isophthalic acid and salicylic acid were realized without sacrificial agent.

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