CN114736179B - ZnIn 2 S 4 Nanosheet photocatalytic C-H activation and CO 2 Reduction of - Google Patents

ZnIn 2 S 4 Nanosheet photocatalytic C-H activation and CO 2 Reduction of Download PDF

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CN114736179B
CN114736179B CN202210472132.9A CN202210472132A CN114736179B CN 114736179 B CN114736179 B CN 114736179B CN 202210472132 A CN202210472132 A CN 202210472132A CN 114736179 B CN114736179 B CN 114736179B
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CN114736179A (en
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蒋和雁
盛美林
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Chongqing Technology and Business University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • B01J35/39—
    • B01J35/51—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/08—Formation or introduction of functional groups containing oxygen of carboxyl groups or salts, halides or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a ZnIn rich in sulfur vacancy 2 S 4 By C-H activation and CO under the action of the nano-sheet 2 A method for preparing carboxylated products by reduction. The preparation method of the catalyst comprises the following steps: the morphology is regulated and controlled by adding a surfactant sodium citrate, and then sulfur vacancies are introduced by adjusting the proportion of S-source thioacetamide. For synthetic ZnIn 2 S 4 Nanoplatelets are well characterized and are used for photocatalytic CO 2 In carboxylation reaction with biomass platform compound and aryl compound, under irradiation of visible light, znIn rich in sulfur vacancy 2 S 4 Nano sheet in alkali additive K 2 CO 3 Exhibits excellent activity and chemoselectivity for conversion to the corresponding carboxylated product in the presence. ZnIn rich in sulfur vacancies 2 S 4 The excellent catalytic activity of the nanoplatelets should be attributed to the fact that the reduction of the nanoplatelet thickness promotes the rapid migration of the photogenerated electrons to the catalyst surface, and the introduction of sulfur vacancies promotes the adsorption of the substrate and the enrichment of electrons. The carboxylation product has simple synthesis method and catalyst preparation formulaThe method is simple and easy to operate, the reaction condition is mild, and the catalyst is easy to recycle.

Description

ZnIn 2 S 4 Nanosheet photocatalytic C-H activation and CO 2 Reduction of
Technical Field
The invention relates to a ZnIn 2 S 4 Nanosheet photocatalytic C-H activation and CO 2 And (5) reduction.
Background
Large-scale carbon dioxide emissions, which are waste carbon resources, are accompanied by an increase in fossil fuel utilization, resulting in global warming and energy crisis. Carbon dioxide reduction synthesis of value-added carboxylic acid products using off-the-shelf and safe waste C1 resources is a solutionNew means for solving the above problems. In contrast, conventional carboxylic acid production is generally accomplished by complex multi-step formylation and oxidation, and there is an urgent need to find new environmentally friendly, convenient carboxylic acid production and preparation methods. In recent years heterogeneous catalytic systems have received increasing attention for their advantages in terms of separation and recovery in liquid phase reaction mixtures. ZnIn 2 S 4 Because of their appropriate band gap, good visible light absorption capability, high solar energy utilization and unique photoelectric properties, there is a great deal of interest in heterogeneous catalysis. Based on p-ZnIn 2 S 4 In the research of (2), due to the characteristics of the lamellar structure, the modification strategy of morphology regulation and vacancy introduction is used for ZnIn 2 S 4 Modification to further investigate its use in biomass platform compounds with CO 2 The role in the synthesis of high value-added carboxylic acid products has significant practical significance and challenges.
Disclosure of Invention
According to the invention, the morphology is regulated and controlled by adding the surfactant sodium citrate, and then the sulfur vacancy is introduced by adjusting the proportion of S-source thioacetamide. And catalytic materials are used for photocatalytic CO 2 In carboxylation reaction with biomass platform compound and aryl compound, under irradiation of visible light, znIn rich in sulfur vacancy 2 S 4 Nano sheet in alkali additive K 2 CO 3 Exhibits excellent activity and chemoselectivity for conversion to the corresponding carboxylated product in the presence. ZnIn rich in sulfur vacancies 2 S 4 The excellent catalytic activity of the nanoplatelets should be attributed to the fact that the reduction of the nanoplatelet thickness promotes the rapid migration of the photogenerated electrons to the catalyst surface, and the introduction of sulfur vacancies promotes the adsorption of the substrate and the enrichment of electrons.
