CN115414965B - Preparation method and application of terpyridyl supermolecular photocatalyst - Google Patents
Preparation method and application of terpyridyl supermolecular photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 76
- 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 45
- 230000001699 photocatalysis Effects 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000009467 reduction Effects 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 125000001246 bromo group Chemical group Br* 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000007146 photocatalysis Methods 0.000 claims abstract description 8
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 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 abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 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
- 238000005406 washing Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 239000002994 raw material 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
- 238000005286 illumination Methods 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 2
- 238000011068 loading method 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 7
- 238000001556 precipitation Methods 0.000 abstract description 6
- 230000005684 electric field Effects 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 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 description 14
- 239000004065 semiconductor Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000000523 sample Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 238000000879 optical micrograph Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000001291 vacuum drying 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
- 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
- -1 cobalt oxime Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004799 bromophenyl group Chemical group 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000002135 nanosheet 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
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005160 1H 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
- 238000009825 accumulation Methods 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229940038879 chelated zinc Drugs 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003638 chemical reducing agent 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 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
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000126 substance Substances 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
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The preparation method of the terpyridyl supermolecule photocatalyst is characterized in that the terpyridyl supermolecule is a terpyridyl conjugated supermolecule containing bromo, and the preparation method comprises the following steps: step a, preparing 4'- (4-bromophenyl) -2,2':6',2' -terpyridine conjugated molecules through a Krohnke intermediate cyclization method, then adding the conjugated molecules into benign organic solvent, and stirring and dissolving the solution at room temperature to form transparent solution; step b, dropwise adding 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 precipitating a white precipitate; and c, after obtaining the bromo terpyridine conjugated supermolecule sample, characterizing the sample, and judging the structural characteristics of the sample. The invention prepares the terpyridyl supermolecular photocatalyst with single component, high crystallinity, strong built-in electric field and more negative reduction potential by adopting the dissolution-precipitation process, and the terpyridyl assembly is not only a catalyst but also a photosensitizer, thus being capable of efficiently reducing CO by photocatalysis 2 To form 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 supermolecule photocatalyst.
Background
Currently, the energy crisis problem is deeply trapped worldwide. Semiconductor photocatalyst uses solar energy to convert CO 2 Photocatalytic decomposition into CO and CH 4 The technology of waiting for fuel provides an ideal scheme for solving the energy shortage. The key of the smooth implementation of the technical scheme is to develop the photocatalyst which is efficient and stable, environment-friendly and rich in raw material source. In recent years, terpyridyl compounds have the characteristics of large pi-conjugated structure, structural diversity, controllability and excellent electron transport ability, and have attracted wide attention as building blocks for photocatalytic materials.
However, in terms of photocatalysis, terpyridyl acts primarily as a photosensitizer, which forms a photo-capture-carrier transport-catalytic system with the catalyst, primarily by chelating metal ions. For example, garry S.Hanan was prepared as [ Ru (Tolyltpy) (Bipytpy) (PF 6 ) 2 The system which is a photosensitizer, takes cobalt oxime complex as a catalyst and triethanolamine as a sacrificial agent can efficiently reduce H by photocatalysis 2 O produces hydrogen (Inorganic Chemistry,2019,58,9127-9134). Synthesis of Jianzhuang Jiang et al [ Ru (bpy) 3 ]Cl 2 ·6H 2 The O and COF-367-Co NS nanosheets and the system composed of the nanosheets can realize stable visible light catalytic reduction of CO 2 The reduction product was mainly CO- (78%) (Journal of American Chemical Society,2019,141,17431-17440) in accordance with the brackets format above. The following problems exist in the above system: firstly, the existing photocatalysis system needs to synthesize two parts of materials, namely a catalyst and a photosensitizer, and the synthesis process is complex; secondly, interface contact between the photosensitive unit and the catalytic unit is regulated, so that photo-generated electrons can be promoted to transfer from the photosensitive agent to the catalyst so as to drive the reaction to proceed, and the regulation and control technology has strict requirements and is not easy to control.
Disclosure of Invention
The invention provides a triple combination for overcoming the defects in the prior artPreparation method and application of pyridyl supermolecular photocatalyst, and preparation method and application of pyridyl supermolecular photocatalyst by using dissolution-precipitation process 2 To form renewable fuel.
