CN114736179A - ZnIn2S4Nanosheet photocatalytic C-H activation and CO2Reduction of - Google Patents
ZnIn2S4Nanosheet photocatalytic C-H activation and CO2Reduction of Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims description 23
- 238000010499 C–H functionalization reaction Methods 0.000 title claims description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000002135 nanosheet Substances 0.000 claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 13
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 11
- 239000002028 Biomass Substances 0.000 claims abstract description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 230000021523 carboxylation Effects 0.000 claims abstract description 7
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
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- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 125000003118 aryl group Chemical class 0.000 claims abstract description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 7
- 239000011941 photocatalyst Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000033228 biological regulation Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 42
- 239000012298 atmosphere Substances 0.000 description 33
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 description 31
- 238000004128 high performance liquid chromatography Methods 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
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- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
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- 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
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- 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
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Abstract
The invention discloses a method for preparing ZnIn rich in sulfur vacancy2S4Under the action of nanosheets, activation is carried out through C-H and CO2A process for the reduction of a carboxylated product. The preparation method of the catalyst comprises the following steps: the appearance is regulated by adding a surfactant sodium citrate, and sulfur vacancy is introduced by regulating the proportion of S-source thioacetamide. For synthetic ZnIn2S4The nanosheets were well characterized and used to photocatalyze CO2ZnIn rich in sulfur vacancies under visible light irradiation in carboxylation reactions with biomass platform compounds and aryl compounds2S4Nanosheet in alkaline additive K2CO3Exhibit excellent activity and chemoselectivity in the presence of conversion to the corresponding carboxylated product. ZnIn rich in sulfur vacancies2S4The excellent catalytic activity of the nanosheets should be attributed to the fact that the reduction in nanosheet thickness promotes rapid migration of photo-generated electrons to the catalyst surface, and the introduction of sulfur vacancies promotes adsorption and electron enrichment of the substrate. The synthetic method of the carboxylation product is simple, the preparation method of the catalyst is simple and easy to operate, the reaction condition is mild, and the catalyst is easy to recycle.
Description
Technical Field
The invention relates to ZnIn2S4Nanosheet photocatalytic C-H activation and CO2And (4) reducing.
Background
The large scale carbon dioxide emissions of waste carbon resources are accompanied by an increase in the utilization of fossil fuels, leading to global warming and energy crisis. The carbon dioxide reduction synthesis of value-added carboxylic acid products using the ready-made and safe waste C1 resource is a new approach to solve the above problems. In contrast, conventional carboxylic acid production is generally achieved by complicated multistep formylation and oxidation, and there is an urgent need to find a new, environmentally friendly and convenient method for producing carboxylic acid. In recent years, heterogeneous catalytic systems have received increasing attention because of their advantages in separation and recovery in liquid phase reaction mixtures. ZnIn2S4Due to its appropriate band gap, good visible light absorption capability, high solar energy utilization rate and unique photoelectric properties, it has drawn much attention in heterogeneous catalysis. Based on p-ZnIn2S4In the research, due to the characteristics of the layered structure, the modification strategy of shape regulation and vacancy introduction is used for ZnIn2S4Modification was performed to further investigate its use with biomass platform compounds and CO2The role in the synthesis of high value added carboxylic acid products is of great practical significance and challenge.
Disclosure of Invention
The appearance is regulated by adding a surfactant sodium citrate, and the sulfur vacancy is introduced by regulating the proportion of S-source thioacetamide. And using the catalytic material for photocatalytic CO2ZnIn rich in sulfur vacancies under visible light irradiation in carboxylation reactions with biomass platform compounds and aryl compounds2S4Nanosheet in alkaline additive K2CO3Exhibit excellent activity and chemoselectivity in the presence of conversion to the corresponding carboxylated product. ZnIn rich in sulfur vacancies2S4The excellent catalytic activity of the nanosheets should be attributed to the fact that the reduction in nanosheet thickness promotes rapid migration of photo-generated electrons to the catalyst surface, and the introduction of sulfur vacancies promotes adsorption and electron enrichment of the substrate.
The invention provides a method for preparing ZnIn rich in sulfur vacancy2S4The synthesis of the carboxylation product under the action of the nanosheets is simple, the preparation method of the catalyst is simple and easy to operate, the reaction conditions are mild, and the catalyst is easy to recycle.
