CN110437459A - A kind of catalytic degradation mustard gas analogies material and preparation method thereof - Google Patents
A kind of catalytic degradation mustard gas analogies material and preparation method thereof Download PDFInfo
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- CN110437459A CN110437459A CN201910706558.4A CN201910706558A CN110437459A CN 110437459 A CN110437459 A CN 110437459A CN 201910706558 A CN201910706558 A CN 201910706558A CN 110437459 A CN110437459 A CN 110437459A
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- mustard gas
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- silver
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- 239000000463 material Substances 0.000 title claims abstract description 53
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 230000015556 catabolic process Effects 0.000 title claims abstract description 39
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 11
- -1 sulfoxide compound Chemical class 0.000 claims abstract description 9
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- GBNVXYXIRHSYEG-UHFFFAOYSA-N 1-chloro-2-ethylsulfanylethane Chemical compound CCSCCCl GBNVXYXIRHSYEG-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 150000003378 silver Chemical class 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000013256 coordination polymer Substances 0.000 claims description 2
- 229920001795 coordination polymer Polymers 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims 1
- 231100000252 nontoxic Toxicity 0.000 abstract description 5
- 230000003000 nontoxic effect Effects 0.000 abstract description 5
- 239000013259 porous coordination polymer Substances 0.000 abstract description 3
- 239000002575 chemical warfare agent Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- 238000007210 heterogeneous catalysis Methods 0.000 abstract 1
- PGWMQVQLSMAHHO-UHFFFAOYSA-N sulfanylidenesilver Chemical class [Ag]=S PGWMQVQLSMAHHO-UHFFFAOYSA-N 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- LIPRCTSGLFLUNJ-UHFFFAOYSA-N 1-chloro-2-ethylsulfinylethane Chemical compound CCS(=O)CCCl LIPRCTSGLFLUNJ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 231100000004 severe toxicity Toxicity 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910017488 Cu K Inorganic materials 0.000 description 2
- 229910017541 Cu-K Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- SSZGZNMFUXOAFG-UHFFFAOYSA-N 1-chloro-2-ethylsulfonylethane Chemical compound CCS(=O)(=O)CCCl SSZGZNMFUXOAFG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 238000013507 mapping 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- B01J35/39—
-
- 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
- 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
- B01J2531/17—Silver
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of new catalytic degradation mustard gas analogies materials and preparation method thereof, belong to the crossing domain of nano material, Coordinative Chemistry and catalytic chemistry.The material is the silver-colored sulphur cluster base Porous coordination polymer of four tooth porphyrin ligand bridgings using 12 core silver sulphur clusters as node.The chemical formula of the compound is [Ag12(S t Bu)6(CF3COO)6(TPyP)4] n , belong to anorthic system, space group isP-1.The material has good catalytic degradation performance to mustard gas analogies, can selective photocatalysis degradation mustard gas analogies be in a short time nontoxic sulfoxide compound, be 1.5 minutes in oxygen atmosphere half-life, be 6 minutes under air environment.And the material is with good stability, can be recycled as heterogeneous catalysis.It is had a good application prospect in terms of chemical warfare agent catalytic degradation.
Description
Technical field
The invention belongs to the crossing domains of nano material, Coordinative Chemistry and catalytic chemistry, and in particular to a kind of new catalytic
Degradation mustard gas analogies material and preparation method thereof.
Background technique
Since the World War I, chemical warfare agent (CWAs) causes to seriously threaten to international community always.2,2'- bis-
Chlorine diethyl thioether (being commonly called as mustard gas or HD) is a kind of hypertoxic foaming agent, can be reacted with human body protein even DNA, so as to cause
Skin blister stimulates eyes and respiratory tract or even causing death.Mustard gas or its analogies (2- chloroethylethyl thioether,
CEES it) can be selectively oxidized as nontoxic sulfoxide compound, but excessive oxidation then generates the sulfone compound of severe toxicity.Cause
This, the technology of discovery and development environment close friend, efficiently and safely degrade mustard gas and its analogies do not generate other toxic pairs
Product is still challenging project.
