CN114558618B - Preparation method of azide-alkyne cycloaddition multi-acid-based photocatalyst - Google Patents
Preparation method of azide-alkyne cycloaddition multi-acid-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 11
- 239000002253 acid Substances 0.000 title description 4
- 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 41
- 229920006830 POM-M Polymers 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 8
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 6
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 claims abstract description 4
- WGYFACNYUJGZQO-UHFFFAOYSA-N aminomethanetriol Chemical group NC(O)(O)O WGYFACNYUJGZQO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001907 polarising light microscopy Methods 0.000 claims abstract 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- 239000010949 copper Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 22
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003446 ligand Substances 0.000 claims description 17
- 239000013077 target material 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
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 230000001699 photocatalysis Effects 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 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
- UDLLFLQFQMACJB-UHFFFAOYSA-N azidomethylbenzene Chemical compound [N-]=[N+]=NCC1=CC=CC=C1 UDLLFLQFQMACJB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005580 one pot reaction Methods 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 238000003756 stirring 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
- 230000009471 action Effects 0.000 claims description 3
- 238000009792 diffusion process 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
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000005481 NMR spectroscopy Methods 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 5
- 239000003504 photosensitizing agent Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000001345 alkine derivatives Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- -1 polyoxymethylene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 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
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 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
- 150000001540 azides Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 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
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux 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
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 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
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 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
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- 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
- 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
- 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
-
- 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
- C07D409/02—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
- 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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- 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
- B01J2231/30—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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- B—PERFORMING OPERATIONS; TRANSPORTING
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a preparation method of an azide-alkyne cycloaddition polyacid based photocatalyst, belonging to the technical field of catalysis of POMs (pre-oriented polymer) materials. The self-assembly of Cu (I) -POM-M-based POM constructed by a trihydroxy aminomethane part and Anderson polyacid and 4-pyridylaldehyde serving as connecting nodes is carried out to obtain a Cu (I) -POM-M POM material which is crystallized into orange-red blocky crystals, and redox active Cu (I) in the structure can be used as a catalytic site for catalyzing cycloaddition. In a three-component system with polyacid groups as photosensitizers and Triethylamine (TEA) as electronic sacrificial agents, the three-component system can be used as a heterogeneous catalyst for light-enhanced CuAAC reaction, and the obtained functional material has stable chemical properties and good catalytic performance, and provides possibility for enhancing the catalytic reaction of the CuAAC under visible light.
Description
Technical Field
The invention relates to a preparation method and application of a multi-acid-base photocatalyst based on azide-alkyne cycloaddition, belonging to the technical field of catalysis of POMs (polyoxymethylene) materials.
Background
The azide-alkyne cycloaddition (AAC) synthesized 1,2, 3-triazole compound is an attractive reaction in organic synthesis, and has wide application in the fields of medicine, biotechnology, polymer, material science and the like. In general, the catalytically active Cu (I) sites play an important role in the cycloaddition process, and the reaction between the azide and the terminal alkyne can be catalyzed directly by Cu (I) based salts/compounds or reduced by Cu (II) based compounds to Cu (I) ions during the catalysis process. For the latter method, various reducing agents, such as functional ligands, nanoparticles or bases, need to be supplemented in the system to increase the catalytic activity of the catalyst. Recently, photo-induced electron transfer (PET) of photochemical processes has been developed as a new method of AAC catalysis, i.e. the desired Cu (I) active site is obtained from the photoactive unit to the Cu (II) center by intramolecular PET, effectively avoiding the direct use of labile Cu (I) ions.
