CN115414965A - Preparation method and application of terpyridyl supramolecular photocatalyst - Google Patents
Preparation method and application of terpyridyl supramolecular photocatalyst Download PDFInfo
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- CN115414965A CN115414965A CN202211158025.5A CN202211158025A CN115414965A CN 115414965 A CN115414965 A CN 115414965A CN 202211158025 A CN202211158025 A CN 202211158025A CN 115414965 A CN115414965 A CN 115414965A
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- terpyridyl
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- terpyridine
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- 230000009467 reduction Effects 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 125000001246 bromo group Chemical group Br* 0.000 claims abstract description 20
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 5
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- KMWSAMYGITWUFW-UHFFFAOYSA-N BrC=1C(=NC=CC=1)C1=NC=CC=C1C1=NC=CC=C1 Chemical compound BrC=1C(=NC=CC=1)C1=NC=CC=C1C1=NC=CC=C1 KMWSAMYGITWUFW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004817 gas chromatography Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000003504 photosensitizing agent Substances 0.000 abstract description 9
- 230000005684 electric field Effects 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 4
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- -1 cobalt oxime Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004799 bromophenyl group Chemical group 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229940038879 chelated zinc Drugs 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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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- 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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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
A preparation method of a terpyridyl supramolecular photocatalyst, wherein the terpyridyl supramolecule is a terpyridyl conjugated supramolecule containing a bromo group, comprises the following steps: step a, preparing 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecules by a Krohnke intermediate cyclization method, then adding the conjugated molecules into a benign organic solvent, and stirring and dissolving at room temperature to obtain a transparent solution; step b, dripping poor solvent water into the 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine organic solution in the step a to obtain suspension, stirring, standing, and gradually precipitating white precipitatePrecipitating; and c, after obtaining a bromine-based terpyridine conjugated supermolecule sample, characterizing the sample, and judging the structural characteristics of the sample. The invention adopts a dissolving-precipitating process to prepare the terpyridyl supramolecular photocatalyst with high crystallinity, strong built-in electric field and more negative reduction potential and single component, and the terpyridyl assembly is both a catalyst and a photosensitizer and can efficiently carry out photocatalytic reduction on CO 2 And becomes a renewable fuel.
Description
Technical Field
The invention relates to a preparation method of a photocatalyst, in particular to a preparation method and application of a terpyridyl supramolecular photocatalyst.
Background
At present, the energy crisis problem is deeply sunk all over the world. Semiconductor photocatalyst for generating CO by using solar energy 2 Photocatalytic decomposition into CO and CH 4 The technology of waiting for fuel provides an ideal scheme for solving the problem of energy shortage. The key to the smooth implementation of the technical scheme is to develop the photocatalyst which is efficient, stable, environment-friendly and rich in raw material sources. In recent years, terpyridyl compounds have the characteristics of large pi conjugated structure, structural diversity, controllability and excellent electron transport capacity, and have attracted wide attention as building units of photocatalytic materials.
However, in the aspect of photocatalysis, terpyridine mainly serves as a photosensitizer, and a light capture-carrier transmission-catalysis system is formed by chelating metal ions and then combining the metal ions with a catalyst. For example, garry s.hanan was prepared with [ Ru (tollyltpy) (Bipytpy) (PF) 6 ) 2 The system which is a photosensitizer, takes a cobalt oxime complex as a catalyst and takes triethanolamine as a sacrificial agent can efficiently carry out photocatalytic reduction on H 2 O hydrogen production (Inorganic Chemistry,2019,58, 9127-9134). Jianzhuang Jiang et al [ Ru (bpy) 3 ]Cl 2 ·6H 2 The system consisting of O and COF-367-Co NS nanosheets can realize stable visible light catalytic reduction of CO 2 The reduced product was mainly CO- (78%) (Journal of American Chemical Society,2019,141, 17431-17440) in accordance with the above bracket format. The following problems exist in the above systems: firstly, the existing photocatalytic system needs two parts of materials, namely a catalyst and a photosensitizer, and the synthesis process is complex; secondly, the interface contact between the photosensitive unit and the catalytic unit is regulated to promote the transfer of the photo-generated electrons from the photosensitizer to the catalyst so as to drive the reaction to proceed, and the regulation and control technology is rigorous in requirement and is not easy to control.