The invention provides ZnIn rich in sulfur vacancy 2 S 4 And the carboxylation product is synthesized under the action of the nanosheets, the synthesis method of the carboxylation product is simple, the catalyst preparation method is simple and easy to operate, the reaction condition is mild, and the catalyst is easy to recycle.
The adopted technical scheme is as follows: spherical ZnIn synthesis by hydrothermal method 2 S 4 After that, the shape is regulated by adding the surfactant sodium citrateAnd the S source thioacetamide is regulated to introduce sulfur vacancy to prepare the catalytic material. The photocatalytic preparation of carboxylated products is characterized in that: to synthesize ZnIn 2 S 4 Catalytic material for photocatalytic CO 2 In the carboxylation reaction with biomass/aryl compounds, C-H activation and CO were found under irradiation with visible light 2 The reduction energy is in the presence of a base additive K 2 CO 3 Excellent selectivity and conversion are achieved with the aid of mild conditions. ZnIn rich in sulfur vacancies 2 S 4 The excellent catalytic activity of the nanoplatelets should be attributed to the fact that the reduction of the nanoplatelet thickness promotes the rapid migration of the photogenerated electrons to the catalyst surface, and the introduction of sulfur vacancies promotes the adsorption of the substrate and the enrichment of electrons. The carboxylation product has the advantages of simple synthesis method, simple and easy operation of the catalyst preparation method, mild reaction conditions and easy recycling of the catalyst.
ZnIn as described above 2 S 4 Nanosheet photocatalytic C-H activation and CO 2 A method of reduction, characterized by: little catalytic activity is achieved in the absence of light, and the catalytic activity is greatly improved under the promotion of light.
ZnIn as described above 2 S 4 Nanosheet photocatalytic C-H activation and CO 2 A method of reduction, characterized by: in common ZnIn 2 S 4 The FDCA yield is lower under the action of the nanospheres, and the yield is greatly increased after morphology regulation and vacancy introduction.
ZnIn as described above 2 S 4 Nanosheet photocatalytic C-H activation and CO 2 A method of reduction, characterized by: CO 2 With biomass/aryl compounds without sacrificial agents and with H 2 The carboxylated product with high yield is successfully synthesized under the condition that O is a solvent.
ZnIn as described above 2 S 4 Nanosheet photocatalytic C-H activation and CO 2 A method of reduction, characterized by: in alkaline additive K 2 CO 3 Can smoothly realize furan ring sp under the assistance of 2 C-H activation and CO 2 The alkaline additive may be K 3 PO 4 、Na 2 CO 3 、KOH。
ZnIn as described above 2 S 4 Nanosheet photocatalytic C-H activation and CO 2 A method of reduction, characterized by: znIn rich in sulfur vacancies 2 S 4 Nanosheet catalyzed CO 2 Other biomass platform compounds, aromatics and olefins that synthesize carboxylated products include: furfuryl alcohol, furoic acid, phenylacetylene, styrene, chlorobenzene, bromobenzene, 4-bromoanisole, benzene, toluene.
ZnIn as described above 2 S 4 Nanosheet photocatalytic C-H activation and CO 2 A method of reduction, characterized by: the catalyst has good recycling performance, and ZnIn rich in sulfur vacancy is recycled for 5 times 2 S 4 The nanosheet photocatalyst still maintains a high photocatalytic activity.