The technical scheme adopted for solving the technical problems is as follows:
a preparation method of a terpyridyl supermolecule photocatalyst, wherein the terpyridyl supermolecule is a terpyridyl conjugated supermolecule containing bromo, and the preparation method comprises the following steps:
step a, preparing 4'- (4-bromophenyl) -2,2':6',2' -terpyridine conjugated molecules through a Krohnke intermediate cyclization method, then adding the conjugated molecules into benign organic solvent, and stirring and dissolving the solution at room temperature to form transparent solution;
step b, dropwise adding 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 precipitating a white precipitate;
and c, after obtaining the bromo 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 a Krohnke intermediate cyclization method is as follows:
in the step a, the Krohnke intermediate cyclization method is used for preparing 4'- (4-bromophenyl) -2,2':6',2' -terpyridine conjugated molecules, which are prepared by the following steps: the 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 ammonia water with the concentration of 25% -28% and 3.4-4.0g of KOH, stirring and reacting at room temperature, heating to 80-90 ℃ and stirring and reacting for 3-10h, filtering and washing with ethanol to obtain the 4'- (4-bromophenyl) -2,2':6',2' -terpyridine conjugated molecule.
In the preparation method of the terpyridyl supermolecular photocatalyst, in the step a, the benign organic solvent is DMF, ethylene glycol methyl ether or THF.
In the step a, the mass volume ratio of 4'- (4-bromophenyl) -2,2':6',2' -terpyridine conjugated molecule to benign organic solvent is 500mg: (7-14) mL.
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.
In the preparation method of the terpyridyl supermolecular photocatalyst, in the step b, the continuous stirring time of the suspension is 3-10h, and the standing time is 2h.
Application of terpyridyl supermolecular photocatalyst, and CO is reduced by photocatalysis of prepared terpyridyl supermolecular photocatalyst 2 The photocatalysis steps are as follows: 20mg of the bromo-conjugated terpyridine supermolecule was dispersed in a dish, to which 2mL of H was added 2 O; loading the surface dish into a reaction kettle, vacuumizing the reaction kettle to remove air, and filling CO 2 Vacuumizing and filling CO 2 The process of (2) is repeated three times; xenon lamp light reaction is carried out for 6 hours, sampling is carried out every 1 hour, and reduction products CO and CH in the sample are taken out through gas chromatography 4 Is a product of the above process.
The beneficial effects of the invention are as follows:
(1) The terpyridyl supermolecule semiconductor photocatalyst is prepared by a dissolution-precipitation method for the first time, and is assembled into the photocatalyst with single structural orientation, high crystallinity and strong built-in electric field through pi-pi stacking interaction, and the special structure is favorable for the efficient separation of photogenerated carriers and obviously improves the photocatalytic activity.
(2) The terpyridine compound is usually used as a photosensitizer, and can promote the transfer of photo-generated electrons from the photosensitizer to the catalyst to drive the reaction to proceed after the terpyridine compound acts with the photocatalyst, so that the regulation and control technical requirements are strict and difficult to control; the invention provides a photocatalyst which takes single-component terpyridine as a main body, and the system does not relate to the strict regulation and control of the transfer and the regulation of photo-generated electrons between a photosensitizer and a catalyst; in addition, the preparation steps of the single component are simple, the structure is easy to regulate and control, and the modification cost is low. In addition, the invention provides a theoretical basis for enriching the organic supermolecule types.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a white solid of 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine;
FIG. 2 is an optical picture of 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine dissolved in DMF and after dropwise addition of 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 image 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 Forming a rate graph of CO;
FIG. 7 is an optical microscope image of a Tpy-Br-2 photocatalyst;
FIG. 8 is a scanning electron microscope image of a Tpy-Br-2 photocatalyst;
FIG. 9 is a schematic diagram of the photocatalytic reduction of CO by Tpy-Br-2 2 Forming a rate graph of CO;
FIG. 10 is an optical microscope image of a Tpy-Br-3 photocatalyst;
FIG. 11 is a scanning electron microscope image of a Tpy-Br-3 photocatalyst;
FIG. 12 is a schematic diagram of the photocatalytic reduction of CO by Tpy-Br-3 2 Forming a rate graph of CO;
FIG. 13 is an optical microscope image of a Tpy-Br-4 photocatalyst;
FIG. 14 is a scanning electron microscope image of a Tpy-Br-4 photocatalyst;
FIG. 15 is a schematic diagram of the photocatalytic reduction of CO by Tpy-Br-4 2 Fast CO formationA rate map;
FIG. 16 is an optical microscope image 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 And (5) forming a rate graph of CO.