Disclosure of Invention
The invention provides a preparation method of a terpyridyl supramolecular photocatalyst and application thereof for overcoming the defects of the prior art, the terpyridyl supramolecular photocatalyst with single component and high crystallinity, strong built-in electric field and more negative reduction potential is prepared by adopting a dissolving-precipitating process, and a terpyridyl assembly is both a catalyst and a photosensitizer and can efficiently carry out photocatalytic reduction on CO 2 And becomes a renewable fuel.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of a terpyridyl supramolecular photocatalyst, wherein the terpyridyl supramolecule is a terpyridyl conjugated supramolecule containing a bromine group, comprises the following steps:
step a, preparing 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecules by a Krohnke intermediate cyclization method, then adding the conjugated molecules into a benign organic solvent, and stirring and dissolving at room temperature to obtain a transparent solution;
step b, dripping poor solvent water into the 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine organic solution in the step a to obtain a suspension, stirring, standing, and gradually separating out a white precipitate;
and c, after obtaining a bromine-based terpyridine conjugated supermolecule sample, characterizing the sample, and judging the structural characteristics of the sample.
In the step a, the structural formula of the 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecule prepared by the Krohnke intermediate ring-forming method is shown as the following formula (I):
in the step a, the Krohnke intermediate cyclization method is used for preparing 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecules, and the steps are as follows: p-bromobenzaldehyde and 2-acetylpyridine are used as raw materials, and the molar ratio of the p-bromobenzaldehyde to the 2-acetylpyridine is 1:2, adding the two raw materials into 50-100mL of ethanol, stirring, sequentially and slowly adding 80-100mL of 25-28% ammonia water and 3.4-4.0g of KOH, stirring at room temperature for reaction, heating to 80-90 ℃, stirring for reaction for 3-10h, filtering, and washing with ethanol to obtain 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecules.
In the preparation method of the terpyridyl supramolecular photocatalyst, in the step a, the benign organic solvent is DMF, ethylene glycol monomethyl ether or THF.
In the step a, the mass-to-volume ratio of the 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecule to the benign organic solvent is 500mg: (7-14) mL.
In the step b, the mass-to-volume ratio of the 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecule to the poor solvent water is 500mg: (63-126) mL.
In the step b, the suspension is continuously stirred for 3-10 hours, and the standing time is 2 hours.
Application of terpyridyl supramolecular photocatalyst, and CO photocatalytic reduction by using prepared terpyridyl supramolecular photocatalyst 2 The photocatalysis step is as follows: 20mg of bromo-terpyridine conjugated supramolecules were dispersed in petri dishes, to which 2mL of H was added 2 O; putting the watch glass into a reaction kettleVacuumizing to remove air, and introducing CO 2 Vacuumizing and charging CO 2 The process of (2) is repeated three times; performing xenon lamp illumination reaction for 6h, sampling every 1h, and taking out reduction products CO and CH in the sample through gas chromatography 4 The yield of (2).
The beneficial effects of the invention are:
(1) The invention prepares the terpyridyl supramolecular semiconductor photocatalyst by a dissolution-precipitation method for the first time, and the terpyridyl supramolecular semiconductor photocatalyst which is single in structural orientation, high in crystallinity and provided with a strong built-in electric field is assembled by pi-pi stacking interaction.
