CN109134877A - A kind of exhibiting optical function composite material, preparation method and photocatalytic applications of connecting - Google Patents
A kind of exhibiting optical function composite material, preparation method and photocatalytic applications of connecting Download PDFInfo
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- CN109134877A CN109134877A CN201811019700.XA CN201811019700A CN109134877A CN 109134877 A CN109134877 A CN 109134877A CN 201811019700 A CN201811019700 A CN 201811019700A CN 109134877 A CN109134877 A CN 109134877A
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- optical function
- composite material
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- ntb
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- 230000001747 exhibiting effect Effects 0.000 title claims abstract description 69
- 230000003287 optical effect Effects 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 150000003462 sulfoxides Chemical class 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 77
- 238000007146 photocatalysis Methods 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 24
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 238000000354 decomposition reaction Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 235000004237 Crocus Nutrition 0.000 claims description 10
- 241000596148 Crocus Species 0.000 claims description 10
- 238000010523 cascade reaction Methods 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000003504 photosensitizing agent Substances 0.000 claims description 10
- 239000007853 buffer solution Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- -1 Wherein Chemical compound 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 150000004832 aryl thioethers Chemical class 0.000 claims description 4
- 238000002050 diffraction method Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000001425 triazolyl group Chemical group 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 229920006324 polyoxymethylene Polymers 0.000 description 35
- 238000001907 polarising light microscopy Methods 0.000 description 34
- 239000000047 product Substances 0.000 description 15
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000013259 porous coordination polymer Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000001052 transient effect Effects 0.000 description 5
- BZSVVCFHMVMYCR-UHFFFAOYSA-N 2-pyridin-2-ylpyridine;ruthenium Chemical compound [Ru].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 BZSVVCFHMVMYCR-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910004882 Na2S2O8 Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 206010020772 Hypertension Diseases 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 3
- 229940124549 vasodilator Drugs 0.000 description 3
- 239000003071 vasodilator agent Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002371 cardiac agent Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- CZCSLHYZEQSUNV-UHFFFAOYSA-N [Na].OB(O)O Chemical compound [Na].OB(O)O CZCSLHYZEQSUNV-UHFFFAOYSA-N 0.000 description 1
- 230000000507 anthelmentic effect Effects 0.000 description 1
- 230000000879 anti-atherosclerotic effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 230000000767 anti-ulcer Effects 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940126409 proton pump inhibitor Drugs 0.000 description 1
- 239000000612 proton pump inhibitor Substances 0.000 description 1
- 239000004089 psychotropic agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
Abstract
The invention discloses a kind of exhibiting optical function composite materials, preparation method and photocatalytic applications of connecting.The exhibiting optical function composite material has following chemical formula: [Cu2(NTB)2(W6O19)] DMF, NTB is 4- (4H-1,2,4- triazole-4-yls)-N, N- bis- [4- (4H-1,2,4- triazole-4-yls) phenyl]-aniline, and the skeleton symbol of NTB is as follows:The exhibiting optical function composite material crystallization is in monoclinic system, and space group is P2 (1)/c, and cell parameter is Exhibiting optical function composite material of the invention has the sequential catalyst performance that photochemical catalyzing generates oxygen and selectively oxidizing sulfur ether prepares sulfoxide, and preparation method is simple, yield is high.
Description
Technical field
The present invention relates to a kind of exhibiting optical function composite materials, more particularly to a kind of exhibiting optical function POM@PCP composite material
And preparation method thereof and the composite material series connection photocatalysis in application, belong to catalysis material technical field.
Background technique
Sulfide oxidation can generate two kinds of products of sulfoxide and sulfone, and wherein sulfoxide is among a kind of highly useful organic synthesis
Body, they are in antiulcer (proton pump inhibitor), antibacterial, antimycotic, antiatherosclerosis, anthelmintic, anti-hypertension, heart
Drug, psychotropic agent and vasodilator etc. play an important role.Sulfoxide is usually by corresponding sulfide selectivity oxygen
What change was prepared, generally use the oxidation system of halogen, nitric acid or nitrate.However, it can be noted that these oxidant oxygen
Change system along with many unfavorable factors, such as reaction time length, severe reaction conditions, oxidant it is expensive, be more toxic, by-product
The disadvantages of object is more, seriously polluted.People make great efforts always development green, mild, economic selective catalytic oxidation system in recent years
System, wherein starting to be valued by people by the green clean catalytic oxidization system of oxidant of molecular oxygen.
