CN114558618A - Preparation method of azide-alkyne cycloaddition polyacid-based photocatalyst - Google Patents
Preparation method of azide-alkyne cycloaddition polyacid-based photocatalyst Download PDFInfo
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- 238000010461 azide-alkyne cycloaddition reaction Methods 0.000 title claims abstract description 31
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 10
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 6
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 5
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001907 polarising light microscopy Methods 0.000 claims abstract 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- 229920006830 POM-M Polymers 0.000 claims description 19
- 239000013077 target material Substances 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 6
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 238000010586 diagram Methods 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 3
- 239000002262 Schiff base Substances 0.000 claims description 3
- 150000004753 Schiff bases Chemical class 0.000 claims description 3
- UDLLFLQFQMACJB-UHFFFAOYSA-N azidomethylbenzene Chemical compound [N-]=[N+]=NCC1=CC=CC=C1 UDLLFLQFQMACJB-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000010354 integration Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005580 one pot reaction Methods 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
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- 230000001105 regulatory effect Effects 0.000 claims description 2
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- 239000006228 supernatant Substances 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- -1 polyoxymethylene Polymers 0.000 abstract description 5
- 239000003504 photosensitizing agent Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001345 alkine derivatives Chemical group 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000203 mixture 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
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- 238000010992 reflux Methods 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- BOJMHHBWYPDQQH-UHFFFAOYSA-N 3-ethenylthiophene Chemical compound C=CC=1C=CSC=1 BOJMHHBWYPDQQH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
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- 150000001540 azides Chemical class 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
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- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
- B01J2231/328—Cycloadditions involving more than 2 components or moieties, e.g. intra-/intermolecualar [2+2+2] or [2+2+1], e.g. Pauson-Khand type
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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Abstract
The invention relates to a preparation method of azide-alkyne cycloaddition polyacid-based photocatalyst, belonging to the technical field of catalysis of POMs (polyoxymethylene) materials. The Cu (I) -POM POMs are obtained by self-assembly of Cu (I) -based POMs constructed by trihydroxyaminomethane parts, Anderson type polyacid and 4-pyridylaldehyde as connecting nodes, the materials are crystallized into orange red blocky crystals, and redox active Cu (I) in the structure can be used as catalytic sites for catalyzing cycloaddition. In a three-component system with a polyacid group as a photosensitizer and Triethylamine (TEA) as an electronic sacrificial agent, the functional material can be used as a heterogeneous catalyst for photo-enhanced CuAAC reaction, the obtained functional material has stable chemical property and good catalytic performance, and the possibility is provided for enhancing the catalytic reaction of CuAAC under visible light.
Description
Technical Field
The invention relates to preparation and application of azide-alkyne cycloaddition polyacid-based photocatalyst, and belongs to the technical field of POMs (polyoxymethylene) material catalysis.
Background
The 1,2, 3-triazole compound synthesized by the azide-alkyne cycloaddition (AAC) is an attractive reaction in organic synthesis, and has wide application in the fields of medicine, biotechnology, polymer, material science and the like. Generally, the catalytically active cu (i) site plays an important role in the cycloaddition process, and the reaction between the azide compound and the terminal alkyne can be catalyzed directly by the cu (i) based salt/compound or can be reduced by the cu (ii) based compound to cu (i) ions in the catalytic process. With the latter method, it is necessary to supplement various reducing agents, such as functional ligands, nanoparticles or bases, in the system to increase the catalytic activity of the catalyst. Recently, photo-induced electron transfer (PET) of photochemical process has been developed as a new method for AAC catalysis, i.e. the desired cu (i) active site can be obtained from photosensitive unit to cu (ii) center by intramolecular PET, effectively avoiding direct use of unstable cu (i) ions.
Polyoxometalates (POMs), an important subset of anionic metal-oxygen clusters, are of great interest because of their diverse structures and abundant properties, and are easily modified with various functional groups or metal ions, and are widely used in the fields of catalysis, photochemistry, biomedicine, magnetics, and the like. In particular, POMs exhibit good photoactivity, enabling multi-electron transfer to other species under visible light irradiation, and are considered to be excellent photo-redox reagents in many photocatalytic systems. Wherein, the introduction of organic ligands into the POMs unit not only can be used as a linker to enrich structural configurations of different sizes and shapes, but also can construct unique organic-inorganic hybrid materials, and combines the characteristics of inorganic and organic functions into a single system. These multifunctional benign features give them a wider range of applications as promising molecular devices for green chemistry, which may greatly simplify the additive components required for catalysis, such as reducing or oxidizing agents, acids, bases, co-catalysts, initiators or organic solvents. Therefore, the development of novel multifunctional POMs molecular devices is of great significance.