The adopted technical scheme is as follows: spherical ZnIn synthesized by hydrothermal method2S4And then, adding a surfactant sodium citrate to regulate the morphology, and introducing sulfur vacancies by regulating the proportion of S-source thioacetamide to realize the preparation of the catalytic material. The photocatalytic preparation of the carboxylated product is characterized in that: ZnIn to be synthesized2S4Catalytic material for photocatalytic CO2In the carboxylation reaction with the Biomass Compound/aryl Compound, under visible light irradiation, C-H activation and CO were found2Reducing energy in alkaline additive K2CO3With the help of mild conditions, excellent selectivity and conversion rate are obtained. ZnIn rich in sulfur vacancies2S4The excellent catalytic activity of the nanosheets should be attributed to the fact that the reduction in nanosheet thickness promotes rapid migration of photo-generated electrons to the catalyst surface, and the introduction of sulfur vacancies promotes adsorption and electron enrichment of the substrate. The synthetic method of the carboxylation product is simple, the preparation method of the catalyst is simple and easy to operate, the reaction condition is mild, and the catalyst is easy to recycle.
ZnIn as defined above2S4Nanosheet photocatalytic C-H activation and CO2A method of reduction, characterized by: almost no catalytic activity is generated in the absence of illumination, and the catalytic activity is greatly improved under the acceleration of light.
ZnIn as defined above2S4Nanosheet photocatalytic C-H activation and CO2A method of reduction, characterized by: in generalGeneral ZnIn2S4The yield of the FDCA is low under the action of the nanospheres, and is greatly increased after morphology regulation and vacancy introduction.
ZnIn as defined above2S4Nanoplatelet photocatalytic C-H activation and CO2A method of reduction, characterized by: CO 22With biomass/aryl compounds in the absence of a sacrificial agent and with H2The carboxylation product is successfully synthesized with high yield under the condition that O is a solvent.
ZnIn as defined above2S4Nanosheet photocatalytic C-H activation and CO2A method of reduction, characterized by: in the presence of a basic additive K2CO3Can smoothly realize furan ring sp under the assistance of2C-H activation and CO2The basic additive may be K3PO4、Na2CO3、KOH。
ZnIn as defined above2S4Nanosheet photocatalytic C-H activation and CO2A method of reduction, characterized by: in ZnIn rich in sulfur vacancies2S4With CO under catalysis of nanosheet2Other biomass platform compounds, aromatics and olefins for the synthesis of carboxylated products include: furfuryl alcohol, furoic acid, phenylacetylene, styrene, chlorobenzene, bromobenzene, 4-bromoanisole, benzene and toluene.
ZnIn as defined above2S4Nanosheet photocatalytic C-H activation and CO2A method of reduction, characterized by: the catalyst has better recycling performance, is recycled for 5 times and is rich in ZnIn with sulfur vacancy2S4The nano-sheet photocatalyst still maintains high photocatalytic activity.
ZnIn as defined above2S4Nanosheet photocatalytic C-H activation and CO2A method of reduction, characterized by: ZnIn rich in sulfur vacancies2S4The excellent catalytic activity of the nanosheets is attributed to the fact that the reduction of the thickness of the nanosheets promotes the rapid migration of photo-generated electrons to the surface of the catalyst, and the introduction of sulfur vacancies promotes the adsorption and electron enrichment of the substrate.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the photocatalyst comprises the following steps: mixing 68 mg ZnCl2And 293 mg InCl3•4H2O was dissolved in 25 mL of deionized water and 5 mL of ethylene glycol. After stirring vigorously 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 50 mL Teflon lined stainless steel autoclave and held in an 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 CO2A method of reduction, generally comprising the steps of: 10 mg of PVs-ZIS photocatalyst and 0.1 mmol of alkali additive were added to a 10 mL two-necked round-bottomed flask, and the reaction solution was treated with 1 atm CO2Saturated, then 0.2 mmol furfural and 2 mL deionized water were added to the round bottom flask. The mixture was heated at 0.75W/cm-2Stirring was carried out for 24 hours under a blue LED (460 nm). The product was analyzed by HPLC and NMR for yield and structure.
Drawings
FIG. 1 is SEM images of a) ZIS, b) P-ZIS, and c) PVs-ZIS and d) TEM images of PVs-ZIS for the preparation of catalyst 1 in example 1. 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 is an XPS a) survey 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 embodiments.