Water is decomposed using manual simulation's photosynthesizer and prepares oxygen, is a kind of not only economic but also promising side
Method, and caused the concern of numerous researchers.One of half-reaction of water decomposition is water oxidation reaction, due to its process
Complexity is always the bottleneck for restricting water decomposition.It becomes so finding efficient, stable water oxidation catalyst in order to break through the bottleneck
Key.
In recent years, have the characteristics that the tandem reaction synthetic strategy of greenization, high efficiency and Atom economy causes
Art circle and industry keen interest achieve many important achievements, become Synthetic Organic Chemistry research Disciplinary Frontiers it
One.The more traditional substep synthesis of tandem reaction advantageously such as eliminates separation, the purification process of intermediate product, makes multiple reactions
Process occurs etc. in same reactor.Catalysis multicomponent tandem reaction can efficiently construct that structure is complicated from simple one step of raw material with
The organic molecule of various structures has attracted the great interest and extensive concern of chemists.But it yet there are no related catalysis
The report of the material of multicomponent tandem reaction.
Summary of the invention
The main purpose of the present invention is to provide a kind of exhibiting optical function POM@PCP composite material and preparation method, with gram
Take the deficiencies in the prior art.
Another object of the present invention is to provide aforementioned exhibiting optical function POM@PCP composite material answering in series connection photocatalysis
With.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of exhibiting optical function composite materials, with following chemical formula: [Cu2(NTB)2
(W6O19)] DMF, wherein DMF N, N '-dimethylformamide, NTB are 4- (4H-1,2,4- triazole-4-yls)-N, N- bis-
[4- (4H-1,2,4- triazole-4-yls) phenyl]-aniline, the skeleton symbol of NTB are as follows:
In monoclinic system (monoclinic), space group is P2 (1)/c, structure cell ginseng for the exhibiting optical function composite material crystallization
Number is β=111.272 (8) °,
Further, the basic structure of the exhibiting optical function composite material is three-dimensional net structure, wherein CuIIon difference
It is coordinated with four nitrogen-atoms from four triazolyls, ligand NTB and CuIIon forms three-dimensional net structure, in crystallography
Two kinds of the regular pore canal, [W of oxidized form are shown along b axis direction6O19]2–Polyoxoanion occupies one of duct,
Another duct is convenient for the experiment of photocatalysis tandem reaction.
The embodiment of the invention also provides the preparation methods of the exhibiting optical function composite material comprising: by molar ratio
It is sufficiently mixed in a solvent for the polyoxometallate of 1:5:5~1:5:10, mantoquita and NTB ligand, later at 110~130 DEG C
60~84h of lower curing process obtains crocus bulk crystals, as the exhibiting optical function composite material.
The embodiment of the invention also provides the exhibiting optical function composite materials in photochemical catalyzing or selective photocatalysis
Application in synthesizing sulfoxide by oxidation of thioether.
Further, the embodiment of the invention also provides the exhibiting optical function composite material in prepare oxygen and selectivity system
Purposes in standby sulfoxide.
The embodiment of the invention also provides a kind of photocatalysis Decomposition aquatic products VPO catalysts comprising exhibiting optical function above-mentioned is multiple
Condensation material.
Further, the embodiment of the invention also provides a kind of photocatalysis Decomposition aquatic products oxygen methods comprising: it will be above-mentioned
Exhibiting optical function composite material is as catalyst, and sodium peroxydisulfate is as electron acceptor, [Ru (bpy)3]Cl2As photosensitizer, with visible
Light is light source, in borate buffer system, carries out photochemical catalyzing and obtains oxygen.
It connects the embodiment of the invention also provides a kind of photocatalysis and synthesizes the catalyst of sulfoxide, it includes smooth functions above-mentioned
Property composite material.