Based on these considerations, in the present invention, organic-inorganic hybrid compounds were successfully synthesized based on the assembly of α -B-Anderson type POM with cu (i) ions. The most attractive feature of α -B-Anderson-type POMs is the presence of three substitutable hydroxyl groups on each side, which provides potential functional sites for modification by hydroxyl substitution reactions. The compound design includes Anderson MMo6O18](M = Mn, Fe, Cu, Co, Ni, Cr) cluster as photosensitizer, organic [ (OCH) synthesized by Schiff base reaction2)3CN=CH-4-Py]Partially grafted on both sides, and the partial oxidation of the starting Cu (I) salt to give Cu (I)/Cu (II) ions. Oxidized Cu (II) ions can be transferred from [ MnMo ] as photosensitizer by photoinduced electron transfer6O18]The cell is regenerated to cu (i), and this in situ reduction process provides enhanced heterogeneous catalytic performance for the AAC reaction.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide preparation and application of a class of azide-alkyne cycloaddition polyacid-based photocatalysts. In a three-component system with polyacid groups as a photosensitizer and Triethylamine (TEA) as an electronic sacrificial agent, the material can be used as a heterogeneous catalyst for photo-enhancement of AAC reaction, and the obtained functional material has stable chemical properties and good catalytic performance, and provides possibility for enhancing the catalytic reaction of AAC under visible light.
In order to achieve the purpose of the invention and solve the problems in the prior art, the invention adopts the technical scheme that: a preparation method of azide-alkyne cycloaddition polyacid-based photocatalyst comprises the steps of taking a hydroxyl group as a coordination site, reacting the hydroxyl group with trihydroxyaminomethane through a hydroxyl substitution reaction to obtain a polyacid precursor EEDQ-M, taking an amino group in the obtained polyacid precursor EEDQ-M as the coordination site, connecting the amino group with 4-pyridylaldehyde (4-Py) through a Schiff base reaction to obtain a polyacid ligand POM-M, taking Cu (I) with an efficient reaction site as a node, and preparing a POMs material based on metallic copper and Anderson type polyacid precursors by utilizing a one-pot method or a poor solvent diffusion method through regulating the ratio of the polyacid ligand POM-M to a metal salt and the type and ratio of a reaction solvent, wherein the synthesis route is as follows:
Cu + POM-M→Cu-POM-M；
the prepared POMs are used as heterogeneous catalysts for applying visible light enhanced AAC, the new compound is a copper metal Anderson type polyacid complex with a zero-dimensional framework structure, and visible light enhanced AAC catalysis with a quasi-first order reaction rate in a heterogeneous state shows high catalytic activity and reaction stability;
the metal salt is selected from one of CuI and CuCl;
the polyacid precursor (TBA)3[MMo6O18((OCH2)3CNH2)2]Is EEDQ-M (M = one of Mn, Ni, Fe and Co), and the structural formula of the ball rod is shown in figure 1;
the polyacid ligand POM-M is (TBA)3[XMo6O18 ((OCH2)3CN=CH-4-Py)2](M = one of Mn, Ni, Fe, Co); the three-dimensional structure diagram is shown in figure 2;
the chemical formula of the POMs material Cu-POM-M is CuI2(TBA)2POM-Mn·DMA；CuCl2(TBA)2POM-Co·DMA；CuCl2(TBA)2POM-Ni·DMA；CuI2(TBA)2POM-Fe. DMA.
The preparation method of the azide-alkyne cycloaddition polyacid-based photocatalyst comprises the following steps:
(1) polyacid ligand POM-M and Cu metal salt were dissolved in 24mL of N, N-Dimethylacetamide (DMA) in a volume ratio of 2:1, at a molar ratio of 0.12: 1.2: to the mixed solvent of acetonitrile, Triethylamine (TEA) was added in a volume of 0.5mL, and 1.44mmoL of tetrabutylammonium iodide (TBAI) was added;
(2) the solution is heated at a temperature of 75 ℃, N2Stirring for 3h under protection, filtering the reacted solvent after stirring, putting 3mL of solution into a test tube each time, putting the test tube into a wide-mouth bottle filled with a poor solvent, and diffusing for 7 days to obtain a target material after crystal precipitation;
(3) separating out the crystal prepared in the above steps, washing with ethanol, removing the solvent in the pore channel, and drying in the air to obtain the final product.