ZnIn as described above 2 S 4 Nanosheet photocatalytic C-H activation and CO 2 A method of reduction, characterized by: znIn rich in sulfur vacancies 2 S 4 The excellent catalytic activity of the nanoplatelets is attributed to the fact that the reduction in the thickness of the nanoplatelets promotes the rapid migration of the photogenerated electrons to the catalyst surface, and the introduction of sulfur vacancies promotes the adsorption of the substrate and the enrichment of electrons.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the photocatalyst comprises the following steps: 68mg of ZnCl 2 And 293 mg of InCl 3 •4H 2 O was dissolved in 25mL deionized water and 5mL ethylene glycol. After vigorous stirring at room temperature for 30 minutes, 150 mg Thioacetamide (TAA) was added to the solution. After stirring for an additional 30 minutes, the solution was transferred to a 50mL teflon lined stainless steel autoclave and held in the oven at 120 ℃ for 12 hours. After natural cooling, the product was collected by centrifugation, washed twice with ethanol and distilled water, and then freeze-dried.
Visible light catalyzed C-H activation and CO 2 A method of reduction, generally comprising the steps of: 10mg PVs-ZIS photocatalyst and 0.1mmol base additive were added to a 10 mL two neck round bottom flask and the reaction solution was quenched with 1 atm CO 2 Fill to saturation, then add 0.2 mmol furfural and 2mL deionized waterInto a round bottom flask. The mixture was stirred at 0.75W/cm -2 The mixture was stirred for 24 hours under a blue LED (460 nm). The yield and structure of the product were analyzed by HPLC and NMR.
Drawings
FIG. 1 is a SEM image of the preparation of catalysts of example 1 a) ZIS, b) P-ZIS and c) PVs-ZIS and d) TEM image of PVs-ZIS. e) HRTEM image of PVs-ZIS and f) AFM image of PVs-ZIS.
FIG. 2 is an X-ray diffraction pattern of the catalyst a) ZIS, P-ZIS, PVs-ZIS prepared in example 1.
FIG. 3 shows XPS a) full spectrum of catalysts ZIS, P-ZIS, PVs-ZIS, b) S2P, c) Zn2P and d) In3d prepared In example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Embodiment case 1:
ZnIn 2 S 4 (ZIS) preparation of photocatalyst:
ZnIn 2 S 4 (ZIS) photocatalyst 68mg ZnCl was synthesized according to the hydrothermal method reported in the literature 2 And 293 mg of InCl 3 •4H 2 O was dissolved in 25mL deionized water and 5mL ethylene glycol. After vigorous stirring at room temperature for 30 minutes, 150 mg Thioacetamide (TAA) was added to the solution. After stirring for an additional 30 minutes, the solution was transferred to a 50mL teflon lined stainless steel autoclave and held in the oven at 120 ℃ for 12 hours. After natural cooling, the product was collected by centrifugation, washed twice with ethanol and distilled water, and then freeze-dried.
ZnIn 2 S 4 Preparation of nanoplatelets (P-ZIS):
P-ZIS is prepared by a hydrothermal method. 68mg of ZnCl 2 、293 mg InCl 3 •4H 2 O and 300mg trisodium citrate were dissolved in 25mL deionized water and 5mL ethylene glycol. After vigorous stirring at room temperature for 30 minutes, 150 mg Thioacetamide (TAA) was added to the solution. After stirring for an additional 30 minutes, the heterogeneous solution was transferred to a 50mL teflon lined stainless steel autoclave and in an oven at 120 ℃Hold for 12 hours. After natural cooling, the product was collected by centrifugation, washed twice with ethanol and distilled water, and then freeze-dried.
ZnIn with S vacancy 2 S 4 Nanoplatelets (PVs-ZIS) preparation:
PVs-ZIS was prepared by hydrothermal method. In a typical synthesis, 68mg ZnCl is added 2 、293 mg InCl 3 •4H 2 O and 300mg trisodium citrate were dissolved in 25mL deionized water and 5mL ethylene glycol. After vigorous stirring at room temperature for 30 minutes, 300mg Thioacetamide (TAA) was added to the solution. After stirring for an additional 30 minutes, the heterogeneous solution was transferred to a 50mL teflon lined stainless steel autoclave and held in the oven at 120 ℃ for 12 hours. After natural cooling, the product was collected by centrifugation, washed twice with ethanol and distilled water, and then freeze-dried.