Further, the embodiment of the invention also provides a kind of series connection photocatalysis Decomposition aquatic products oxygen and selectivity synthesis sulfoxide
Method comprising: using exhibiting optical function composite material above-mentioned as catalyst, aryl thioethers are as reaction substrate, persulfuric acid
Sodium is as electron acceptor, [Ru (bpy)3]Cl2As photosensitizer, using visible light as light source, in borate buffer system, gone here and there
Join light-catalyzed reaction.
Compared with prior art, the invention has the advantages that
(1) exhibiting optical function POM PCP composite material provided by the invention realizes photocatalysis Decomposition aquatic products oxygen and choosing for the first time
Selecting property prepares the tandem reaction of sulfoxide, has in terms of the pharmaceutical synthesis such as anti-hypertension, cardiac drug and vasodilator good
Application prospect；
(2) the NTB ligand that the present invention uses not only has three-dimensional spiral paddle structure, electron rich and structural stability, and
And there is high fluorescence property and photoluminescence efficiency, in the series connection photocatalysis of the exhibiting optical function POM@PCP composite material
Play the role of in the process vital；
(3) the Lindqvist type polyacid enhancing filled in exhibiting optical function POM@PCP composite material duct provided by the invention
The structure and chemical property stability of composite material, to improve photocatalysis efficiency and reusable property；
(4) the preparation process synthesis step of exhibiting optical function POM@PCP composite material provided by the invention it is simple, it is easy to operate,
It consumes energy less, yield height, synthesis material is cheap and easy to get, and reaction condition is mild, and selectivity is good, is suitble to the need of industrial mass production
It asks.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention 1 obtains [Cu2(NTB)2(W6O19)] the series connection photocatalysis schematic diagram of DMF.
Fig. 2 is that the embodiment of the present invention 1 obtains [Cu2(NTB)2(W6O19)] the crystal structure figure of DMF.
Fig. 3 is that the embodiment of the present invention 1 obtains [Cu2(NTB)2(W6O19)] transient photocurrents-time plot of DMF.
Fig. 4 is that the embodiment of the present invention 1 obtains [Cu2(NTB)2(W6O19)] oxygen-producing amount of DMF change over time curve graph with
And photocatalysis oxygen generator reason figure.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution as follows will be further explained the technical solution, its implementation process and principle etc..
Polyoxometallate (Polyoxometalates, POMs) abbreviation polyacid is that oxo transition metal cluster is one kind in the past
The multi-metal oxygen cluster compound that basic unit is formed.It can not compare since polyoxometallate has in terms of physics, chemical property
Quasi- characteristic so that its catalysis, drug, nanosecond science and technology and in terms of be widely used.In addition, porous match
Position polymer (Porous Coordination Polymers, PCPs) has the pore structure similar to molecular sieve, big due to it
Specific surface area, the adjustability of structure snd size and excellent thermal stability and the advantages that chemical stability, PCPs material is
It is used in the fields such as heterogeneous catalysis, separating-purifying, ion exchange and gas storage.
Water decomposition is produced into oxygen reaction and sulfide oxidation reaction organically combines and constitutes sequential catalyst reaction, is to realize selectivity system
The new method of standby sulfoxide.
A kind of exhibiting optical function POM@PCP composite material that the one aspect of the embodiment of the present invention provides, with followingization
Formula: [Cu2(NTB)2(W6O19)] DMF, wherein DMF N, N '-dimethylformamide, NTB are 4- (4H-1,2,4- triazoles-
4- yl)-N, N- bis- [4- (4H-1,2,4- triazole-4-yls) phenyl]-aniline, the skeleton symbol of NTB is as follows:
Exhibiting optical function POM@PCP composite material crystallization in monoclinic system (monoclinic), space group be P2 (1)/
C, cell parameter areβ=111.272 (8) °,
Further, the basic structure of the exhibiting optical function POM@PCP composite material is three-dimensional net structure, wherein CuI
Ion is coordinated with four nitrogen-atoms from four triazolyls respectively, ligand NTB and CuIIon forms three-dimensional net structure,
Two kinds of the regular pore canal, [W of oxidized form are shown along b axis direction in crystallography6O19]2–Polyoxoanion occupies wherein one
Kind duct, another duct are convenient for the experiment of photocatalysis tandem reaction.