Detailed Description
The invention synthesizes a terpyridyl molecule (4 '- (4-bromophenyl) -2,2':6',2' -terpyridyl conjugated molecule) containing a bromo group by a simple Krohnke intermediate cyclization method, and then prepares a terpyridyl supermolecule by a dissolution-precipitation method, which is a self-assembled semiconductor photocatalyst. The method is characterized in that the bromo-containing terpyridyl molecule is dissolved in a benign organic solvent (DMF, ethylene glycol methyl ether or THF), the bromo-containing terpyridyl molecule in this state is free to move, and then a poor solvent (water) is added dropwise thereto, and as water molecules diffuse into the organic solvent, the bromo-containing terpyridyl molecule is no longer in a free state and is forced to aggregate into pi aggregates. The driving force for generating pi aggregate is pi-pi stacking effect among pyridine conjugated rings, and terpyridine molecules under the effect of the force are orderly arranged and have certain compactness, and the characteristics enable pi electrons on the pyridine rings to be expanded into pyridine rings of adjacent molecules, namely pi electrons can be transmitted and flow across the rings along orderly arranged conjugated molecules, so that the terpyridine molecules show certain conductivity and have the property of semiconductors. The substituent-Br can influence the dipolarity of molecules, so as to regulate and control the built-in electric field of the catalyst and promote the effective separation of photo-generated electrons and holes. In summary, the terpyridyl photocatalyst constructed by the simple dissolution-precipitation method provided by the patent has the advantages of high crystallinity, strong built-in electric field and more negative reduction potential, and the advantages of the terpyridyl photocatalyst can efficiently reduce CO by photocatalysis 2 The fuel is renewable, and has great application value and social significance.
The amount of benign organic solvent and poor solvent and the stirring time have a certain influence on the terpyridine assembly structure. The self-assembly process of the terpyridyl supermolecule is that the terpyridyl molecule is directionally assembled into a nucleus through pi-pi accumulation and the action between halogen-Br and benzene rings, and then more molecules grow in the nucleus direction and then 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 is insufficient molecules and time to promote continued growth of the assembly into a rod-like structure and the assembly process may only stay in the nucleation stage. If the amount of poor solvent water is too small, the terpyridyl molecule is more easily dissolved in the organic solvent according to the similar principle of miscibility, and no assembly behavior occurs. Therefore, the optimal conditions for obtaining a stable terpyridine rod-like structure according to the invention are: the mass volume ratio of the terpyridyl compound to the benign organic solvent to the poor solvent water is 500mg respectively: (7-14) mL and 500mg: (63-126) mL, and stirring time is 3-10h.
In the process of preparing terpyridyl supermolecule by dissolving-precipitating, 4'- (4-bromophenyl) -2,2':6',2' -terpyridine is dissolved by benign organic solvent, and surfactant can be added into poor solvent water, for example, after Sodium Dodecyl Benzene Sulfonate (SDBS) serving as surfactant is dissolved in water, the solution is added into organic mixed solution in a dropwise manner to obtain the white precipitated photocatalyst self-assembly. Or during the precipitation stage, a metal compound (e.g., zn (NO) 3 ) 2 ·6H 2 O), the terpyridyl conjugated supermolecule for chelating metal ions is prepared, has a lamellar structure and is piled up into a porous block structure, and has higher conductivity and better photocatalytic performance.
The invention is further illustrated below with reference to examples.
Example 1
1. 4.0g of p-bromobenzaldehyde is dissolved in 50mL of ethanol, then 4.86mL of 2-acetylpyridine is added, after stirring for 5min, 3.4g of KOH and 80mL of ammonia water are slowly added dropwise in sequence, after stirring for 2h at room temperature, heating is carried out to 80 ℃ for 24h, white precipitate is collected by filtration, and unreacted reactant and impurities are removed by washing with ethanol for multiple times, so that 4'- (4-bromophenyl) -2,2':6',2' -terpyridine is obtained as white solid. The nuclear magnetic resonance test is carried out on the white solid, the obtained nuclear magnetic resonance spectrum is shown in figure 1, and the figure shows that the target product 4'- (4-bromophenyl) -2,2':6',2' -terpyridine is 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. 500mg of the 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine prepared above was weighed, 7mL of DMF was added, and after sonication or heating, was completely dissolved;
3. 63mL of H was slowly added dropwise 2 O is added into the stirred 4'- (4-bromophenyl) -2,2':6',2' -terpyridine organic solution, and white precipitate is gradually separated out; after stirring for 8 hours at normal temperature, standing for 2 hours, filtering and collecting white solid, and vacuum drying for 10 hours to obtain the 4'- (4-bromophenyl) -2,2':6',2' -terpyridine supermolecule self-assembled photocatalyst, which is marked as Tpy-Br-1.