Polyoxometallates (POMs) are an important subclass of anionic metal oxygen clusters, and are widely used in the fields of catalysis, photochemistry, biological medicine, magnetism, etc. because of their diverse structures and abundant properties, polyoxometallates are easily modified by various functional groups or metal ions to pay attention. In particular, POMs exhibit good photoactivity, enabling multiple electron transfer to other species under irradiation with visible light, and are considered as excellent photoredox reagents in many photocatalytic systems. Wherein, the organic ligand is introduced into the POMs unit, which not only can be used as a connector to enrich the structural configuration of different sizes and shapes, but also can construct a unique organic-inorganic hybrid material, and the characteristics of inorganic and organic functions are fused into a single system. These multifunctional benign features give them a broader application 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, cocatalysts, initiators or organic solvents. Therefore, the development of novel multifunctional POMs molecular devices is of great importance.
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 alpha-B-Anderson POMs is the presence of three substitutable hydroxyl groups on both sides, which provides a potential functional site for modification by hydroxyl substitution reactions. The compound design includes Anderson [ MMo ] 6 O 18 ](m= Mn, fe, cu, co, ni, cr) cluster as photosensitizer, organic [ (OCH) synthesized by schiff base reaction 2 ) 3 CN＝CH-4-Py]Partially grafted on both sides and the Cu (I)/Cu (II) ions generated by partial oxidation of the Cu (I) salt as a raw material. Oxidized Cu (II) ions can be transferred from [ MnMo as photosensitizer by photoinduced electron transfer 6 O 18 ]The unit regenerates to Cu (I), which 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 a preparation method and application of an azide-alkyne cycloaddition polyacid based photocatalyst, and the metallic copper-Anderson polyacid precursor POMs material obtained by the preparation method is synthesized by adopting a one-pot method, so that the method is simple and easy to operate, and the redox active Cu (I) in the structure can be used as a catalytic site for catalyzing cycloaddition. In a three-component system with polyacid groups as photosensitizers and Triethylamine (TEA) as electronic sacrificial agents, the polyacid groups can be used as heterogeneous catalysts for photo-enhanced 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 above object, the present invention solves the problems existing in the prior art, and adopts the technical scheme that: a preparation method of an azide-alkyne cycloaddition multi-acid based photocatalyst comprises the steps of taking a hydroxyl group as a coordination action site, reacting the hydroxyl group with trihydroxy aminomethane through a hydroxyl substitution reaction to obtain a polyacid precursor EEDQ-M, connecting amino in the obtained polyacid precursor EEDQ-M with 4-pyridine formaldehyde (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 precursor by a one-pot method or poor solvent diffusion method through regulating the proportion of the polyacid ligand POM-M to metal salt and the type and proportion of a reaction solvent, wherein the synthetic route is as follows:
Cu+POM-M→Cu-POM-M；
the prepared POMs material is used as a heterogeneous catalyst for visible light enhanced catalysis (AAC), the novel compound is a copper metal Anderson type polyacid complex with a zero-dimensional framework structure, and the 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;
said polyacid precursor (TBA) 3 [MMo 6 O 18 ((OCH 2 ) 3 CNH 2 ) 2 ]EEDQ-M (one of M= Mn, ni, fe, co), and the structural formula of the club is shown in figure 1;
the polyacid ligand POM-M is (TBA) 3 [MMo 6 O 18 ((OCH 2 ) 3 CN＝CH-4-Py) 2 ](one of m= Mn, ni, fe, co); the three-dimensional structure diagram is shown in figure 2;
the chemical formula of the Cu-POM-M of the POMs material is CuI 2 (TBA) 2 POM-Mn·DMA；CuCl 2 (TBA) 2 POM-Co·DMA；CuCl 2 (TBA) 2 POM-Ni·DMA；CuI 2 (TBA) 2 POM-Fe·DMOne of A.