The embodiment of the present invention another aspect provides the preparation method of exhibiting optical function composite material above-mentioned, packet
It includes: polyoxometallate, mantoquita and NTB ligand that molar ratio is 1:5:5~1:5:10 being sufficiently mixed in a solvent, Zhi Hou
60~84h of curing process at 110~130 DEG C obtains crocus bulk crystals, as the exhibiting optical function composite material.
In some embodiments, the molar ratio of the polyoxometallate, mantoquita and NTB ligand is (0.01~0.05):
(0.05~0.10): (0.05~0.10), specifically, the amount of the substance of the polyoxometallate, mantoquita and NTB ligand is distinguished
For 0.01~0.05mmol, 0.05~0.10mmol and 0.05~0.10mmol.
Further, the mantoquita includes nitric hydrate copper, preferably Gerhardite, but not limited to this.
Further, the polyoxometallate includes (TBA)4[W10O32], but not limited to this.
Further, the solvent includes DMF, water etc., but not limited to this.
In some embodiments, the preparation method includes: to be uniformly mixed mantoquita, TPB ligand and polyoxometallate
Mixture is obtained, is then added in solvent, wherein the amount ratio of the mixture and solvent is 60mg:2mL~90mg:5mL, is used
1~2molL–1HCl regulation system pH value be 2.5~3.0,20~40min of stirring at normal temperature, after being sufficiently mixed, then carry out
Curing process.
In some more specific case study on implementation, the preparation method includes: by Gerhardite, NTB ligand
With (TBA)4[W10O32] polyacid be uniformly mixed obtain mixture, be then added in DMF and water mixed solvent, stirring at normal temperature 20~
40min, with 1~2molL–1HCl regulation system pH value be 2.5~3.0, obtain mixed liquor；It is baked at 120 DEG C later
Then 60~84h separates solid；Above-mentioned solid is washed 3~5 times with DMF, crocus bulk crystals material can be obtained,
The as described exhibiting optical function POM@PCP composite material.
The other side of the embodiment of the present invention additionally provides aforementioned exhibiting optical function POM@PCP material in photochemical catalyzing
With the application in selective photocatalysis synthesizing sulfoxide by oxidation of thioether.
Preferably, the application includes that series connection photochemical catalyzing generation oxygen and selectively oxidizing sulfur ether are prepared in sulfoxide
Application.
Further, the embodiment of the invention also provides the exhibiting optical function POM@PCP materials in preparing oxygen and selection
Property prepares the purposes in sulfoxide.
The other side of the embodiment of the present invention additionally provides a kind of photocatalysis Decomposition aquatic products VPO catalysts comprising aforementioned
Exhibiting optical function composite material.
Further, the other side of the embodiment of the present invention additionally provides a kind of photocatalysis Decomposition aquatic products oxygen method,
It include: using exhibiting optical function composite material above-mentioned as catalyst, sodium peroxydisulfate is as electron acceptor, [Ru (bpy)3]Cl2As
Photosensitizer in borate buffer system, carries out the experiment of photocatalysis oxygen, photochemical catalyzing obtains oxygen using visible light as light source
Gas.
Further, in some more specific case study on implementation, the method for the photocatalysis Decomposition aquatic products oxygen include: by
The exhibiting optical function POM@PCP material is as catalyst, sodium peroxydisulfate (Na2S2O8) it is used as electron acceptor, tris (bipyridine) ruthenium
([Ru(bpy)3]Cl2) it is used as photosensitizer, using LED light as light source, sodium borate buffer solution (8.0 × 10–2M total volume) is
10mL, degassing process 10min in argon atmosphere, then carry out light-catalyzed reaction in the case where a LED light is irradiated, and the oxygen of generation is logical
GC7900 gas chromatographic detection is crossed, argon gas is as carrier gas.
The other side of the embodiment of the present invention additionally provides a kind of catalyst of photocatalysis series connection synthesis sulfoxide, it includes
Exhibiting optical function composite material above-mentioned.