The preparation method of the azide-alkyne cycloaddition polyacid-based photocatalyst comprises the following steps:
(1) dissolving a polyacid ligand POM-M in 3-5mL of DMA solvent to prepare a lower layer solution, adding copper metal salt into 3-5mL of acetonitrile to prepare an upper layer solution, wherein the middle layer is a mixed solution of DMA and acetonitrile, and the molar ratio of the polyacid ligand to the metal salt Cu is 0.05-0.15: 0.1-1.5, and the volume ratio of the acetonitrile to the DMA is 1.0-2.0: 1.0-3.0;
(2) and (3) placing the prepared reaction solution in a test tube, reacting for 1-2 weeks at room temperature, and separating out crystals to obtain the target material.
The structural characteristics of the azide-alkyne cycloaddition polyacid-based photocatalyst are as follows:
the molecular formula C of the material 1108H220Cu2I4MnMo6N11O26The chemical formula is CuI2(TBA)2POM-Mn; the crystal structure data of the material is: the crystal is monoclinic system, and the space group isC2/cCell parameter ofa=37.664(3) Å，b=16.8978(15) Å，c=23.1201(8) Å，α=90°，β=90.747°，γ=90°。
The prepared POMs are used for visible light catalysis AAC reaction, and the catalysis steps are as follows:
(1) at room temperature, a 20W household incandescent lamp is used as a reaction light source, and 1 mmol per thousand of material 1, 138 mu L (1.0 mmol) of substrate benzyl azide, 114 mu L (1.0 mmol) of phenylacetylene and 7.1mL of TEA are added into a 10mL quartz reaction tube for heterogeneous photocatalysis;
(2) after the AAC reaction had taken place, CHCl was added to the reaction tube3To dissolve the solid product, the catalyst was separated by centrifugation and the supernatant was evaporated in vacuo. By passing1H NMR Spectroscopy (CDCl)3As solvent) the reaction was monitored and the conversion of the cycloaddition reaction was monitored by integration of a single peak at 4.3 ppm in the starting substrate and a single peak at 5.5 ppm in the final product.
The POMs are selected from CuI prepared2(TBA)2POM-Mn；
The selected solvent is one of water, methanol, ethanol, acetonitrile, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and acetone;
the metal cation is selected from one of CuI and CuCl.
Advantageous results of the invention
The invention has the advantages that: taking N in an Anderson type polyacid precursor as a connecting node, selecting copper metal salt with high catalytic activity, and self-assembling to obtain Cu-POM-M POMs by using a one-pot method or a layered diffusion synthesis method; the novel compound has a zero-dimensional framework structure, has a quasi-first-order reaction rate in a heterogeneous catalysis state, and has high catalytic activity and reaction stability in visible light enhanced AAC catalysis; compared with the prior art, the POMs catalyst obtained by reacting easily prepared and low-cost monovalent copper metal salt can be applied to green, pollution-free and sustainable photocatalysis AAC reaction, can realize reaction without solvent and by-product generation through performance evaluation, and has good application prospect.
Drawings
FIG. 1 is a schematic diagram of the structure of a ball stick of the polyacid precursor EEDQ-M used.
FIG. 2 is a schematic representation of the steric structure of the polyacid ligand POM-M used.
Fig. 3 is a schematic perspective view of the target material of example 1.
Fig. 4 is an XPS spectrum of metallic copper as the target material of example 1.
FIG. 5 is a pre-and post-catalytic FT-IR contrast spectrum of the target material of example 1.
Figure 6 is a graph of the catalytic kinetics of the target material of example 1 as a catalyst.
Fig. 7 is a cycle chart of the target material of example 1.
FIG. 8 is a schematic diagram of the development of the substrate in example 1.
Fig. 9 is a hypothetical catalytic reaction scheme for catalyzing AAC with the target material of example 1 as a heterogeneous catalyst.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1 (Synthesis of Cu-POM-Mn)
A mixture of polyacid ligand POM-Mn (0.252 g, 0.12 mmol), CuI (0.240 g, 1.2 mmol), 0.5mL of TEA and TBAI (0.54 g, 1.44 mmol) was added to 24mL of DMA/acetonitrile (2: 1) solvent. After refluxing under nitrogen at 75 ℃ for 3 hours, the solution was filtered, one tube per 3mL of solvent, and the tube was placed in a jar containing the poor solvent. After one week orange red crystals were obtained, washed with ethanol, dried in air and weighed, with a yield of 60%.
