CN113477278B - Pyridine quaternary ammonium salt and inorganic semiconductor hybrid system photocatalytic reduction CO2Applications of - Google Patents
Pyridine quaternary ammonium salt and inorganic semiconductor hybrid system photocatalytic reduction CO2Applications of Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 49
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000004065 semiconductor Substances 0.000 title claims abstract description 45
- 230000009467 reduction Effects 0.000 title claims abstract description 28
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- -1 Pyridine quaternary ammonium salt Chemical class 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005286 illumination Methods 0.000 claims abstract description 6
- 229910001868 water Inorganic materials 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 4
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 238000005956 quaternization reaction Methods 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 229960004592 isopropanol Drugs 0.000 claims description 4
- 229920000885 poly(2-vinylpyridine) Polymers 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 150000005837 radical ions Chemical class 0.000 claims description 4
- 229910004613 CdTe Inorganic materials 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 2
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 2
- 229960005055 sodium ascorbate Drugs 0.000 claims description 2
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 28
- 239000001569 carbon dioxide Substances 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000002096 quantum dot Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 238000007146 photocatalysis Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
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- 238000013032 photocatalytic reaction Methods 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- FQXAVEOQCSTZSK-UHFFFAOYSA-N BrCCCC.BrCCCC Chemical compound BrCCCC.BrCCCC FQXAVEOQCSTZSK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100278332 Dictyostelium discoideum dotA gene Proteins 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
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- BXEMXLDMNMKWPV-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1 BXEMXLDMNMKWPV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 101150116173 ver-1 gene Proteins 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
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- 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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- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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Abstract
The invention relates to a pyridine quaternary ammonium salt and inorganic semiconductor hybrid system for photocatalytic reduction of CO2Belonging to the technical field of photocatalytic carbon dioxide reduction. Adding a quaternary pyridinium salt, an inorganic semiconductor material and an electronic sacrificial body into a solvent, placing the solvent into a light-transmitting reaction vessel, and then sealing the reaction vessel; bubbling CO into a sealed reaction vessel2Under the action of illumination, the quaternary ammonium salt of pyridine is used as a cocatalyst, the inorganic semiconductor is used as a photocatalyst, and CO is used2Reducing to CO. The photocatalytic hybrid system has the characteristics of simple synthesis method of the cocatalyst, no metal, and excellent effect of reducing carbon dioxide in a water phase with the photocatalytic system constructed by the photocatalytic hybrid system and inorganic semiconductor materials.
Description
Technical Field
The invention relates to the technical field of photocatalytic carbon dioxide reduction, in particular to photocatalytic reduction of CO by a pyridine quaternary ammonium salt and inorganic semiconductor hybrid system2The use of (1).
Background
In the development process of human beings, the combustion of fossil fuels not only causes energy shortage, but also causes the constant increase of the concentration of carbon dioxide in the air in a greenhouse gas, which has great influence on the development and survival of the human society. Thus, CO is converted by means of photocatalysis2The conversion into the carbon-containing product with high added value is an effective way for the resource utilization of the carbon dioxide.
At present, photocatalytic reduction of CO2The method can be mainly divided into three types according to different materials used by a system: 1) Homogeneous systems based on molecules; 2) heterogeneous systems based on inorganic materials; 3) hybrid systems that combine molecules with inorganic materials. Inorganic semiconductors have been widely used in photocatalytic reduction of carbon dioxide systems due to their simple synthesis method, good photoresponse, adjustable band gap, high photostability, easy modification of surface ligands, and the like. The introduction of the cocatalyst into the inorganic semiconductor material system can effectively inhibit the recombination of electron-hole pairs and improve the photocatalytic efficiency. The cocatalyst can be metal complex, nano-particle, high molecular polymer and the like.