Example 1:
ZnIn2S4(ZIS) preparation of photocatalyst:
ZnIn2S4(ZIS) photocatalyst was synthesized according to the hydrothermal method reported in the literature, using 68 mg of ZnCl2And 293 mg InCl3•4H2O dissolved in 25 mL deionized waterAnd 5 mL of ethylene glycol. After stirring vigorously 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 50 mL Teflon lined stainless steel autoclave and held in an 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.
ZnIn2S4Preparation of nanoplatelets (P-ZIS):
P-ZIS was prepared by a hydrothermal method. Mixing 68 mg ZnCl2、293 mg InCl3•4H2O and 300 mg trisodium citrate were dissolved in 25 mL deionized water and 5 mL ethylene glycol. After stirring vigorously 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 50 mL 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 having S vacancies2S4Nanosheet (PVs-ZIS) preparation:
PVs-ZIS was prepared by a hydrothermal method. In a typical synthesis, 68 mg ZnCl will be used2、293 mg InCl3•4H2O and 300 mg trisodium citrate were dissolved in 25 mL deionized water and 5 mL ethylene glycol. After stirring vigorously at room temperature for 30 minutes, 300 mg Thioacetamide (TAA) was added to the solution. After stirring for an additional 30 minutes, the heterogeneous solution was transferred to a 50 mL 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 photograph of ZIS, P-ZIS and PVs-ZIS synthesized in the above steps (1), (2) and (3), wherein ZIS has a different morphology from P-ZIS and PVs-ZIS and is related to ZnIn2S4ZnIn of general interest, similarly to the literature2S4In a typical flower-like microsphere structure, by the size of the surfactant sodium citrateTuning power, P-ZIS, is a nanoplate with an average size of about 100 nm. The introduction of sulfur vacancies had no effect on the sheet structure, and PVs-ZIS exhibited a sheet structure similar to P-ZIS. (d) Is a TEM pattern of the prepared PVs-ZIS catalytic material, and the TEM shows a sheet structure of the PVs-ZIS. (e) It is the HRTEM image that shows significant lattice fringes for interplanar spacing (d =0.32 nm), which corresponds to hexagonal ZnIn2S4(102) A crystal plane. FIG. f shows that the thickness of PVs-ZIS was analyzed by Atomic Force Microscopy (AFM), and the thickness of PVs-ZIS was about 1.45-2.45 nm.
XRD analysis is respectively carried out on the ZIS, P-ZIS and PVs-ZIS catalytic materials prepared in the embodiment as shown in figure 2, XRD peaks of the ZIS, P-ZIS and PVs-ZIS in the figure are clear and well-defined, and all diffraction peaks correspond to ZnIn2S4Hexagonal structure (JCPDS number 65-2023). Indicating that the catalytic material has high phase purity and retains the original crystalline phase. Peaks at 8.7 °, 20.4 °, 27.3 ° and 47.0 ° correspond to (002), (006), (102) and (110) planes, respectively. The surfactant sodium citrate promoted crystallinity and (110) crystal face exposure of P-ZIS with modification of morphology, as compared to flower ZIS. In addition, as the defect structure is constructed, the exposure amount of the PVs-ZIS (110) crystal face is reduced, which can be explained by that the growth of the (110) crystal face is inhibited to a certain extent by the increase of the thioacetamide concentration in the preparation process of the PVs-ZIS.
FIG. 3 is an XPS plot of the P-ZIS, PVs-ZIS catalytic material prepared as described above, and X-ray photoelectron spectroscopy (XPS) confirmed the presence of Zn, In and S peaks In both P-ZIS and PVs-ZIS. P-ZIS has S2P 3/2 and 2P1/2 of 161.23 and 162.48 eV, respectively. After the introduction of the S vacancies to the ZIS nanosheets, significant negative shifts of S2p 3/2 and 2p1/2 by 0.18 eV and 0.22 eV were detected. The S vacancy has strong electron absorption capacity, and as ZIS nanosheet electrons are transferred to the S vacancy, the S atom equilibrium electron cloud density is reduced. Therefore, the S atom binding energy decreases after the formation of the S vacancy. The binding energies of Zn2P 3/2 and Zn2P 1/2 of P-ZIS were at 1021.59 and 1044.65 eV, respectively (FIG. 3 c), which are divalent zinc (Zn)2+) The characteristic peak of (1). While the peaks 444.60 and 452.11 eV In FIG. 3d are assigned to In P-ZIS3+In3d 3/2 and In3d 1/2. It is noted that there is a slight negative change In the binding energies of Zn2p and In3d In PVs-ZIS, indicating that the S vacancies lead to a certain reduction In the coordination numbers of Zn and In.