FIG. 2 is an optical image of a 4'- (4-bromophenyl) -2,2':6',2 "-terpyridine molecule dissolved in DMF, followed by dropwise addition of water to a DMF solution of 4' - (4-bromophenyl) -2,2':6',2" -terpyridine. As is evident from the figure, the addition of water dropwise to a solution of 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine in DMF resulted in a white precipitate.
4. Characterization test is carried out on crystal structure and morphology of the prepared Tpy-Br-1 photocatalyst
FIG. 3 is an XRD pattern of a Tpy-Br-1 photocatalyst, and from the pattern, it can be seen that the Tpy-Br-1 photocatalyst shows a remarkable diffraction peak, indicating that the Tpy-Br-1 supermolecule self-assembly body shows excellent crystallization performance. The d value corresponding to the diffraction angle of 21.6℃is 0.41nm, which is a typical pi-pi stacking spacing. The excellent crystallization performance of Tpy-Br-1 is derived from the fact that terpyridyl conjugated molecules are assembled into an ordered structure through strong pi-pi stacking interaction. Pi electrons of terpyridine can move across the ring along the conjugated ordered structure, so that Tpy-Br-1 shows a certain conductivity, and the conductivity is 4.95S cm through four-probe testing -1 Exhibits semiconductor properties, the conductivity of the semiconductor being in the range of 10 -8 ～10 3 S cm -1 。
FIGS. 4 and 5 are optical and scanning electron microscope spectra of a Tpy-Br-1 photocatalyst, respectively. As can be seen from the figure, the Tpy-Br-1 photocatalyst shows an orderly arranged rod-like structure with a length of about 2 μm and a width of 200nm. The ordered rod-shaped assembling structure of the catalyst is formed by assembling terpyridyl supermolecules through strong pi-pi stacking among molecules. The regular rod-shaped structure is beneficial to constructing a built-in electric field, so that photogenerated carriers are 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 and reduces 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 And (5) forming a rate graph of CO. From the figure, the Tpy-Br-1 photocatalyst is used for photocatalytic reduction of CO for 6 hours 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 2.1 times of the CO rate; little CO was produced in dark conditions, indicating that the CO produced was from a photocatalytic process; in addition, a small amount of CO was generated under Ar-filled conditions, probably because a small amount of CO remained in the reaction vessel 2 Which is reduced to CO under illumination; while in the absence of catalyst, a small amount of CO is produced, probably because under illumination, water can act as a reducing agent to reduce CO 2 Into CO (Nature Energy,2017,2,17087-17096).
Example 2
1. 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine was prepared in the same manner as in example 1;
2. 500mg of 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine are weighed, added with 14mL of DMF, and completely dissolved after sonication or heating;
3. 126mL of H was slowly added dropwise 2 O is added into the stirred 4'- (4-bromophenyl) -2,2':6',2' -terpyridine organic solution, and white precipitate is gradually separated out; 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 molecule self-assembled photocatalyst, designated as Tpy-Br-2.
4. In the embodiment, the profile map of the Tpy-Br-2 photocatalyst
FIGS. 7 and 8 are optical and scanning electron microscope maps, respectively, of a Tpy-Br-2 photocatalyst. As can be seen from the figure, the assembled Tpy-Br-2 photocatalyst still shows an orderly arranged rod-like structure with a length of about 4 μm and a width of 200nm. Conductivity of 3.98S cm -1 Exhibiting semiconductor properties.