Usually in inorganic semiconductor photocatalystsAfter the introduction of the cocatalyst into the system, most of the photocatalytic reactions take place in the organic phase. For example, in a mixed solution of DMSO and water, CuInS is added2The combination of ZnS and iron metal complexes achieves high selectivity (over 99%) for the photocatalytic conversion of carbon dioxide to carbon monoxide, but the amount of carbon monoxide produced is very low (<1μmol)[J.Am.Chem.Soc.2017,139, 8931-8938]。
Metal-free pyridine structures, together with Pt, for electrocatalytic reduction of carbon dioxide ACS Catal. 2017,7,5410-5419]Proved to be useful for the reduction of carbon dioxide; in a recent article [ Stand-Alone CdS Nanocrystals for Photocatalytic CO2 Reduction with High Efficiency and selection, ACS Appl. Mater. interfaces,2021,13,22, 26573-26580-]In the method, pyridine is used as a ligand to be modified on the surface of CdS QDs and on CH3Efficient photocatalytic reduction of carbon dioxide is achieved in CN. However, photocatalytic reduction systems for carbon dioxide based on quaternary pyridinium salts and inorganic semiconductor materials have not been reported to date.
Therefore, it is needed to provide a method for photocatalytic reduction of carbon dioxide by using a quaternary pyridinium salt and an inorganic semiconductor hybrid system.
Disclosure of Invention
The invention solves the technical problems that most of the photocatalytic reduction carbon dioxide systems in the prior art are only suitable for organic phases and have low catalytic activity. The invention takes quaternary pyridinium salt as a cocatalyst and an inorganic semiconductor as a photocatalyst, and CO is reacted under the action of illumination2Reducing to CO. The catalyst of the photocatalytic system of the invention does not contain metal and can be used for photocatalytic reduction of CO2The efficiency is greatly improved.
According to the purpose of the invention, a quaternary pyridinium salt and inorganic semiconductor hybrid system for photocatalytic reduction of CO is provided2The application of (2), comprising the following steps:
(1) adding a quaternary pyridinium salt, an inorganic semiconductor material and an electronic sacrificial body into a solvent, placing the solvent into a light-transmitting reaction vessel, and then sealing the reaction vessel;
(2) blowing CO into the sealed reaction vessel in the step (1)2Under the action of light, the pyridine seasonTaking ammonium salt as a cocatalyst, taking an inorganic semiconductor material as a photocatalyst, and taking CO as a catalyst2Reducing to CO.
Preferably, the quaternized pyridinium salt is a quaternized product of poly (4-vinylpyridine) or a quaternized product of poly (2-vinylpyridine).
Preferably, the quaternization product of the poly (4-vinylpyridine) has the formula I:
wherein R is1Is an aliphatic carbon chain of C1-C16, X-Is halogen ion or acid radical ion.
Preferably, the quaternization product of the poly (2-vinylpyridine) has the formula II:
wherein R is2Is an aliphatic carbon chain of C1-C16, X-Is halogen ion or acid radical ion.
Preferably, the inorganic semiconductor material used as the photocatalyst is CdSe, CdS, ZnS, ZnSe, InP, a core-shell structure with CdSe as a core and CdS as a shell, a core-shell structure with CdSe as a core and ZnS as a shell, CdTe, CuInS2With CuInS2At least one of a core-shell structure with ZnS as a core and perovskite quantum dots;
preferably, the perovskite quantum dot is CsPbX3Wherein X is a halogen atom.
Preferably, the surface of the inorganic semiconductor material as a photocatalyst has a ligand;
preferably, the ligand is a sulfhydryl compound.
Preferably, the electron sacrificial body is at least one of triethylamine, triethanolamine, sodium ascorbate, ascorbic acid, sodium sulfide, sodium sulfite, isopropanol and methanol.
Preferably, the solvent is at least one of water, methanol, ethanol, acetonitrile, tetrahydrofuran, and N, N-dimethylformamide.
Preferably, the illumination is visible light having a wavelength of more than 380 nm.
Preferably, the concentration of the quaternary ammonium salt of pyridine is more than or equal to 1 × 10-7mol/L; the inorganic semiconductor has a concentration of 1 × 10 or more-7mol/L; the volume ratio of the solvent to the electronic sacrificial body is 4: (0.1-1);
preferably, the concentration of the quaternary ammonium salt of pyridine is 1 × 10-7～1×10-3mol/L; the concentration of the inorganic semiconductor is 1 × 10-7～1×10-3mol/L。
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) the pyridine quaternary ammonium salt in the photocatalytic system is simple to prepare, the raw materials are cheap and do not contain metals.