Example 2 (reaction reference Table 1, entry 1)
At 1 atmosphere of CO2Furfural (0.02 mmol), ZIS (10 mg) and K under irradiation of visible light in an atmosphere2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.15W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. Furfural conversion and selectivity to FDCA (2, 5-furandicarboxylic acid) were analyzed by HPLC. The conversion of furfural was 37% and the selectivity of FDCA was 30%.
Example 3 (see Table 1 for reaction, entry 2) CO at 1 atm2Furfural (0.02 mmol), ZIS (10 mg) and K under irradiation of visible light in an atmosphere2CO3(0.1 mmol) was dispersed in 2 mLH2And reacting in O in the absence of light for 24 hours. Furfural conversion and FDCA selectivity were analyzed by HPLC. Furfural was not converted.
Example 4 (reaction reference Table 1, entry 3)
At 1 atmosphere of CO2Under visible light irradiation in the atmosphere, furfural (0.02 mmol), ZIS (10 mg) was dispersed in 2 mLH2In O at 0.15W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. Furfural conversion and FDCA selectivity were analyzed by HPLC. The conversion of furfural was 28% and the selectivity of FDCA was 25%.
EXAMPLE 5 (Ref. Table 1, entry 4)
At 1 atmosphere of CO2Under visible light irradiation in the atmosphere, furfural (0.02 mmol), K2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.15W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. Furfural conversion and FDCA selectivity were analyzed by HPLC. Furfural was not converted.
Example 6 (reaction reference Table 1, entry 5)
At 1 atmosphere N2Under visible light irradiation in the atmosphere, furfural (0.02 mmol), ZIS (10 mg) was dispersed in 2 mLH2In O at 0.15W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. Furfural conversion and FDCA selectivity were analyzed by HPLC. The conversion of furfural was 100%, and no FDCA was produced.
Example 7 (reaction reference Table 1, entry 6)
At 1 atmosphere of CO2Furfural (0.02 mmol), ZIS (10 mg) and K under irradiation of visible light in an atmosphere2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.75W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. Furfural conversion and FDCA selectivity 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)
At 1 atmosphere of CO2In the atmosphere, under visible light irradiation, furfural (0.02 mmol), P-ZIS (10 mg) and K2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.75W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. Furfural conversion and FDCA selectivity 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)
At 1 atmosphere of CO2Furfural (0.02 mmol), PVs-ZIS (10 mg) and K under visible light irradiation in an atmosphere2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.75W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. Furfural conversion and FDCA selectivity were analyzed by HPLC. The conversion of furfural was 97% and the selectivity of FDCA was 100%.
Example 10 (reaction reference Table 2, entry 1)
At 1 atmosphere of CO2Furoic acid (0.02 mmol), PVs-ZIS (10 mg) and K under visible light irradiation in an atmosphere2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.75W cm-2 LED blue light illuminationAnd reacting for 24 hours. 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)
At 1 atmosphere of CO2Furfuryl alcohol (0.02 mmol), PVs-ZIS (10 mg) and K under visible light irradiation in an atmosphere2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.75W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. 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 (Ref. Table 2, entry 3)
At 1 atmosphere of CO2Phenylacetylene (0.02 mmol), PVs-ZIS (10 mg) and K under irradiation of visible light in an atmosphere2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.75W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. 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)
At 1 atmosphere of CO2Styrene (0.02 mmol), PVs-ZIS (10 mg) and K in an atmosphere under irradiation of visible light2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.75W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. 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)
At 1 atmosphere of CO2Bromobenzene (0.02 mmol), PVs-ZIS (10 mg) and K under visible light irradiation in an atmosphere2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.75W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. The bromobenzene conversion was analyzed by HPLC. Of bromobenzeneThe conversion was 86% and the isolated yield of carboxylated product was 83%.
Example 15 (reaction reference Table 2, entry 6)
At 1 atmosphere of CO2Chlorobenzene (0.02 mmol), PVs-ZIS (10 mg) and K in an atmosphere under visible light irradiation2CO3(0.1 mmol) to 2 mLH2In O at 0.75W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. The chlorobenzene conversion was analyzed by HPLC. The conversion of chlorobenzene was 85% and the isolated yield of the carboxylated product was 82%.