5. In this example, the TPy-Br-2 photocatalyst catalyzes and reduces CO 2 Activity test of (2)
FIG. 9 is a schematic diagram of the photocatalytic reduction of CO by Tpy-Br-2 2 And (5) forming a rate graph of CO. From the figure, it can be seen that Tpy-Br-2 in simulated sunlight, 6h photocatalytic reduction of CO 2 The rate of CO formation was 6.6. Mu. Mol g -1 。
Example 3
1. 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine was prepared in the same manner as in example 1;
2. 500mg of 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine are weighed, added with 14mL of ethylene glycol methyl ether, and completely dissolved after ultrasonic treatment or heating;
3. 63mL of H was slowly added dropwise 2 O is added into the stirred 4'- (4-bromophenyl) -2,2':6',2' -terpyridine organic solution, and white precipitate is gradually separated out; after stirring for 8h at normal temperature, standing for 2h, filtering and collecting white solid, and vacuum drying for 10h to obtain the 4'- (4-bromophenyl) -2,2':6',2' -terpyridine molecule self-assembled photocatalyst, which is marked as Tpy-Br-3.
4. In the embodiment, the profile map of the Tpy-Br-3 photocatalyst
FIGS. 10 and 11 are optical 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 shows ordered rod-like structure, and its conductivity was measured to be 4.82S cm -1 Has the property of a semiconductor.
5. In this example, the TPy-Br-3 photocatalyst catalyzes and reduces CO 2 Activity test of (2)
FIG. 12 is a schematic diagram of the photocatalytic reduction of CO by Tpy-Br-3 2 And (5) forming a rate graph of CO. From the figure, it can be seen that under simulated sunlight, the Tpy-Br-3 photocatalyst performs photocatalytic reduction on CO for 6h 2 The rate of CO formation was 14.7. Mu. Mol g -1 。
Example 4
Surfactant (SDBS) was added: preparation of Tp y-B r-4 photocatalyst
1. Preparation of 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine white solid was performed in the same manner as in example 1;
2. 500mg of 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine are weighed, 7mL of ethylene glycol methyl ether is added, and after ultrasonic treatment or heating, the ethylene glycol methyl ether is completely dissolved;
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 to collect white solid, washing with water for 2 times to remove SDBS on the surface of a sample, and vacuum drying for 10h to obtain the 4'- (4-bromophenyl) -2,2':6',2' -terpyridine molecular self-assembled photocatalyst, which is marked as Tpy-Br-4.
4. In the embodiment, the profile map of the Tpy-Br-4 photocatalyst
FIGS. 13 and 14 are optical and scanning electron microscope spectra of a Tpy-Br-4 photocatalyst, respectively. As can be seen from the figure, the Tpy-Br-4 photocatalyst still shows an orderly arranged rod-like structure with a length and a width of 10 μm and 200nm, respectively, but the Tpy-Br-4 photocatalyst is assembled more uniformly than the former three examples because the hydrophilic heads are connected in the aqueous solution to form a spherical shell during the auxiliary assembly process of the surfactant, the hydrophobic tails are gathered at a place far from the solution to form a cavity, and the terpyridine is more likely to stay in the micelle cavity through the hydrophobic and pi-pi actions between the terpyridine alkyl chain and the benzene ring. The ordered nature of the micelle cavities causes the terpyridine assemblies to exhibit a morphology of uniform structural size. In addition, tpy-Br-4 has semiconducting properties with a conductivity of 4.63S cm -1 。
5. In this example, the TPy-Br-4 photocatalyst catalyzes and reduces CO 2 Activity test of (2)
FIG. 15 is a schematic diagram of the photocatalytic reduction of CO by Tpy-Br-4 2 And (5) forming a rate graph of CO. As can be seen from the figure, under the condition of simulated sunlight, after the surfactant is added, the Tpy-Br-4 photocatalyst reduces CO for 6 hours 2 The rate of CO formation was 16.9. Mu. Mol g -1 。
Example 5
Chelating metal ions: preparation of Zn-Tpy-Br conjugated super-molecular photocatalyst
1. Preparation of 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine white solid was performed in the same manner as in example 1;
2. 200mg of 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine were 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 was 2:1, 76.63mg Zn (NO 3 ) 2 ·6H 2 O was then dissolved in 4.66mL of methanol, and Zn (NO 3 ) 2 ·6H 2 Slowly dripping the O solution into 4'- (4-bromophenyl) -2,2':6',2' -terpyridine solution; stirring at normal temperature for 8h, generating white precipitate after rotary evaporation, washing the precipitate with hot dichloromethane for 2 times, removing unreacted reactant, and vacuum drying overnight to finally obtain 4'- (4-bromophenyl) -2,2':6',2' -terpyridine supermolecule photocatalyst of chelated zinc ion, which is marked as Zn-Tpy-Br.