Further, the other side of the embodiment of the present invention additionally provides a kind of series connection photocatalysis Decomposition aquatic products oxygen and choosing
The method of selecting property synthesis sulfoxide comprising: using exhibiting optical function composite material above-mentioned as catalyst, aryl thioethers are as reaction
Substrate, sodium peroxydisulfate is as electron acceptor, [Ru (bpy)3]Cl2As photosensitizer, using visible light as light source, in borate buffer body
In system, series connection light-catalyzed reaction is carried out.
Further, in some more specific case study on implementation, the light-catalysed preparation method of series connection includes: by institute
The exhibiting optical function POM@PCP material stated is used as reaction substrate, sodium peroxydisulfate as catalyst, aryl thioethers (Ar-S-Ar)
(Na2S2O8) it is used as electron acceptor, tris (bipyridine) ruthenium ([Ru (bpy)3]Cl2) it is used as photosensitizer, using LED light as light source, boric acid
Sodium buffer solution (8.0 × 10–2M total volume) is 10mL, degassing process 10min in argon atmosphere, is then shone in a LED light
Lower carry out light-catalyzed reaction is penetrated, then by separation, extraction, concentration, and carries out nuclear-magnetism test.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated, the method in the following example, is the conventional method of this field unless otherwise instructed.
Embodiment 1: the preparation of exhibiting optical function POM@PCP composite material
By (TBA)4[W10O32](33.2mg,0.01mmol)、Cu(NO3)2·3H2O (12.1mg, 0.05mmol) and NTB
(22.3mg, 0.05mmol) is added in the mixed liquor of N,N-dimethylformamide (DMF, 2.0mL) and water (0.5mL) and is stirred
It mixes, uses 1molL–1The pH value of HCl regulation system is 2.6, then above-mentioned suspension is added to one by stirring at normal temperature 20min
In the ptfe autoclave of 25mL, 72h is baked at 120 DEG C, is finally cooled to room temperature, it is blocky brilliant that crocus can be obtained
Body washs 3 times with DMF and is dried at room temperature for, and yield is about 49%.
Embodiment 2: the preparation of exhibiting optical function POM@PCP composite material
By (TBA)4[W10O32](33.2mg,0.01mmol)、Cu(NO3)2·3H2O (12.1mg, 0.05mmol) and NTB
(44.6mg, 0.10mmol) is added in the mixed liquor of N,N-dimethylformamide (DMF, 3.0mL) and water (2.0mL) and is stirred
It mixes, uses 1molL–1The pH value of HCl regulation system is 2.5, then above-mentioned suspension is added to one by stirring at normal temperature 30min
In the ptfe autoclave of 25mL, 84h is baked at 110 DEG C, is finally cooled to room temperature, it is blocky brilliant that crocus can be obtained
Body washs 3 times with DMF and is dried at room temperature for, and yield is about 51%.
Embodiment 3: the preparation of exhibiting optical function POM@PCP composite material
By (TBA)4[W10O32](33.2mg,0.01mmol)、Cu(NO3)2·3H2O (12.1mg, 0.05mmol) and NTB
(26.8mg, 0.06mmol) is added in the mixed liquor of N,N-dimethylformamide (DMF, 3.0mL) and water (1.0mL) and is stirred
It mixes, uses 1molL–1The pH value of HCl regulation system is 3.0, then above-mentioned suspension is added to one by stirring at normal temperature 40min
In the ptfe autoclave of 25mL, 60h is baked at 130 DEG C, is finally cooled to room temperature, it is blocky brilliant that crocus can be obtained
Body washs 3 times with DMF and is dried at room temperature for, and yield is about 50%.
Embodiment 4: the preparation of exhibiting optical function POM@PCP composite material
By (TBA)4[W10O32](33.2mg,0.01mmol)、Cu(NO3)2·3H2O (12.1mg, 0.05mmol) and NTB
(35.7mg, 0.08mmol) is added in the mixed liquor of N,N-dimethylformamide (DMF, 2.0mL) and water (1.0mL) and is stirred
It mixes, uses 1molL–1The pH value of HCl regulation system is 2.8, then above-mentioned suspension is added to one by stirring at normal temperature 25min
In the ptfe autoclave of 25mL, 75h is baked at 115 DEG C, is finally cooled to room temperature, it is blocky brilliant that crocus can be obtained
Body washs 3 times with DMF and is dried at room temperature for, and yield is about 49%.