EXAMPLE 16 (Ref. Table 2, entry 7)
At 1 atmosphere of CO2Under the irradiation of visible light in the atmosphere, p-bromoanisole (0.02 mmol), PVs-ZIS (10 mg) and K2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.75W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. Conversion of p-bromoanisole was analyzed by HPLC. The conversion to bromoanisole was 82% and the isolated yield of carboxylated product was 76%.
EXAMPLE 17 (Ref. Table 2, entry 8)
At 1 atmosphere of CO2Benzene (0.02 mmol), PVs-ZIS (10 mg) and K in an atmosphere under visible light irradiation2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.75W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. Benzene conversion was analyzed by HPLC. The conversion of benzene was 87% and the isolated yield of carboxylated product was 85%.
Example 18 (reaction reference Table 2, entry 9)
At 1 atmosphere of CO2In an atmosphere of visible light, toluene (0.02 mmol), PVs-ZIS (10 mg) and K2CO3(0.1 mmol) was dispersed in 2 mLH2In O at 0.75W cm-2 And reacting for 24 hours under the irradiation of an LED blue lamp. The conversion of toluene was analyzed by HPLC. The conversion of toluene was 83% and the isolated yield of carboxylated product was 80%.
Claims (7)
1. The invention discloses a method for preparing ZnIn rich in sulfur vacancy2S4Made of nano-sheetWith effective C-H activation and CO2A process for the reduction of a carboxylated product, the catalyst being prepared by: the morphology is regulated by adding a surfactant sodium citrate, and sulfur vacancies are introduced by regulating the proportion of S-source thioacetamide to realize the preparation of the catalytic material, wherein the preparation of the carboxylation product by photocatalysis is characterized in that: the synthesized ZnIn2S4Catalytic material for photocatalytic CO2In the carboxylation reaction with biomass/aryl compounds, C-H activation and CO were found2The reduction can be carried out under mild conditions with excellent selectivity and conversion.
2. The ZnIn of claim 12S4Nanosheet photocatalytic C-H activation and CO2Reduction, which is characterized in that: almost no catalytic activity is generated in the absence of light, and the catalytic activity is greatly improved under the acceleration of light.
3. The ZnIn of claim 12S4Nanosheet photocatalytic C-H activation and CO2Reduction, characterized in that: in the general ZnIn2S4The yield of carboxylation products under the action of nanospheres is low, and the yield is greatly increased through shape regulation and vacancy introduction.
4. The ZnIn of claim 12S4Nanosheet photocatalytic C-H activation and CO2Reduction, characterized in that: CO 22With biomass/aryl compounds without sacrificial agents and with H2The carboxylation product is successfully synthesized with high yield under the condition that O is a solvent.
5. The ZnIn of claim 12S4Nanosheet photocatalytic C-H activation and CO2Reduction, characterized in that: in the presence of a basic additive K2CO3Can smoothly realize furan ring sp under the assistance of2C-H activation and CO2The basic additive may be K3PO4、Na2CO3、KOH。
6. The ZnIn of claim 12S4Nanosheet photocatalytic C-H activation and CO2Reduction, characterized in that: in ZnIn rich in sulfur vacancies2S4With CO under catalysis of nanosheet2Other biomass platform compounds, aromatics and olefins for the synthesis of carboxylated products include: furfuryl alcohol, furoic acid, phenylacetylene, styrene, chlorobenzene, bromobenzene, 4-bromoanisole, benzene and toluene.
7. The ZnIn of claim 12S4Nanosheet photocatalytic C-H activation and CO2Reduction, characterized in that: the catalyst has better recycling performance, is recycled for 5 times and is rich in ZnIn with sulfur vacancy2S4The nano-sheet photocatalyst still maintains high photocatalytic activity.
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| CN114713264A (en) * | 2022-05-06 | 2022-07-08 | 重庆工商大学 | Photocatalytic carboxylation of chlorophenols and carbon dioxide on carbon nitride nanotubes |
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| CN115090299A (en) * | 2022-07-25 | 2022-09-23 | 陕西科技大学 | ZnIn with sulfur defect 2 S 4 Preparation method of photocatalyst and application of photocatalyst in degrading antibiotics |
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| CN117599854A (en) * | 2023-11-22 | 2024-02-27 | 昆明理工大学 | Indium zinc sulfide/tetra (4-carboxyphenyl) zinc porphyrin Z-type heterojunction containing sulfur vacancies, and preparation method and application thereof |
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