(2) The terpyridine compound is usually used as a photosensitizer, and can promote photoproduction electrons to be transferred from the photosensitizer to a catalyst to drive reaction to proceed after the terpyridine compound reacts with a photocatalyst, and the regulation and control technology is rigorous in requirement and is not easy to control; the invention provides a photocatalyst taking single-component terpyridine as a main body, and the system does not relate to the harsh regulation and control of the transfer and the regulation and control of photo-generated electrons between a photosensitizer and a catalyst; in addition, the single component has simple preparation steps, easily regulated structure and low modification cost. In addition, the invention provides a theoretical basis for enriching the organic supermolecule variety.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine white solid;
FIG. 2 is an optical picture of 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine dissolved in DMF and after dropping water to its DMF solution;
FIG. 3 is an X-ray diffraction pattern of a Tpy-Br-1 photocatalyst;
FIG. 4 is an optical microscope photograph of a Tpy-Br-1 photocatalyst;
FIG. 5 is a scanning electron microscope image of a Tpy-Br-1 photocatalyst;
FIG. 6 shows Tpy-Br-1 and g-C under different experimental conditions 3 N 4 Photocatalytic reduction of CO 2 A plot of rate of formation of CO;
FIG. 7 is an optical microscope photograph of a Tpy-Br-2 photocatalyst;
FIG. 8 is a scanning electron microscope image of a Tpy-Br-2 photocatalyst;
FIG. 9 shows the photocatalytic reduction of CO by Tpy-Br-2 2 A plot of rate of formation of CO;
FIG. 10 is an optical microscope photograph of a Tpy-Br-3 photocatalyst;
FIG. 11 is a scanning electron micrograph of a Tpy-Br-3 photocatalyst;
FIG. 12 shows the photocatalytic reduction of CO by Tpy-Br-3 2 A rate map to CO;
FIG. 13 is an optical microscope photograph of a Tpy-Br-4 photocatalyst;
FIG. 14 is a scanning electron microscope image of a Tpy-Br-4 photocatalyst;
FIG. 15 shows the photocatalytic reduction of CO by Tpy-Br-4 2 A plot of rate of formation of CO;
FIG. 16 is an optical microscope photograph of a Zn-Tpy-Br photocatalyst;
FIG. 17 is a scanning electron microscope image of a Zn-Tpy-Br photocatalyst;
FIG. 18 shows the photocatalytic reduction of CO by Zn-Tpy-Br 2 Into a graph of the rate of CO.
Detailed Description
The invention firstly synthesizes bromine-containing terpyridyl molecule (4 '- (4-bromophenyl) -2,2':6', 2' -terpyridyl conjugate molecule) by a simple Krohnke intermediate cyclization method, and then prepares the terpyridyl supramolecule which is a self-assembled semiconductor photocatalyst by a dissolution-precipitation method. The method is characterized in that a terpyridyl molecule containing a bromine group is dissolved in a benign organic solvent (DMF, ethylene glycol monomethyl ether or THF), the terpyridyl molecule containing the bromine group in the state can move freely, then poor solvent (water) is dripped into the terpyridyl molecule containing the bromine group, and the terpyridyl molecule containing the bromine group is not in the free state any more and is forced to be aggregated into pi aggregates along with the diffusion of water molecules into the organic solvent. The driving force for generating the pi aggregate is pi-pi accumulation effect between pyridine conjugated rings, terpyridine molecules are orderly arranged under the action of the force and have certain compactness, and pi electrons on the pyridine rings are expanded into the pyridine rings of adjacent molecules by the characteristics, namely the pi electrons can be subjected to trans-ring transmission and flow along the orderly arranged conjugated molecules, so that the terpyridine molecules show certain compactnessConductive, having the properties of semiconductors. The substituent-Br can influence the dipole property of molecules, so that the built-in electric field of the catalyst is regulated and controlled, and the effective separation of photoproduction electrons and holes is promoted. In summary, the terpyridyl photocatalyst constructed by the simple dissolution-precipitation method provided by the patent has high crystallinity, strong built-in electric field and more negative reduction potential, and the advantages of the terpyridyl photocatalyst can efficiently carry out photocatalytic reduction on CO 2 Becomes renewable fuel and has great application value and social significance.
The dosage of benign organic solvent and poor solvent and the stirring time have certain influence on the terpyridine assembling structure. The self-assembly process of the terpyridyl supramolecule is characterized in that terpyridyl molecules are directionally assembled and nucleated through pi-pi accumulation and the action between halogen-Br and benzene rings, and then more molecules grow along the nuclear direction and grow again to form a rod-shaped structure. If the concentration of benign solvent is too low and the stirring time is too short, there are not enough molecules and time to encourage the assembly to continue growing into rod-like structures and the assembly process may only stay in the nucleation phase. If the amount of the poor solvent water is too small, the terpyridyl molecule is more easily dissolved in the organic solvent according to the principle of similarity and intermiscibility, and no assembly action occurs. Therefore, the best conditions for obtaining a stable terpyridine rod-like structure in the invention are as follows: the mass volume ratio of the terpyridyl compound to the benign organic solvent and the poor solvent water is respectively 500mg: (7-14) mL and 500mg: (63-126) mL, and the stirring time is 3-10h.