Example 2 (Synthesis of Cu-POM-Co)
Dissolving polyacid ligand POM-Co (0.105 g, 0.05 mmol) in 3mL of DMA solvent to prepare a lower layer solution, adding CuI (0.100 g, 0.5 mmol) into 3mL of acetonitrile to prepare an upper layer solution, adding 6mL of mixed solution of DMA and acetonitrile in the middle layer at a volume ratio of 1:2, placing the prepared reaction solution in a test tube, reacting at room temperature for 1-2 weeks, washing with ethanol after crystal precipitation, drying, weighing, and calculating the yield.
Example 3 (Synthesis of Cu-POM-Fe)
A mixture of polyacid ligand POM-Fe (0.252 g, 0.12 mmol), CuCl (0.120 g, 1.2 mmol), 0.5mL TEA and TBAI (0.54 g, 1.44 mmol) was added to 24mL DMA/acetonitrile (2: 1) solvent. After refluxing under nitrogen at 75 ℃ for 3 hours, the solution was filtered, one tube per 3mL of solvent, and the tube was placed in a jar containing the poor solvent. After one week, crystals were obtained, washed with ethanol, dried in air and weighed, and the yield was calculated.
Example 4 (stability of target Material 1)
To further understand the stability of 1, we performed 10 ℃ in nitrogen flow from room temperature to 800 ℃ in nitrogen atmosphereoC min-1The temperature rise rate of (a) was subjected to thermogravimetric analysis, and it can be seen from the TGA curve that the skeleton of 1 is stable at least 200 ℃. The observed weight loss process was mainly three steps, between 80 and 200 ℃, the slow weight loss of 6.8% was due to two free DMA and three free H in 12Removal of the O molecule (calculated to be 6.86%). 51.51% (calculated to be 51.27%) in the range of 200 to 630 deg.CThe large weight loss can be attributed to the removal of 5 TEA ions and 4 coordinating I ions. In the temperature range of 630 to 830 ℃, organic [ (OCH)2)3CN=CH-4-Py]The partial decomposition and polyanionic disintegration was about 17.8% by weight, which was the last step of the loss. This analysis shows that 1 has good thermal stability.
Example 5 (target Material 1 photocatalytic AAC reaction)
At room temperature, a 20W household incandescent lamp is used as a reaction light source, and 1 mmol per thousand of material 1, 138 mu L (1.0 mmol) of substrate benzyl azide, 114 mu L (1.0 mmol) of phenylacetylene and 7.1mL of TEA are added into a 10mL quartz reaction tube for heterogeneous photocatalysis; after the AAC reaction has taken place, by1H NMR Spectroscopy (CDCl)3As solvent) the reaction was monitored and the conversion of the cycloaddition reaction was monitored by integration of a single peak at 4.3 ppm in the starting substrate and a single peak at 5.5 ppm in the final product.
Example 6 (substrate development of target Material 1)
The target material 1 shows good photocatalytic activity for various alkyne substrates under the same conditions. When phenyl in alkyne is substituted for fluorine atom or methoxy in para position, there is no significant change in conversion. The catalytic performance of the chlorine atom or methyl substituted alkyne is slightly reduced, the conversion rate of the corresponding product is 91 percent and 96 percent respectively, and the conversion rate when the carbon chain length is increased to n-butyl or t-butyl is 95 percent or 90 percent. Under the same conditions, catalyst 1 also gives better final products when the phenyl group in the alkyne substitutes the fluorine atom or methoxy group in the central position. In addition, 3-vinylthiophene was also selected as a substrate for the study of AAC, and a product after complete conversion could be observed. This result further indicates that the catalytic reaction using 1 as a catalyst has a very general substrate range for different alkynes and azides, and the synthesized target material 1 shows that the photocatalysis can be further applied to practical potential.
Example 7 (recovery and recycle experiment of target Material 1)
For heterogeneous catalysts, recoverability is an essential feature for practical use, after 4 hours by illumination, our target material 1 was isolated from the reaction by addition of ethyl acetate followed by centrifugation and re-used under the same conditions in a fresh photocatalytic system with addition of reaction substrate and TEA, these cycling tests showed that the target material 1 could be reused for 4 cycles without any significant loss of photocatalytic activity, and after the end of the reaction, the used catalyst was subjected to FT-IR measurements with spectra consistent with that of the fresh catalyst 1, indicating that the main framework was retained and that 1 had excellent stability after four cycles.