Embodiment 5: the preparation of exhibiting optical function POM@PCP composite material
By (TBA)4[W10O32](33.2mg,0.01mmol)、Cu(NO3)2·3H2O (12.1mg, 0.05mmol) and NTB
(31.2mg, 0.07mmol) is added in the mixed liquor of N,N-dimethylformamide (DMF, 2.5mL) and water (0.5mL) and is stirred
It mixes, uses 1molL–1The pH value of HCl regulation system is 2.7, then above-mentioned suspension is added to one by stirring at normal temperature 35min
In the ptfe autoclave of 25mL, 72h is baked at 120 DEG C, is finally cooled to room temperature, it is blocky brilliant that crocus can be obtained
Body washs 3 times with DMF and is dried at room temperature for, and yield is about 48%.
Embodiment 6: the preparation of exhibiting optical function POM@PCP composite material
By (TBA)4[W10O32](33.2mg,0.01mmol)、Cu(NO3)2·3H2O (12.1mg, 0.05mmol) and NTB
(40.1mg, 0.09mmol) is added in the mixed liquor of N,N-dimethylformamide (DMF, 2.5mL) and water (1.0mL) and is stirred
It mixes, uses 1molL–1The pH value of HCl regulation system is 2.6, then above-mentioned suspension is added to one by stirring at normal temperature 30min
In the ptfe autoclave of 25mL, 65h is baked at 125 DEG C, is finally cooled to room temperature, it is blocky brilliant that crocus can be obtained
Body washs 3 times with DMF and is dried at room temperature for, and yield is about 47%.
Exhibiting optical function POM@PCP composite material obtained in the embodiment of the present invention 1 is taken to further characterize, process and result
It is as follows:
(1) crystal structure determination
Under petrographic microscope, the monocrystalline for choosing suitable size at room temperature carries out the experiment of X-ray single crystal diffraction.Crystallography
Data are collected by Agilent Supernova type X-ray single crystal diffractometer, which has graphite monochromator and copper target light
Source.The parsing of mono-crystalline structures is calculated by SHELXS (direct method) program in Olex2 software, and the refine of structure passes through Olex2
SHELXL program (complete matrix least square method) in software calculates.All non-hydrogen atoms pass through anisotropy refine.By several
Hydrogen atom is added in structure by the mode of what plus hydrogen, and with parameters self-tuning model come refine, detailed axonometry data are shown in
Table 1, important bond distance and bond angle data are shown in Table 2 and table 3, and crystal structure is shown in Fig. 1 and Fig. 2.
The predominant crystal data of the obtained exhibiting optical function POM@PCP composite material of 1 embodiment of table 1
aR1=Σ | | Fo|–|Fc||/Σ|Fo|.b wR2=| Σ w (| Fo|2–|Fc|2)|/Σ|w(Fo)2|1/2,where w
=1/ [σ2(Fo 2)+(aP)2+ bP] .P=(Fo 2+2Fc 2)/3.
The main bond distance of the obtained exhibiting optical function POM@PCP composite material of 2 embodiment of table 1
* symmetry operation code: #1-x ,-y+1 ,-z+1；#2–x+2,–y,–z+1；#3x–1,–y+1/2,z–1/2；#4x–1,y,
z；#5x+1,–y+1/2,z+1/2；#6x+1,y,z.
Main bond angle [°] * of the obtained exhibiting optical function POM@PCP material of 3 embodiment of table 1
* symmetry operation code: #1-x ,-y+1 ,-z+1；#2–x+2,–y,–z+1；#3x–1,–y+1/2,z–1/2；#4x–1,y,
z；#5x+1,–y+1/2,z+1/2；#6x+1,y,z.
(2) transient photocurrents-time graph test
Transient photocurrents-time graph test result existsIt is measured on XM type electrochemical workstation.Using mark
Quasi- three-electrode system, working electrode are conventionally made, 0.1molL–1KCl solution as supporting electrolyte.
300W xenon lamp is as excitation light source.