In the process of preparing the terpyridyl supramolecule by dissolving-precipitation, 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine is dissolved by benign organic solvent, and then surfactant can be added into poor solvent water, for example, surfactant Sodium Dodecyl Benzene Sulfonate (SDBS) is dissolved into water, and then the mixture is dripped into organic mixed solution to obtain white precipitated photocatalyst self-contained body. Or adding metal compound (such as Zn (NO) in precipitation stage 3 ) 2 ·6H 2 O), the prepared terpyridyl conjugated supramolecules chelate metal ions have a porous blocky structure formed by stacking lamellar structures, and are higher in conductivity and better in photocatalytic performance.
The present invention will be further described with reference to the following examples.
Example 1
1. Dissolving 4.0g of p-bromobenzaldehyde in 50mL of ethanol, adding 4.86mL of 2-acetylpyridine, stirring for 5min, then slowly dropwise adding 3.4g of KOH and 80mL of ammonia water in sequence, stirring for 2h at room temperature, heating to 80 ℃ for reaction for 24h, filtering to collect a white precipitate, and washing with ethanol for multiple times to remove unreacted reactants and impurities to obtain a white solid of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine. The white solid was subjected to nuclear magnetic test, and the obtained nuclear magnetic spectrum is shown in FIG. 1, from which it can be seen that the target product, 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine, was successfully synthesized. The structural information of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine is as follows:
1 H-NMR(500MHz,CDCl 3 )：δ＝8.73(d,J＝4.5Hz,2H, terpyridine 3,3”-H),8.70(s,2H,terpyridine 3',5'-H),8.67(d,J＝8.0Hz,2H, terpyridine 6,6”-H),7.88(t,J＝8.0Hz,2H, terpyridine 4,4”-H),7.78(d,J＝8.0Hz,2H, bromophenyl 2,2”-H),7.64(d,J＝7.5Hz,2H, bromophenyl 1,1”-H),8.36(t,J＝6.0Hz,2H, terpyridine 5,5”-H)。
2. weighing 500mg of the prepared 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine, adding 7mL of DMF, and completely dissolving the mixture after ultrasonic treatment or heating;
3. 63mL of H was slowly added dropwise 2 Adding O into a stirred organic solution of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine, and gradually separating out a white precipitate; stirring at normal temperature for 8h, standing for 2h, filtering to collect white solid, and vacuum drying for 10h to obtain 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine supermolecular self-assembled photocatalyst, which is recorded as Tpy-Br-1.
FIG. 2 is an optical image of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine molecules dissolved in DMF and then water added dropwise to a DMF solution of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine. As is evident from the figure, a white precipitate formed upon addition of water to a DMF solution of 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine.
4. The crystal structure and the appearance of the prepared Tpy-Br-1 photocatalyst are characterized and tested
FIG. 3 is an XRD pattern of a Tpy-Br-1 photocatalyst, and the pattern shows that the Tpy-Br-1 photocatalyst shows obvious diffraction peaks, which shows that the Tpy-Br-1 supermolecule self-assembly body shows excellent crystallization performance. The value of d for a diffraction angle of 21.6 corresponds to 0.41nm, which is typical for the spacing of a pi-pi stack. The excellent crystallization performance of the Tpy-Br-1 comes from the assembly of terpyridyl conjugated molecules into an ordered structure through strong pi-pi stacking interaction. The pi electrons of the terpyridine can perform trans-ring motion along a conjugated ordered structure, so that the Tpy-Br-1 shows certain conductivity, and the conductivity of the terpyridine is 4.95S cm through a four-probe test -1 Showing the property of a semiconductor having an electrical conductivity in the range of 10 -8 ～10 3 S cm -1 。
FIGS. 4 and 5 are optical microscope and scanning electron microscope spectra of a Tpy-Br-1 photocatalyst, respectively. As can be seen from the figure, the Tpy-Br-1 photocatalyst exhibited an ordered rod-like structure with a length of about 2 μm and a width of 200nm. The ordered rod-like assembly structure of the catalyst is formed by assembling the terpyridyl supramolecules through strong pi-pi stacking among molecules. The regular rod-shaped structure is beneficial to constructing a built-in electric field, so that a photon-generated carrier is transmitted and separated along the regular structure, and powerful guarantee is provided for the high-efficiency photocatalytic performance of the Tpy-Br-1 photocatalyst.