The preparation method of the azide-alkyne cycloaddition polyacid-based photocatalyst comprises the following steps:
(1) Polyacid ligand POM-M and Cu metal salt are dissolved in 24mL of N, N-Dimethylacetamide (DMA) with volume ratio of 2:1 according to the mol ratio of 0.12:1.2: adding Triethylamine (TEA) with the volume of 0.5mL into the acetonitrile mixed solvent, and adding tetrabutylammonium iodide (TBAI) with the volume of 1.44 mmoL;
(2) The solution is heated to 75 ℃ and N 2 Stirring under protection for 3h, filtering the reacted solvent after stirring, putting 3mL of the solution into a test tube each time, putting the test tube into a wide-mouth bottle filled with a poor solvent, diffusing, and obtaining a target material after crystallization, wherein the reaction time is 7 days;
(3) And (3) separating the crystals prepared in the steps, washing with ethanol, removing the solvent in the pore canal, and drying in air to obtain a 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 solution, adding copper metal salt into 3-5mL of acetonitrile to prepare an upper 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, wherein the volume ratio of acetonitrile to DMA is 1.0-2.0:1.0 to 3.0;
(2) And placing the prepared reaction solution into 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:
formula C of the material 1 108 H 220 Cu 2 I 4 MnMo 6 N 11 O 26 The chemical formula is CuI 2 (TBA) 2 POM-Mn; the crystal structure data of the material are: the crystal is monoclinic system, the space group is C2/C, and the unit cell parameter is α＝90°，β＝90.747°，γ＝90°。
The prepared POMs material is 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 1mmol permillage 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 has taken place, CHCl is added to the reaction tube 3 To dissolve the solid product, the catalyst was separated by centrifugation and the supernatant evaporated in vacuo. By passing through 1 H NMR Spectroscopy (CDCl) 3 As solvent) the reaction was monitored and the conversion of the cycloaddition reaction was monitored by integration of the single peak at 4.3ppm in the starting substrate and the single peak at 5.5ppm in the final product.
The POMs material is selected from the prepared CuI 2 (TBA) 2 POM-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: n in an Anderson type polyacid precursor is used as a connecting node, copper metal salt with high catalytic activity is selected, and a one-pot synthesis method is utilized to obtain a Cu-POM-M POMs material by self-assembly; the novel compound has a zero-dimensional framework structure, has a quasi-first-order reaction rate in a heterogeneous catalysis state, and has very high catalytic activity and reaction stability in the catalysis of visible light enhanced AAC; compared with the prior art, the POMs catalyst which is obtained by using the monovalent copper metal salt which is easy to prepare and low in price to react can be applied to the environment-friendly pollution-free POMs catalyst in the sustainable photocatalytic AAC reaction, and the catalyst can realize the reaction under the condition of no solvent and has no byproduct generation after performance evaluation, so that the catalyst has good application prospect.
Drawings
FIG. 1 is a schematic diagram of the structure of a club of the polyacid precursor EEDQ-M used.
FIG. 2 is a schematic diagram of the three-dimensional 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 of the target material of example 1.
FIG. 5 is a FT-IR comparison plot of the materials of interest of example 1 before and after catalysis.
FIG. 6 is a graph of 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 of substrate development for example 1.
Fig. 9 is a hypothetical catalytic reaction route for catalyzing AAC with the target material of example 1 as a heterogeneous catalyst.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1 (Synthesis of Cu-POM-Mn)
A mixture of the polyacid ligands POM-Mn (0.252 g,0.12 mmol), cuI (0.240 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 for 3 hours under nitrogen at 75 ℃, the solution was filtered, one tube per 3mL of solvent, and the tube was placed in a jar containing poor solvent. After one week, orange-red crystals were obtained, washed with ethanol, dried in air and weighed in 60% yield.
Example 2 (Synthesis of Cu-POM-Co)
The polyacid ligand POM-Co (0.105 g,0.05 mmol) is dissolved in 3mL of DMA solvent to prepare a lower solution, cuI (0.100 g,0.5 mmol) is added into 3mL of acetonitrile to prepare an upper solution, the middle layer is a mixed solution of 6mL of DMA and acetonitrile with the volume ratio of 1:2, the prepared reaction solution is placed in a test tube to react for 1-2 weeks at room temperature, ethanol is used for washing after crystals are separated out, and the yield is calculated after drying and weighing.