FIG. 1 is an SEM image of the synthesized ZIS, P-ZIS, PVs-ZIS of steps (1), (2), (3), ZIS having a morphology different from that of the P-ZIS, PVs-ZIS, and ZnIn reported 2 S 4 Similar to the literature, common ZnIn 2 S 4 In a typical flower-like microsphere structure, P-ZIS is a nanosheet with an average size of about 100nm, due to the size-adjusting capability of the surfactant sodium citrate. The introduction of sulfur vacancies had no effect on the lamellar structure, and PVs-ZIS exhibited a lamellar structure similar to P-ZIS. (d) Is a TEM spectrum of the prepared PVs-ZIS catalytic material, and the TEM shows a lamellar structure of PVs-ZIS. (e) Is a distinct lattice fringe of HRTEM images showing interplanar spacing (d=0.32 nm), which corresponds to hexagonal ZnIn 2 S 4 (102) Crystal planes. FIG. (f) shows that the thickness of PVs-ZIS was analyzed by Atomic Force Microscope (AFM), and PVs-ZIS was about 1.45-2.45 nm.
XRD analysis is carried out on the ZIS, P-ZIS and PVs-ZIS catalytic materials prepared in the embodiment respectively as shown in figure 2, wherein the XRD peaks of the ZIS, P-ZIS and PVs-ZIS are clear and well-defined, and all diffraction peaks correspond to ZnIn 2 S 4 Hexagonal structure (JCPLDS No. 65-2023). Indicating that the catalytic material has high phase purity and retains the original crystalline phase. At 8.7 °, 20.4 °, 27.3 ° andthe 47.0 peak corresponds to the (002), (006), (102) and (110) planes, respectively. The surfactant sodium citrate promotes crystallinity and (110) plane exposure of P-ZIS with morphology modification compared to flower ZIS. In addition, as the defect structure is constructed, the exposure of the PVs-ZIS (110) crystal face is reduced, which can be explained by the fact that the growth of the (110) crystal face is inhibited to a certain extent by the increase of the thioacetamide concentration in the PVs-ZIS preparation process.
FIG. 3 is an XPS plot of the P-ZIS, PVs-ZIS catalytic material prepared as described above, with X-ray photoelectron spectroscopy (XPS) confirming the simultaneous presence of Zn, in and S peaks In P-ZIS and PVs-ZIS. The S2P 3/2 and 2P1/2 of P-ZIS are 161.23 and 162.48 eV, respectively. After introducing the S vacancies into the ZIS nanosheets, significant negative shifts of S2p 3/2 and 2p1/2 of 0.18 eV and 0.22eV were detected. The S vacancy has strong electron absorption capability, and as ZIS nanometer sheet electrons are transferred to the S vacancy, the S atom balance electron cloud density is reduced. Thus, the S atom binding energy decreases after the S vacancies are formed. The binding energies of Zn2P 3/2 and Zn2P 1/2 of P-ZIS are at 1021.59 and 1044.65 eV, respectively (FIG. 3 c), which is divalent zinc (Zn 2+ ) Is a characteristic peak of (2). Whereas the peaks of 444.60 and 452.11 eV In FIG. 3d are assigned to In P-ZIS 3+ In3d 3/2 and In3d1/2. Notably, there was a slight negative change In the binding energy of Zn2p and In3d In PVs-ZIS, indicating that the S vacancies lead to some decrease In the coordination number of Zn and In.
Example 2 (reaction reference Table 1, entry 1)
CO at 1 atmosphere 2 Furfural (0.02 mmol), ZIS (10 mg) and K under irradiation of visible light in an atmosphere 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.15W cm -2 The LED blue light was irradiated to react 24 h. The conversion of furfural and the selectivity of FDCA (2, 5-furandicarboxylic acid) were analyzed by HPLC. The conversion of furfural was 37% and the selectivity of FDCA was 30%.