(2) The photocatalytic system of the invention carries out photocatalytic reduction on CO2The efficiency is greatly improved and can reach 40.19 mmol/g-1·h-1(relative to the amount of the added quaternary ammonium pyridine salt cocatalyst), and the system composition is simple, and the reaction conditions are mild.
(3) In the pyridine quaternary ammonium salt in the photocatalytic system, quaternized pyridine can be combined with inorganic semiconductor surface ligands, such as negatively charged ligands for electrostatic assembly, and the carbon dioxide can be subjected to photocatalytic reduction together with the inorganic semiconductor.
(4) The photocatalytic system of the invention not only can carry out photocatalytic reduction on carbon dioxide in an organic solvent, but also has excellent photocatalytic performance in an aqueous solution.
(5) The photocatalysis system of the invention has universality and can be used for CdSe, CdS, ZnS, ZnSe, CdSe/ZnS, CdSe/CdS, CdTe, InP and CuInS2、CuInS2/ZnS or perovskite quantum dotAs a photocatalyst.
Drawings
FIG. 1 is a nuclear magnetic spectrum of P4VP and PB4 of the present invention.
FIG. 2 is a UV and luminescence spectrum of CdSe QDs according to the present invention.
FIG. 3 is a TEM image of CdSe QDs in the present invention.
FIG. 4 is a schematic diagram showing the amount of CO produced in example 1 of the present invention.
FIG. 5 is a schematic diagram showing the amounts of CO produced in examples 2 to 5 of the present invention.
FIG. 6 is a schematic diagram showing the amounts of CO produced in examples 6 to 9 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The quaternary ammonium pyridine salt and inorganic semiconductor hybrid system is used for photocatalytic reduction of CO2The application of (2), comprising the following steps:
(1) adding a quaternary pyridinium salt, an inorganic semiconductor and an electronic sacrificial body into a solvent, placing the solvent into a light-transmitting reaction vessel, and then sealing the reaction vessel;
(2) blowing CO into the sealed reaction vessel in the step (1)2Under the action of illumination, the quaternary ammonium salt of pyridine is used as a cocatalyst, the inorganic semiconductor is used as a photocatalyst, and CO is used2Reducing to CO.
In some embodiments, the inorganic semiconductor is a compound of a group IIB element and a group VIA element, a compound of a group IIIA element and a group VA element, a compound of a group IB element, a group IIIA element and a group VIA element, or a perovskite-type quantum dot;
in some embodiments, the inorganic semiconductor material is a quantum dot, nanorod, nanowire or nanosheet.
The quaternary pyridinium salts of the present invention are characterized by Nuclear Magnetic Resonance (NMR); the inorganic semiconductor is characterized by a high-resolution transmission electron microscope (HRTEM), an ultraviolet visible absorption spectrum (UV) and a fluorescence spectrum (PL); the carbon dioxide reduction product was determined by gas chromatography.
Reference synthesis for preparation of Quaternary pyridinium salt in the present invention [ Journal of Membrane Science, 2010,347, 183-192-]Taking the synthesis of poly (4-vinylpyridine) -bromobutane (PB4) as an example, the structure is as follows:
the method comprises the following steps:
300mg of poly (4-vinylpyridine) (P4VP) was weighed into a 50mL flask, 10mL of ethanol solution was added, 918.7. mu.L of 1-bromon-butane (1-Bromobutane) was added, the temperature was raised to 85 ℃ and the mixture was refluxed for 1 to 24 hours. The successful preparation of poly (4-vinylpyridine) quaternary ammonium salt and the degree of quaternization of poly (4-vinylpyridine) were determined by NMR spectroscopy, as shown in FIG. 1, it can be seen from FIG. 1 that poly (4-vinylpyridine) quaternary ammonium salt (PB4) was successfully prepared and all of the pyridine nitrogens therein were quaternized.