Example 3 (Synthesis of Cu-POM-Fe)
A mixture of the 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 for 3 hours under nitrogen at 75 ℃, the solution was filtered, one tube per 3mL of solvent, and the tube was placed in a jar containing 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 were under nitrogen at room temperature to 800℃in a nitrogen stream for 10℃min -1 Thermogravimetric analysis of the temperature rise rate of 1, it can be seen from the TGA profile that the framework of 1 is stable at least 200 ℃. The observed weight loss process has mainly three steps, between 80 and 200 ℃, with a slow weight loss of 6.8% due to two free DMAs and three free H in 1 2 Removal of O molecules (calculated as 6.86%). The greater weight loss of 51.51% (calculated as 51.27%) over the range of 200 to 630 ℃ was attributable to the removal of 5 TEA ions and 4 coordinated I ions. Organic [ (OCH) at a temperature ranging from 630 to 830 DEG C 2 ) 3 CN＝CH-4-Py]Partial decomposition and polyanion disintegration was about 17.8% by weight, the last step in 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 1mmol permillage 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 occurs, by 1 H NMR Spectroscopy (CDCl) 3 As solvent) the reaction was checked and the conversion of the cycloaddition reaction was monitored by integration of the single peak at 4.3ppm in the starting substrate and the single peak at 5.5ppm in the final product.
Example 6 (substrate extension of target Material 1)
The target material 1 shows good photocatalytic activity for various alkyne substrates under the same conditions. When phenyl groups in alkynes replace fluorine atoms or methoxy groups in the para position, the conversion is not significantly changed. The catalytic performance of chlorine atom or methyl substituted alkyne is slightly reduced, the conversion rate of the corresponding product is 91% and 96%, and the conversion rate is 95% or 90% when the carbon chain length is increased to n-butyl or t-butyl. Under the same conditions, the catalyst 1 can also obtain a better final product when phenyl groups in alkyne replace fluorine atoms or methoxy groups in intermediate positions. In addition, 3-vinylthiophene was also selected as a substrate for the study of AAC, and the completely converted product was observed. This result further shows that the catalytic reaction with 1 as catalyst has a very general substrate range for different alkynes and azides, and the synthesized target material 1 shows the potential of further application of photocatalysis to practical applications.
Example 7 (recovery of target Material 1 and cycle experiment)
For heterogeneous catalysts, recyclability was an essential feature considered for practical use, our target material 1 was separated from the reaction by adding ethyl acetate after 4 hours of light irradiation and reused in fresh photocatalytic system with added reaction substrate and TEA under the same conditions, these cycle tests showed that the target material 1 could be reused for 4 cycles without any significant loss of photocatalytic activity, after the end of the reaction, the used catalyst was subjected to FT-IR measurement with a spectrum 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:
(1) Hydroxyl groups are used as coordination action sites, and are reacted with trihydroxy aminomethane through hydroxyl substitution reaction to obtain an Anderson type polyacid precursor EEDQ-M;
(2) Amino in the obtained polyacid precursor EEDQ-M is used as a coordination action site, and is connected with 4-pyridine formaldehyde 4-Py through Schiff base reaction to obtain a polyacid ligand POM-M;
EEDQ-M+4-Py→POM-M
(3) To Cu with high-efficiency reaction site + As a node, the POM-M 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 by regulating and controlling the proportion of the POM-M ligand to the metallic salt and the types and the proportions of reaction solvents, and the synthetic route is as follows:
Cu+POM-M→Cu-POM-M；
(4) The prepared POMs material is used as a heterogeneous catalyst for the application of visible light enhanced catalysis of azide-alkyne cycloaddition reaction, and is copper metal Anderson type polyacid complex with a zero-dimensional framework structure, and the visible light enhanced AAC with quasi-first-order reaction rate in a heterogeneous state shows high catalytic activity and reaction stability;
the polyacid precursor EEDQ-M is divided into (TBA) 3 [MMo 6 O 18 ((OCH 2 ) 3 CNH 2 ) 2 ]One of m= Mn, ni, fe, co, the structural formula of the club is shown in the following figure:
the polyacid-based ligand POM-M has the formula (TBA) 3 [MMo 6 O 18 ((OCH 2 ) 3 CN＝CH-4-Py) 2 ]One of m= Mn, ni, fe, co, the structure of which is shown in the following figure:
the metal salt is selected from one of CuI and CuCl;
the molecular formula of the Cu-POM-M of the POMs material is CuI 2 (TBA) 2 POM-Mn·DMA；CuCl 2 (TBA) 2 POM-Co·DMA；CuCl 2 (TBA) 2 POM-Ni·DMA；CuI 2 (TBA) 2 POM-Fe.DMA.