Fig. 3 is [Cu2(NTB)2(W6O19)] transient photocurrents-time plot of DMF, the light is tested respectively
Functional POM PCP material (name are as follows: CuW-NTB), CuW-NTB+ [Ru (bpy)3]Cl2With bare electrode transient photocurrents-when
Half interval contour, show in Fig. 3: during photocatalysis Decomposition aquatic products oxygen, the exhibiting optical function POM PCP material plays light and urges
The effect of agent.
(3) photocatalysis is tested
(a) photocatalysis Decomposition aquatic products oxygen is tested
The experiment of photocatalysis Decomposition aquatic products oxygen after the irradiation of PL-LED100_ high-power LED light source by measuring.Photocatalysis produces oxygen and surveys
Examination is carried out in the quartz glass bottle of 25mL.Using the exhibiting optical function POM@PCP material as catalyst (5.0mg),
Sodium peroxydisulfate is as electron acceptor (Na2S2O8, 6.0mg), tris (bipyridine) ruthenium is as photosensitizer ([Ru (bpy)3]Cl2, 10.0mg),
Using LED light as light source, sodium borate buffer solution system (8.0 × 10–2M, 10mL, pH=9), degassing process in argon atmosphere
10min, then a LED light (luminous intensity=16mW, beam diameter=2cm, edge filter λ >=420nm) irradiation under into
Row light-catalyzed reaction, the oxygen of generation is by being equipped withThe GC7900 gas-chromatography of molecular sieve (2m × 3mm) and thermal conductivity detector (TCD)
Detection, argon gas is as carrier gas.Oxygen-producing amount is calculated by external standard method.
Fig. 4 is [Cu2(NTB)2(W6O19)] DMF (and name are as follows: CuW-NTB) oxygen-producing amount change over time curve graph with
And photocatalysis oxygen generator reason is schemed, show in Fig. 4: in 0~25min, the oxygen-producing amount of the material increases increase with time；25
In~30min, oxygen-producing amount is held essentially constant.
(b) one kettle way series connection photocatalysis test
Series connection photocatalysis experiment after the irradiation of PL-LED100_ high-power LED light source by measuring.Series connection photocatalysis test be
It is carried out in the quartz glass bottle of 25mL.Using the exhibiting optical function POM@PCP material as catalyst (5.0mg), aryl sulphur
Ether is as reaction substrate (Ar-S-Ar, 8.0 μm of ol), and sodium peroxydisulfate is as electron acceptor (Na2S2O8, 6.0mg), tris (bipyridine) ruthenium
As photosensitizer ([Ru (bpy)3]Cl2, 10.0mg), using LED light as light source, sodium borate buffer solution system (8.0 × 10– 2M, 10mL, pH=9), degassing process 10min in argon atmosphere, then with LED light (luminous intensity=16mW, beam diameter=
2cm, edge filter λ >=420nm) irradiation 30min after, remove catalyst, extraction and separation, concentrated by rotary evaporation, photocatalysis yield use1HNMR is characterized, and test result is as shown in table 4.
4 exhibiting optical function POM@PCP composite material of table is for light-catalysed conversion ratio of connecting
In conclusion exhibiting optical function POM PCP composite material of the invention realize for the first time photocatalysis Decomposition aquatic products oxygen with
Selectivity prepares the tandem reaction application of sulfoxide, has in terms of the pharmaceutical synthesis such as anti-hypertension, cardiac drug and vasodilator
There is good application prospect；And preparation process synthesis step is simple, easy to operate, energy consumption less, yield it is high, synthesis material is inexpensively easy
, reaction condition is mild, and selectivity is good, is suitble to the demand of industrial mass production；Exhibiting optical function POM@PCP of the invention is compound
The Lindqvist type polyacid filled in material duct enhances the structure and chemical property stability of composite material, to improve
Photocatalysis efficiency and reusable property.Particularly, NTB ligand of the present invention not only have three-dimensional spiral paddle structure,
Electron rich and structural stability, and there is high fluorescence property and photoluminescence efficiency, in the exhibiting optical function POM@
Play the role of in the series connection photocatalytic process of PCP composite material vital.