In the invention, the synthesis of inorganic semiconductor preparation references [ Angew. chem. int. Ed.,2013, 52, 8134-8138 ], taking the synthesis of CdSe quantum dots as an example, comprises the following steps:
(1) synthesis of Na2SeSO3: weighing 189mg Na2SO3Adding 100 mL of ultrapure water and 40mg of selenium powder into a 250mL flask, introducing nitrogen for 30 minutes, heating and refluxing at 130 ℃ until the selenium powder is completely dissolved to obtain clear Na2SeSO3The solution is stored under inert atmosphere and protected from light.
(2) Synthesizing aqueous-phase MPA-CdSe quantum dots: 46mg of CdCl were weighed out2·2.5H2O (0.2mmol) was added to a 500mL round bottom flask, 190mL deionized water and 26. mu.L mercaptopropionic acid (MPA, 0.3mmol) were added, the pH was adjusted to 11 with 1M NaOH solution, and after nitrogen blanket, 10mL Na was added2SeSO3The solution (0.05mmol) was reacted at 130 ℃ for 3 h. After the reaction, the solution is concentrated, added with excessive isopropanol for precipitation and washingWashing, centrifuging and drying to obtain yellow solid. HRTEM, ultraviolet visible absorption spectrum and luminescence spectrum are used for characterizing the synthesized MPA-CdSe quantum dots, as shown in figures 2 and 3, it can be known from figure 2 that the CdSe quantum dots have good visible light response, and it can be known from figure 3 that the size of the CdSe quantum dots is about 1.8 nm.
Example 1
A pyridine quaternary ammonium salt and inorganic semiconductor combined photocatalysis system, which comprises PB4, MPA-CdSe and H2O, IPA (isopropyl alcohol) and a blue LED (λ 450nm) lamp.
The photocatalytic system is used for photocatalytic reduction of carbon dioxide, and specifically comprises the following steps:
the prepared MPA-CdSe quantum dots (0.5mg, 5 × 10)-6mol/L)、PB4(0.5mg、4 ×10-4mol/L)、IPA(1.0mL)、H2O (4.0mL) was added to a sealed photoreaction tube and high purity CO was bubbled230 min, 500. mu.L CH injection4As an internal standard, the CO generation rate was calculated to be 30.67 mmol/g by gas chromatography detection using a blue LED (λ 450nm) lamp for 12h of irradiation-1·h-1(ii) a As shown in fig. 4, it is understood from fig. 4 that the carbon dioxide reduction activity is greatly improved as compared with the system without the promoter.
Examples 2 to 5
A quaternary ammonium pyridine salt and an inorganic semiconductor combined photocatalytic system, which is used for photocatalytic reduction of carbon dioxide in the same way as in example 1, and the steps are the same as in example 1, except that the dosage of a PB4 catalyst in the catalytic system is changed, and the specific formula is shown in the following table 1.
TABLE 1 CO Generation rates for different PB4 additions
As can be seen from example 1, Table 1 and FIG. 5, the CO production rate increased with the increase in the amount of the cocatalyst PB4, increased and then decreased, and the CO production rate reached the maximum at a PB4 addition amount of 0.2 mg. The amount of CO generated is gradually increased along with the increase of the PB4 added amount and the increase of the photocatalytic active sites of the hybrid system, but the CO generation rate is reduced due to the excessive PB4 added amount.
Examples 6 to 9
A quaternized pyridinium pyridine salt and an inorganic semiconductor hybrid photocatalytic system are used for photocatalytic reduction of carbon dioxide in the same way as in example 1, and the steps are the same as in example 1, except that the concentration of CdSe in the photocatalytic system is changed, as shown in the following table 2.
TABLE 2 photocatalytic CO generation rates at different CdSe concentrations
From example 1 and table 2 it can be seen that: with the difference of the addition amount of the inorganic semiconductor photocatalyst CdSe, the CO generation rate has larger difference. As shown in fig. 6, it can be seen from fig. 6 that the CO generation rate decreases with the increase of the CdSe addition amount, mainly because the CdSe concentration is too high, which has a filter effect and is not favorable for the absorption of light and the progress of the photocatalytic reaction.