2. The method for preparing the azide-alkyne cycloaddition polyacid based photocatalyst according to claim 1, which is characterized by comprising the following steps:
(1) The polyacid-based ligand POM-M and the metal salt Cu are dissolved in 24mL of N, N-dimethylacetamide according to the molar ratio of 0.1-0.15:1.0-1.5: adding triethylamine with the volume range of 0.2-1.0mL into the mixed solvent of acetonitrile, wherein the volume ratio of N, N-dimethylacetamide to acetonitrile is 1.5-2.5:0.5-1.5, and adding tetrabutylammonium iodide, wherein the molar range of the tetrabutylammonium iodide is 1.0-2.0mmoL;
(2) The solution is heated to 60-90deg.C, N 2 Stirring under protection for 2-5h, filtering the reacted solvent after stirring, taking 2-4mL of solution, placing the solution into a test tube, placing the test tube into a wide-mouth bottle filled with poor solvent, diffusing, reacting for 5-10 days, and separating out crystals to obtain a target material;
(3) And (3) separating the crystals prepared in the steps, washing with ethanol, removing the solvent in the pore canal, and drying in air to obtain a final product.
3. The method for preparing the azide-alkyne cycloaddition polyacid based photocatalyst according to claim 1, which is characterized by comprising the following steps:
(1) Dissolving a polyacid-based ligand POM-M in 3-5mL of N, N-dimethylacetamide solvent to prepare a lower solution, adding copper metal salt into 3-5mL of acetonitrile to prepare an upper solution, wherein the middle layer is a mixed solution of N, N-dimethylacetamide and acetonitrile, and the mol ratio of the polyacid-based ligand POM-M to the metal salt Cu is 0.05-0.15:0.1-1.5, wherein the volume ratio of acetonitrile to N, N-dimethylacetamide is 1.0-2.0:2.0 to 10.0;
(2) And placing the prepared reaction solution into 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, which is used for catalyzing the azide-alkyne cycloaddition reaction by visible light, comprises the following catalytic steps:
(1) At room temperature, a 20W household incandescent lamp is used as a reaction light source, 1mmol per mill catalyst, 138 mu L of substrate benzyl azide, wherein the amount of the substrate benzyl azide in 138 mu L is 1.0mmol, 114 mu L of phenylacetylene, wherein the amount of the phenylacetylene in 114 mu L is 1.0mmol, and 7.1mL of triethylamine are added into a 10mL quartz reaction tube for heterogeneous photocatalysis;
(2) After the AAC reaction has taken place, CHCl is added to the reaction tube 3 To dissolve the solid product, separating the catalyst by centrifugation and evaporating the supernatant in vacuo, by 1 The reaction was detected by H NMR spectroscopy, wherein 1 H NMR Spectroscopy Using CDCl 3 The conversion of the AAC reaction was monitored as solvent by integration of the single peak at 4.3ppm in the starting substrate and the single peak at 5.5ppm in the final product.
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