In addition, inventor also refers to the mode of Examples 1 to 6, with the other raw materials and item listed in this specification
Part etc. is tested, and equally obtains the tandem reaction application that sulfoxide is prepared with photocatalysis Decomposition aquatic products oxygen and selectivity
Exhibiting optical function POM@PCP composite material.
Remaining embodiment obtained product is characterized using same characteristic manner, also can get similar to Example 1
Test result.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of exhibiting optical function composite material, it is characterised in that it has following chemical formula: [Cu2(NTB)2(W6O19)] DMF,
Wherein, DMF N, N '-dimethylformamide, NTB be 4- (4H-1,2,4- triazole-4-yls)-N, N- bis- [4- (and 4H-1,2,4- tri-
Azoles -4- base) phenyl]-aniline, the skeleton symbol of NTB is as follows:
The exhibiting optical function composite material crystallization is in monoclinic system, and space group is P2 (1)/c, and cell parameter is β=111.272 (8) °,
2. exhibiting optical function composite material according to claim 1, it is characterised in that: the base of the exhibiting optical function composite material
This structure is three-dimensional net structure, wherein CuIIon is coordinated with four nitrogen-atoms from four triazolyls respectively, ligand NTB
With CuIIon forms three-dimensional net structure, shows two kinds of regular pore canal along b axis direction in crystallography, wherein oxygen
[the W of change type6O19]2–Polyoxoanion occupies one of duct, and another duct is at least used to carry out photocatalysis tandem reaction.
3. the preparation method of exhibiting optical function composite material as claimed in claim 1 or 2, characterized by comprising:
Polyoxometallate, mantoquita and NTB ligand that molar ratio is 1:5:5~1:5:10 are sufficiently mixed in a solvent, later
60~84h of curing process at 110~130 DEG C obtains crocus bulk crystals, as the exhibiting optical function composite material.
4. the preparation method of exhibiting optical function composite material according to claim 3, it is characterised in that: the polyoxometallic acid
The molar ratio of salt, mantoquita and NTB ligand is (0.01~0.05): (0.05~0.10): (0.05~0.10)；
And/or the mantoquita includes nitric hydrate copper, preferably Gerhardite；And/or the polyoxometallate packet
Include (TBA)4[W10O32]；And/or the solvent includes DMF and/or water.
5. the preparation method of exhibiting optical function composite material according to claim 3, characterized by comprising: by mantoquita, TPB
Ligand and polyoxometallate, which are uniformly mixed, obtains mixture, is then added in solvent, wherein the use of the mixture and solvent
Amount is than being 60mg:2mL~90mg:5mL, with 1~2molL–1HCl regulation system pH value be 2.5~3.0, stirring at normal temperature
20~40min after being sufficiently mixed, then carries out curing process.
6. exhibiting optical function composite material as claimed in claim 1 or 2 is in photochemical catalyzing or selective photocatalysis sulfur oxide
Ether synthesizes the application in sulfoxide；Preferably, the application includes that series connection photochemical catalyzing generates oxygen and selective oxidation of sulfur
Ether prepares the application in sulfoxide.
7. a kind of photocatalysis Decomposition aquatic products VPO catalysts, it is characterised in that compound comprising exhibiting optical function of any of claims 1 or 2
Material.
8. a kind of photocatalysis Decomposition aquatic products oxygen method, characterized by comprising: answer exhibiting optical function of any of claims 1 or 2
Condensation material is as catalyst, and sodium peroxydisulfate is as electron acceptor, [Ru (bpy)3]Cl2As photosensitizer, using visible light as light source,
In borate buffer system, carries out photochemical catalyzing and obtain oxygen.
9. a kind of catalyst of photocatalysis series connection synthesis sulfoxide, it is characterised in that include exhibiting optical function of any of claims 1 or 2
Composite material.
10. a kind of method of connect photocatalysis Decomposition aquatic products oxygen and selectivity synthesis sulfoxide, characterized by comprising: right
Exhibiting optical function composite material described in asking 1 or 2 is as catalyst, and aryl thioethers are as reaction substrate, and sodium peroxydisulfate is as electronics
Receptor, [Ru (bpy)3]Cl2As photosensitizer, using visible light as light source, in borate buffer system, it is anti-to carry out series connection photocatalysis
It answers.
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