4. Morphology map of Zn-Tpy-Br photocatalyst in this example
FIGS. 16 and 17 are optical and scanning electron microscope spectra of Zn-Tpy-Br photocatalyst, respectively. As can be seen from the figure, and Zn 2+ After chelation, the 4' - (4-bromophenyl) -2,2':6',2 "-terpyridine molecules assemble into a lamellar structure that is packed into a porous block structure. The Zn-Tpy-Br photocatalyst has the property of a semiconductor, and the conductivity of the Zn-Tpy-Br photocatalyst is 9.84S cm -1 。
5. In the embodiment, the Zn-Tpy-Br photocatalyst catalyzes and reduces CO 2 Activity test of (2)
FIG. 18 is a diagram ofZn-Tpy-Br photocatalytic reduction of CO 2 As can be seen from the graph, the rate graph of CO chelates Zn in simulated sunlight 2+ After that, the Zn-Tpy-Br photocatalyst reduces CO for 5h 2 The rate of CO formation can reach 86.9 mu mol g -1 Is 5.4 times that of Tpy-Br-1 photocatalyst.
Claims (5)
1. Terpyridyl supermolecule photocatalyst for photocatalytic reduction of CO 2 Is characterized in that: the terpyridyl supermolecule is a terpyridyl conjugated supermolecule containing bromo, and the preparation method comprises the following steps:
step a, preparing a 4'- (4-bromophenyl) -2,2':6',2' -terpyridine conjugated molecule through a Krohnke intermediate cyclization method, then adding the conjugated molecule into a benign organic solvent, and stirring and dissolving the solution at room temperature to form a transparent solution;
step b, dropwise adding 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 precipitating a white precipitate;
c, after obtaining a bromo-terpyridine conjugated supermolecule sample, characterizing the sample, and judging the structural characteristics of the sample;
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;
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;
in the step b, the sodium dodecyl benzene sulfonate serving as a surfactant is added into poor solvent water.
2. The terpyridyl supramolecular photocatalyst according to claim 1 for photocatalytic reduction of CO 2 Is characterized in that: in the step a, the Krohnke intermediate cyclization method for preparing the 4' - (4-bromophenyl) -2,2':6',2' ' -terpyridine conjugated molecule comprises the following steps: the 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 materialsStirring in 50-100mL ethanol, sequentially slowly adding 80-100mL ammonia water with concentration of 25% -28% and 3.4-4.0g KOH at room temperature, stirring for reaction, heating to 80-90 deg.C, stirring for reaction for 3-10h, filtering, and washing with ethanol to obtain 4' - (4-bromophenyl) -2,2':6',2' ' -terpyridine conjugated molecule.
3. The terpyridyl supramolecular photocatalyst according to claim 2 for photocatalytic reduction of CO 2 Is characterized in that: in the step a, the benign organic solvent is DMF, ethylene glycol methyl ether or THF.
4. The terpyridyl supramolecular photocatalyst as claimed in claim 3, for photocatalytic reduction of CO 2 Is characterized in that: in the step b, the stirring time of the suspension is 3-10h, and the standing time is 2h.
5. The terpyridyl supramolecular photocatalyst according to any of claims 1-4 for photocatalytic reduction of CO 2 Is characterized in that: the photocatalysis steps are as follows: 20mg of the bromo-terpyridine conjugated supramolecules were dispersed in a dish to which 2mL of H was added 2 O; loading the surface dish into a reaction kettle, vacuumizing the reaction kettle to remove air, and filling CO 2 Vacuumizing and filling CO 2 The process of (2) is repeated three times; xenon lamp illumination reaction 6h, sampling every 1h, taking reduction products CO and CH out of the sample by gas chromatography 4 Is a product of the above process.
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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 |
| CN113150036A (en) * | 2021-05-08 | 2021-07-23 | 衡阳师范学院 | Triarylamine substituted terpyridyl ruthenium complex and preparation method and application thereof |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN113150036A (en) * | 2021-05-08 | 2021-07-23 | 衡阳师范学院 | Triarylamine substituted terpyridyl ruthenium complex and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Jianhua Wang et al..A Facile Route to Sterically Hindered and Non-Hindered 4'-Aryl-2,2':6',2''Terpyridines.LETTER.2005,1252-1253页. * |
| Resin with short-range π-π stacking aggregates for an effcient photocatalyst;Lin Wang et al;Chemical Engineering Journal;第1-2页 * |
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