5. In this example, the Tpy-Br-1 photocatalyst catalyzes the reduction of CO 2 Activity test of (2)
FIG. 6 shows Tpy-Br-1 and g-C under different experimental conditions 3 N 4 Photocatalytic reduction of CO 2 To a graph of the rate of CO. As can be seen from the figure, the Tpy-Br-1 photocatalyst can carry out 6h photocatalytic reduction on CO under simulated sunlight 2 The rate of CO formation can reach 17.0 mu mol g -1 Is a common photocatalyst (g-C) 3 N 4 ) Reduction of CO 2 The rate of formation of CO is-2.1 times that of the reaction; little CO was produced under dark conditions, indicating that the CO produced was from a photocatalytic process; in addition, a small amount of CO was produced under Ar-filled conditions, probably because a small amount of CO remained in the reaction vessel 2 Which is reduced to CO under light; and a small amount without catalystCO production, probably due to the fact that water can act as a reducing agent to reduce CO under light irradiation 2 To CO (Nature Energy,2017,2, 17087-17096).
Example 2
1. The preparation process of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine is the same as that in example 1;
2. weighing 500mg of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine, adding 14mL of DMF, and completely dissolving the mixture after ultrasonic treatment or heating;
3. 126mL of H are slowly added dropwise 2 Adding O into the stirred organic solution of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine to gradually separate out white precipitate; stirring at normal temperature for 8h, standing for 2h, filtering to collect a white solid, and vacuum drying for 10h to obtain the photocatalyst of self-assembly of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine molecules, which is recorded as Tpy-Br-2.
4. Morphology map of Tpy-Br-2 photocatalyst in this example
FIGS. 7 and 8 are optical microscope and scanning electron microscope spectra of a Tpy-Br-2 photocatalyst, respectively. As can be seen from the figure, the assembled Tpy-Br-2 photocatalyst still exhibited an ordered rod-like structure with a length of about 4 μm and a width of 200nm. The conductivity was 3.98S cm -1 And the properties of the semiconductor are shown.
5. In this example, the Tpy-Br-2 photocatalyst catalyzes the reduction of CO 2 Activity test of (2)
FIG. 9 shows the photocatalytic reduction of CO by Tpy-Br-2 2 To a graph of the rate of CO. As can be seen from the figure, under simulated sunlight, the Tpy-Br-2 can be used for 6h to carry out photocatalytic reduction on CO 2 The rate of formation of CO was 6.6. Mu. Mol g -1 。
Example 3
1. The preparation process of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine is the same as that of example 1;
2. weighing 500mg of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine, adding 14mL of ethylene glycol monomethyl ether, and completely dissolving the ethylene glycol methyl ether by ultrasonic treatment or heating;
3. 63mL of H was slowly added dropwise 2 O into a stirred organic solution of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine, and white precipitateGradually separating out; stirring at normal temperature for 8h, standing for 2h, filtering to collect a white solid, and vacuum drying for 10h to obtain the 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine molecular self-assembled photocatalyst, which is denoted as Tpy-Br-3.
4. Morphology map of Tpy-Br-3 photocatalyst in this example
FIGS. 10 and 11 are optical microscope and scanning electron microscope spectra of a Tpy-Br-3 photocatalyst, respectively. As can be seen from the figure, the length and width were 2 μm and 200nm, respectively, after changing the solvent. Still exhibit an ordered rod-like structure and have a conductivity of 4.82S cm -1 And has the properties of a semiconductor.
5. In this example, the Tpy-Br-3 photocatalyst catalyzes the reduction of CO 2 Activity test of (2)
FIG. 12 shows the photocatalytic reduction of CO by Tpy-Br-3 2 To a graph of the rate of CO. As can be seen from the figure, under simulated sunlight, the Tpy-Br-3 photocatalyst reduces CO in 6h photocatalysis 2 The rate of formation of CO was 14.7. Mu. Mol g -1 。
Example 4
Surfactant addition (SDBS): preparation of Tp y-Br-4 photocatalyst
1. The preparation process of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine white solid is the same as that of example 1;
2. weighing 500mg of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine, adding 7mL of ethylene glycol monomethyl ether, and completely dissolving the ethylene glycol monomethyl ether by ultrasonic treatment or heating;
3. 488mg of Sodium Dodecyl Benzene Sulfonate (SDBS) is weighed and dissolved in 126mL of water, 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine solution is slowly dripped into the stirred SDBS solution, and white precipitate is gradually separated out; stirring at normal temperature for 8h, standing for 2h, filtering and collecting a white solid, washing with water for 2 times to remove SDBS on the surface of a sample, and drying in vacuum for 10h to obtain the photocatalyst of self-assembly of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine molecules, which is recorded as Tpy-Br-4.