Example 3 (reaction reference Table 1, entry 2)CO at 1 atmosphere 2 Furfural (0.02 mmol), ZIS (10 mg) and K under irradiation of visible light in an atmosphere 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 Reaction 24h in O in the absence of light. The conversion of furfural and the selectivity of FDCA were analyzed by HPLC. Furfural is not converted.
Example 4 (reaction reference Table 1, entry 3)
CO at 1 atmosphere 2 Furfural (0.02 mmol) was dispersed in an atmosphere under irradiation of visible light, ZIS (10 mg) to 2 mLH 2 O at 0.15W cm -2 The LED blue light was irradiated to react 24 h. The conversion of furfural and the selectivity of FDCA were analyzed by HPLC. The conversion of furfural was 28% and the selectivity of FDCA was 25%.
Example 5 (reaction reference Table 1, entry 4)
CO at 1 atmosphere 2 Furfural (0.02 mmol), K under irradiation of visible light in atmosphere 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.15W cm -2 The LED blue light was irradiated to react 24 h. The conversion of furfural and the selectivity of FDCA were analyzed by HPLC. Furfural is not converted.
Example 6 (reaction reference Table 1, entry 5)
At 1 atm N 2 Furfural (0.02 mmol) was dispersed in an atmosphere under irradiation of visible light, ZIS (10 mg) to 2 mLH 2 O at 0.15W cm -2 The LED blue light was irradiated to react 24 h. The conversion of furfural and the selectivity of FDCA were analyzed by HPLC. The conversion rate of the furfural is 100 percent, and no FDCA is generated.
Example 7 (reaction reference Table 1, entry 6)
CO at 1 atmosphere 2 Furfural (0.02 mmol), ZIS (10 mg) and K under irradiation of visible light in an atmosphere 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. The conversion of furfural and the selectivity of FDCA were analyzed by HPLC. The conversion of furfural was 37% and the selectivity of FDCA was 30%.
Example 8 (reaction reference Table 1, entry 10)
CO at 1 atmosphere 2 Furfural (0.02 mmol), P-ZIS (10 mg) and K under irradiation of visible light in an atmosphere 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. The conversion of furfural and the selectivity of FDCA were analyzed by HPLC. The conversion of furfural was 93% and the selectivity of FDCA was 83%.
Example 9 (reaction reference Table 1, entry 11)
CO at 1 atmosphere 2 Furfural (0.02 mmol), PVs-ZIS (10 mg) and K under irradiation of visible light in an atmosphere 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. The conversion of furfural and the selectivity of FDCA were analyzed by HPLC. The conversion of furfural was 97% and the selectivity of FDCA was 100%.
Embodiment case 10 (reaction reference Table 2, entry 1)
CO at 1 atmosphere 2 In the atmosphere, furoic acid (0.02 mmol), PVs-ZIS (10 mg) and K were irradiated with visible light 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. The conversion of furoic acid was analyzed by HPLC. The conversion of furoic acid was 100% and the isolated yield of carboxylated product was 98%.
Example 11 (reaction reference Table 2, entry 2)
CO at 1 atmosphere 2 In the atmosphere, under irradiation of visible light, furfuryl alcohol (0.02 mmol), PVs-ZIS (10 mg) and K 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. The conversion of furfuryl alcohol was analyzed by HPLC. The conversion of furfuryl alcohol was 92% and the isolated yield of carboxylated product was 88%
Example 12 (reaction reference Table 2, entry 3)
CO at 1 atmosphere 2 Phenylacetylene (0.02 mmol), PVs-ZIS (10 mg) and K under irradiation of visible light in an atmosphere 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. The conversion of phenylacetylene was analyzed by HPLC. The conversion of phenylacetylene was 87% and the isolated yield of carboxylated product was 82%.
Example 13 (reaction reference Table 2, entry 4)
CO at 1 atmosphere 2 Under irradiation of visible light, styrene (0.02 mmol), PVs-ZIS (10 mg) and K 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. The conversion of styrene was analyzed by HPLC. The conversion of styrene was 88% and the isolated yield of carboxylated product was 85%.