Examples 10 and 11
A quaternary pyridinium salt and inorganic semiconductor combined photocatalytic system is used for photocatalytic reduction of carbon dioxide as in example 1, and the procedure is the same as in example 1, except that the quaternary pyridinium salt added with the cocatalyst is changed into PB6 (prepared by quaternization reaction of P4VP and bromohexane) and PB8 (prepared by quaternization reaction of P4VP and bromooctane), which is specifically shown in the following table 3.
TABLE 3 photocatalytic CO generation rates under different pyridinium Quaternary ammonium salts
From example 1 and table 3, it is seen that under the same experimental conditions, PB4 has the highest photocatalytic CO production rate compared to PB6 and PB8, indicating that quaternary ammonium salts obtained by quaternizing P4VP with n-butyl bromide having a chain length of 4 are the best catalytic effects.
Examples 12 to 15
A quaternary pyridinium salt and inorganic semiconductor combined photocatalytic system, which is used for photocatalytic reduction of carbon dioxide as in example 1, except that the inorganic semiconductor and the electron sacrificial body added are changed as shown in table 4 below, as in example 1.
TABLE 4 photocatalytic CO generation rates for different inorganic semiconductors and electronic sacrificial bodies
From example 1 and table 4, it is clear that when different inorganic semiconductors are added as photocatalysts, although some CO is generated, the CO generation rate is significantly reduced, indicating that CdSe is the most suitable photocatalyst in the aqueous phase of the system.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. Application of pyridine quaternary ammonium salt and inorganic semiconductor hybrid system in photocatalytic reduction of CO2Characterized by comprising the following steps:
(1) adding a quaternary pyridinium salt, an inorganic semiconductor material and an electronic sacrificial body into a solvent, placing the solvent into a light-transmitting reaction vessel, and then sealing the reaction vessel;
the quaternary ammonium salt of pyridine is a quaternization product of poly (4-vinylpyridine) or a quaternization product of poly (2-vinylpyridine);
the inorganic semiconductor material is CdSe, CdS, CdSe/CdS, CuInS2/ZnAt least one of S and CdTe; the CdSe/CdS is core-shell structure with CdSe as core and CdS as shell, and the CuInS is2the/ZnS is CuInS2A core-shell structure with ZnS as a shell as a core;
the electronic sacrificial body is at least one of triethanolamine, sodium ascorbate, ascorbic acid and isopropanol;
(2) blowing CO into the sealed reaction vessel in the step (1)2Under the action of illumination, the quaternary ammonium pyridine salt is used as a cocatalyst, an inorganic semiconductor material is used as a photocatalyst, and CO is used2Reducing to CO.
2. The use according to claim 1, wherein the quaternization product of poly (4-vinylpyridine) has the formula I:
wherein R is1Is an aliphatic carbon chain of C1-C16, X-Is halogen ion or acid radical ion.
3. The use according to claim 1, wherein the quaternised product of poly (2-vinylpyridine) has the formula ii:
wherein R is2Is an aliphatic carbon chain of C1-C16, X-Is halogen ion or acid radical ion.
4. Use according to claim 1, wherein the inorganic semiconductor material surface acting as a photocatalyst has ligands.
5. The use of claim 4, wherein said ligand is a sulfhydryl compound.
6. The use of claim 1, wherein the solvent is at least one of water, methanol, ethanol, acetonitrile, tetrahydrofuran, and N, N-dimethylformamide.
7. Use according to claim 1, wherein the illumination is of visible light having a wavelength of more than 380 nm.
8. The use according to claim 1, wherein the concentration of said quaternary pyridinium salt is 1 x 10 or more-7mol/L; the inorganic semiconductor has a concentration of 1 × 10 or more-7mol/L; the volume ratio of the solvent to the electronic sacrificial body is 4: (0.1-1).
9. The use of claim 8, wherein the concentration of said quaternary pyridinium salt is 1 x 10-7～1×10- 3mol/L; the concentration of the inorganic semiconductor is 1 × 10-7～1×10-3mol/L。
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