4. The morphology of the Tpy-Br-4 photocatalyst in this example
FIGS. 13 and 14 are optical microscope and scanning electron of a Tpy-Br-4 photocatalyst, respectivelySub-microscopic pattern. As can be seen from the figure, the Tpy-Br-4 photocatalyst still shows a rod-shaped structure with ordered arrangement after the surfactant is added, the length and the width of the rod-shaped structure are respectively 10 mu m and 200nm, but compared with the former three examples, the rod-shaped structure assembled by the Tpy-Br-4 photocatalyst is more uniform, because in the surfactant-assisted assembly process, hydrophilic heads are connected together in an aqueous solution to form a spherical shell, hydrophobic tails are gathered at a place far away from the solution to form a cavity, and terpyridine is more easily retained in the cavity of a micelle through hydrophobic and pi-pi actions between an SDBS alkyl chain and a benzene ring. The ordering of the micelle cavities causes the terpyridine assemblies to show a morphology with uniform structural size. In addition, tpy-Br-4 has the property of a semiconductor, the conductivity of which is 4.63S cm -1 。
5. In the embodiment, the Tpy-Br-4 photocatalyst is used for catalyzing and reducing CO 2 Activity test of (2)
FIG. 15 shows the photocatalytic reduction of CO by Tpy-Br-4 2 Into a graph of the rate of CO. As can be seen from the figure, under simulated sunlight, after the surfactant is added, the Tpy-Br-4 photocatalyst reduces CO for 6h 2 The rate of formation of CO was 16.9. Mu. Mol g -1 。
Example 5
Chelating metal ions: preparation of Zn-Tpy-Br conjugated supermolecule photocatalyst
1. The preparation process of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine white solid is the same as that of example 1;
2. 200mg of 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine was dissolved in 6.67mL of DMF;
3.4 '- (4-bromophenyl) -2,2':6', 2' -terpyridine and Zn (NO) in molar ratio 3 ) 2 ·6H 2 O is 2, 76.63mg of Zn (NO) 3 ) 2 ·6H 2 O, then dissolved in 4.66mL of methanol, zn (NO) was added 3 ) 2 ·6H 2 Slowly and dropwise adding the O solution into a 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine solution; stirring at normal temperature for 8h, performing rotary evaporation to obtain white precipitate, washing the precipitate with hot dichloromethane for 2 times, removing unreacted reactant, vacuum drying overnight to obtain chelated zinc ion 4' - (4-bromobenzeneGroup) -2,2' -terpyridyl supramolecular photocatalyst, noted as Zn-Tpy-Br.
4. Morphology map of Zn-Tpy-Br photocatalyst in the example
FIGS. 16 and 17 are optical microscope and scanning electron microscope spectra of Zn-Tpy-Br photocatalyst, respectively. As can be seen from the figure, and Zn 2+ After chelation, 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine molecules are assembled into a lamellar structure, and the lamellar structure is piled up into a porous blocky structure. The Zn-Tpy-Br photocatalyst has the property of a semiconductor, and the conductivity of the photocatalyst is 9.84S cm -1 。
5. In the embodiment, the Zn-Tpy-Br photocatalyst is used for catalyzing and reducing CO 2 Activity test of
FIG. 18 shows the photocatalytic reduction of CO by Zn-Tpy-Br 2 The rate of formation of CO is shown, and Zn chelation can be seen in the graph under simulated sunlight 2+ Then, the Zn-Tpy-Br photocatalyst reduces CO for 5h 2 The rate of forming CO can reach 86.9 mu mol g -1 Is 5.4 times that of the Tpy-Br-1 photocatalyst.