Example 14 (reaction reference Table 2, entry 5)
CO at 1 atmosphere 2 Bromobenzene (0.02 mmol), PVs-ZIS (10 mg) and K under irradiation of visible light in an atmosphere 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. The conversion of bromobenzene was analyzed by HPLC. The conversion of bromobenzene was 86% and the isolated yield of carboxylated product was 83%.
Example 15 (reaction reference Table 2, entry 6)
CO at 1 atmosphere 2 In the atmosphere, chlorobenzene (0.02 mmol), PVs-ZIS (10 mg) and K were irradiated with visible light 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. The conversion of chlorobenzene was analyzed by HPLC. The conversion of chlorobenzene was 85% and the isolated yield of carboxylated product was 82%.
Example 16 (reaction reference Table 2, entry 7)
CO at 1 atmosphere 2 In the atmosphere, under irradiation of visible light, p-bromoanisole (0.02 mmol), PVs-ZIS (10 mg) and K 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. By HPLC separationAnd separating out the conversion rate of the p-bromoanisole. The conversion of p-bromoanisole was 82% and the isolated yield of carboxylated product was 76%.
Example 17 (reaction reference Table 2, entry 8)
CO at 1 atmosphere 2 Benzene (0.02 mmol), PVs-ZIS (10 mg) and K under irradiation of visible light in an atmosphere 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. Benzene conversion was analyzed by HPLC. The benzene conversion was 87% and the carboxylated product isolated in 85% yield.
Example 18 (reaction reference Table 2, entry 9)
CO at 1 atmosphere 2 Toluene (0.02 mmol), PVs-ZIS (10 mg) and K under irradiation of visible light in an atmosphere 2 CO 3 (0.1 mmol) dispersed to 2 mLH 2 O at 0.75W cm -2 The LED blue light was irradiated to react 24 h. Toluene conversion was analyzed by HPLC. The toluene conversion was 83% and the carboxylated product isolated in 80% yield.

Claims (1)

1. ZnIn rich in sulfur vacancies 2 S 4 Nanosheets for photocatalytic C-H activation and CO 2 The use of reduction to produce carboxylic acids characterized in that:
the ZnIn rich in sulfur vacancy 2 S 4 The nano-sheet PVs-ZIS is prepared by a hydrothermal method: 68mg of ZnCl 2 、293mg InCl 3 ·4H 2 O and 300mg of trisodium citrate are dissolved in 25mL of deionized water and 5mL of ethylene glycol, after intense stirring for 30 minutes at room temperature, 300mg of thioacetamide is added to the solution, after stirring for 30 minutes again, the heterogeneous solution is transferred into a stainless steel autoclave lined with Teflon of 50mL, and kept in an oven at 120 ℃ for 12 hours, after natural cooling, the product is collected centrifugally, washed twice with ethanol and distilled water, and then freeze-dried;
the photocatalytic C-H activation and CO 2 The process for preparing carboxylic acid by reduction is as follows: CO at 1 atmosphere 2 Under the irradiation of visible light, 0.02mmol of substrate, 10mg of PVs-ZIS and 0.1mmol of K are arranged in the atmosphere 2 CO 3 Disperse to 2mL H 2 O at 0.75W cm -2 Reacting for 24 hours under the irradiation of an LED blue lamp, and analyzing the conversion rate of a substrate and the selectivity of a product by HPLC; wherein the substrate is any one of furfural, furoic acid, furfuryl alcohol, phenylacetylene, styrene, bromobenzene, chlorobenzene, p-bromoanisole, benzene and toluene; carboxylation products of the substrates furfural, furoic acid and furfuryl alcohol are 2, 5-furandicarboxylic acid; the carboxylation product of the substrate phenylacetylene is 2-phenylacrylic acid; the carboxylation product of the substrate styrene is 2-phenylpropionic acid; the carboxylation products of bromobenzene, chlorobenzene and benzene are benzoic acid; the carboxylation product of the substrate p-bromoanisole is 4-methoxybenzoic acid; the carboxylation product of the substrate toluene was 4-methylbenzoic acid.
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