Claims (4)
1. The preparation method of the azide-alkyne cycloaddition polyacid-based photocatalyst is characterized by comprising the following steps:
taking a hydroxyl group as a coordination site, and reacting the hydroxyl group with trihydroxyaminomethane through a hydroxyl substitution reaction to obtain an Anderson polyacid precursor EEDQ-M;
taking an amino group in the obtained polyacid precursor EEDQ-M as a coordination site, and connecting the amino group with 4-pyridylaldehyde (4-Py) through Schiff base reaction to obtain a polyacid-based ligand POM-M;
EEDQ-M+ 4-Py → POM-M
with Cu having highly effective reaction sites+As a node, by regulating the proportion of the polyacid-based ligand POM-M and the metal salt and the type and proportion of a reaction solvent, a material based on metallic copper and Anderson type POMs is prepared by a one-pot method, a poor solvent diffusion method or a layered diffusion method, and the synthetic route is as follows:
Cu + POM-M→ Cu-POM-M；
(4) the prepared POMs are used as heterogeneous catalysts for visible light enhanced catalysis of azide-alkyne cycloaddition reaction, the novel compound is a copper metal Anderson type polyacid complex with a zero-dimensional framework structure, and visible light enhanced CuAAC catalysis with a quasi-first-order reaction rate in a heterogeneous state shows high catalytic activity and reaction stability;
the polyacid precursor EEDQ-M is (TBA)3[MMo6O18((OCH2)3CNH2)2](ii) a (M = Mn, Ni, Fe, CoOne) is provided, the structural formula of the ball stick is shown in figure 1;
the polyacid-based ligand POM-M is of the partial formula (TBA)3[XMo6O18 ((OCH2)3CN=CH-4-Py)2](M = one of Mn, Ni, Fe, Co); the structure diagram is shown in figure 2;
the metal salt is selected from one of CuI and CuCl;
the molecular formula of the POMs material Cu-POM-M is CuI2(TBA)2POM-Mn·DMA；CuCl2(TBA)2POM-Co·DMA；CuCl2(TBA)2POM-Ni·DMA；CuI2(TBA)2POM-Fe. DMA.
2. The preparation method of the azide-alkyne cycloaddition polyacid-based photocatalyst according to claim 1 is characterized by comprising the following steps:
the polyacid ligand POM-M and the metal salt Cu are dissolved in 24mL of N, N-Dimethylacetamide (DMA) according to a molar ratio of 0.1-0.15: 1.0-1.5: in the mixed solvent of acetonitrile, the volume ratio range is 1.5-2.5:0.5-1.5, Triethylamine (TEA) with the volume range of 0.2-1.0mL is added into the solution, tetrabutylammonium iodide (TBAI) is added, and the molar range is 1.0-2.0 mmoL;
the solution is heated at 60-90 deg.C, N2Stirring under protection, controlling the stirring time within 2-5h, filtering the reacted solvent after stirring, putting 2-4mL of solution into a test tube, putting the test tube into a wide-mouth bottle filled with a poor solvent, and diffusing, wherein the reaction time is 5-10 days, and crystals are separated out to obtain the target material;
separating out the crystal prepared in the above steps, washing with ethanol, removing the solvent in the pore channel, and drying in the air to obtain the final product.
3. The preparation method of the azide-alkyne cycloaddition polyacid-based photocatalyst according to claim 1 is characterized by comprising the following steps:
dissolving a polyacid ligand POM-M in 3-5mL of DMA solvent to prepare a lower layer solution, adding copper metal salt into 3-5mL of acetonitrile to prepare an upper layer solution, wherein the middle layer is a mixed solution of DMA and acetonitrile, and the molar ratio of the polyacid ligand to the metal salt Cu is 0.05-0.15: 0.1-1.5, and the volume ratio of the acetonitrile to the DMA is 1.0-2.0: 2.0-10.0;
and (3) placing the prepared reaction solution in a test tube, reacting for 1-2 weeks at room temperature, and separating out crystals to obtain the target material.
4. The preparation method of the azide-alkyne cycloaddition polyacid-based photocatalyst according to claim 1, which is used for visible light catalysis of azide-alkyne cycloaddition reaction, and comprises the following catalysis steps:
at room temperature, a 20W household incandescent lamp is used as a reaction light source, and 1 mmol per thousand of material 1, 138 mu L (1.0 mmol) of substrate benzyl azide, 114 mu L (1.0 mmol) of phenylacetylene and 7.1mL of TEA are added into a 10mL quartz reaction tube for heterogeneous photocatalysis; after the CuAAC reaction had taken place, CHCl was added to the reaction tube3To dissolve the solid product, separating the catalyst by centrifugation and evaporating the supernatant in vacuo, by1H NMR Spectroscopy (CDCl)3As solvent) the reaction was monitored and the conversion of the cycloaddition reaction was monitored by integration of a single peak at 4.3 ppm in the starting substrate and a single peak at 5.5 ppm in the final product.
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