Claims (8)
1. A preparation method of a terpyridyl supramolecular photocatalyst is characterized by comprising the following steps: the terpyridyl supramolecule is a terpyridyl conjugated supramolecule containing a bromo group, and the preparation method comprises the following steps:
step a, preparing 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecules by a Krohnke intermediate cyclization method, then adding the conjugated molecules into a benign organic solvent, and stirring and dissolving at room temperature to obtain a transparent solution;
b, dripping poor solvent water into the 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine organic solution in the step a to obtain suspension, stirring, standing, and gradually separating out white precipitate;
and c, after obtaining a bromine-based terpyridine conjugated supermolecule sample, characterizing the sample, and judging the structural characteristics of the sample.
2. The method for preparing a terpyridyl supramolecular photocatalyst according to claim 1, characterized in that: in the step a, the structural formula of the 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecule prepared by the Krohnke intermediate ring-forming method is shown as the following formula (I):
3. the method for preparing a terpyridyl supramolecular photocatalyst according to claim 2, characterized in that: in the step a, the Krohnke intermediate cyclization method is used for preparing a 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecule, and the steps are as follows: p-bromobenzaldehyde and 2-acetylpyridine are used as raw materials, and the molar ratio of the p-bromobenzaldehyde to the 2-acetylpyridine is 1:2, adding the two raw materials into 50-100mL of ethanol, stirring, sequentially and slowly adding 80-100mL of 25-28% ammonia water and 3.4-4.0g of KOH, stirring at room temperature for reaction, heating to 80-90 ℃, stirring for reaction for 3-10h, filtering, and washing with ethanol to obtain the 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecule.
4. The method of preparing a terpyridyl supramolecular photocatalyst as claimed in claim 3, wherein: in the step a, the benign organic solvent is DMF, ethylene glycol monomethyl ether or THF.
5. The method of preparing a terpyridyl supramolecular photocatalyst as claimed in claim 4, wherein: in the step a, the mass-volume ratio of the 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecule to the benign organic solvent is 500mg: (7-14) mL.
6. The method of preparing a terpyridyl supramolecular photocatalyst as claimed in claim 5, wherein: in the step b, the mass-volume ratio of the 4'- (4-bromophenyl) -2,2':6', 2' -terpyridine conjugated molecule to the poor solvent water is 500mg: (63-126) mL.
7. The method of claim 6, wherein the method comprises the steps of: in the step b, the continuous stirring time of the suspension is 3-10h, and the standing time is 2h.
8. The application of the terpyridyl supramolecular photocatalyst is characterized in that: photocatalytic reduction of CO using a terpyridyl supramolecular photocatalyst prepared according to any one of claims 1 to 7 2 The photocatalysis step is as follows: 20mg of bromoterpyridine conjugated supramolecules were dispersed in petri dishes, to which 2mL of H was added 2 O; putting the watch glass into a reaction kettle, vacuumizing the reaction kettle to remove air, and filling CO 2 Vacuumizing and charging CO 2 The process of (2) is repeated three times; performing xenon lamp illumination reaction for 6h, sampling every 1h, and taking out reduction products CO and CH in the sample by gas chromatography 4 The yield of (2).
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| JP2013126653A (en) * | 2011-11-17 | 2013-06-27 | Sumitomo Chemical Co Ltd | Optically functional material, oxidation-reduction photocatalyst, water decomposition photocatalyst, metal complex, and method for production of the metal complex |
| CN111995761A (en) * | 2020-08-18 | 2020-11-27 | 中南大学 | Tripyridyl transition metal organic polymer, preparation method thereof and application thereof in carbon dioxide photocatalytic reduction |
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| JP2022039938A (en) * | 2020-08-28 | 2022-03-10 | 東ソー株式会社 | Core-shell powder, and method for producing the same |
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| JP2013126653A (en) * | 2011-11-17 | 2013-06-27 | Sumitomo Chemical Co Ltd | Optically functional material, oxidation-reduction photocatalyst, water decomposition photocatalyst, metal complex, and method for production of the metal complex |
| CN111995761A (en) * | 2020-08-18 | 2020-11-27 | 中南大学 | Tripyridyl transition metal organic polymer, preparation method thereof and application thereof in carbon dioxide photocatalytic reduction |
| JP2022039938A (en) * | 2020-08-28 | 2022-03-10 | 東ソー株式会社 | Core-shell powder, and method for producing the same |
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