Porphyrins have good light sensitivity, and singlet can be effectively generated under ultraviolet or radiation of visible light
Oxygen.Toxic mustard gas analogies (2- chloroethylethyl thioether, CEES) selective oxidation can be nontoxic 2- by singlet oxygen
Chloroethylethyl sulfoxide (CEESO), the compound 2- chloroethylethyl sulfone (CEESOO) without generating severe toxicity.
Porous coordination polymer is the bridging using metal ion or metal cluster as node by organic ligand, self assembly shape
At the crystalline state porous material of high-sequential.
The unique rigid molecule geometric configuration of sulfydryl nano silver cluster can efficiently control its coordination mode, can be used as node
With organic ligand bridging.Silver-colored cluster Quito is self-assembly of in conjunction with sulfydryl nano silver cluster using porphyrins as bridge ligand
Hole coordination polymer has certain specific surface area and unique cellular structure, can adsorb CEES and oxygen, and can send out
The synergistic effect for waving sulfydryl silver cluster and ligand has been shown greatly in the application in catalytic degradation mustard gas analogies field
Application prospect.
Summary of the invention
To develop the superior mustard gas analogies catalytic degradation materials of performances such as selectivity is high, degradation speed is fast, this hair
Bright is designed to provide the tool constructed based on 12 core nanometer sulfydryl silver clusters and 5,10,15,20- tetra- (4- pyridyl group) porphyrin ligand
There is the porous cluster polymerization of olefin using catalyst polymer and preparation method thereof of efficient degradation mustard gas simulation physical performance.
Purpose to realize the present invention, the invention discloses a kind of cluster Quito hole polycomplexations of catalytic degradation mustard gas analogies
Object is closed, the chemical formula of the cluster base Porous coordination polymer is [Ag12(StBu)6(CF3COO)6(TPyP)4]n, it is tiltedly brilliant to belong to three
System, space group P-1.α=61.4520
(10) °, β=68.2290 (10) °, γ=67.3880 (10) °,Wherein TPyP is 5,10,15,20-
Four (4- pyridyl group) porphyrins, skeleton symbol are as follows:
The preparation method of the catalytic degradation mustard gas analogies material is achieved by the steps of:
Tert-butyl sulphur silver is added in acetonitrile and Isosorbide-5-Nitrae-dioxane mixed solution, is stirred；Silver trifluoroacetate is added, stirs
It mixes to solution and clarifies；Trifluoroacetic acid is added, the chloroformic solution of TPyP is eventually adding, continues to be stirred to react.After reaction, will
Solution is protected from light volatilization at room temperature, obtains crystal, be filtered, washed, after room temperature is dried new catalytic degradation mustard gas analogies material
Material.
Each component molar ratio range: tert-butyl sulphur silver: silver trifluoroacetate: trifluoroacetic acid: TPyP is 0.05~0.15:0.05
~0.15:0.3~0.9:0.001~0.006.Acetonitrile/Isosorbide-5-Nitrae-dioxane (1:1,3ml~12ml), chloroform (1~
3ml)。
The material is one unique using 12 core sulfydryl silver clusters as node, two formed by TPyP tetradentate ligands bridging
Tie up layer structure；It is accumulated in the form of ABAB between layer and layer；The material has duct, and specific surface area reaches 234m2g-1(Fig. 2 above
It is shown).
Meet under illumination, aerobic conditions, material of the present invention is applied to photocatalytic degradation mustard gas analogies.Due to the material
Material is the porous cluster polymerization of olefin using catalyst polymer constructed using sulfydryl silver cluster as node and porphyrin ligand；And porphyrins are a kind of
Classical photosensitizer molecule can make triplet oxygen be converted into singlet oxygen after illumination, and singlet oxygen be capable of selectivity general
CEES is transformed into nontoxic CEESO；And the material has certain duct and specific surface area, specific surface area reaches 234m2g-1More than.
Chlorine element in sulfydryl silver cluster and mustard gas analogies interacts, and can further improve and react advantageous mass transfer to catalysis
And preenrichment.Therefore, this material being capable of efficiently and rapidly photocatalytic degradation mustard gas analogies.
Concrete application is as follows:
It is placed in material of the present invention as catalyst in deuterated methanol solution, is bubbled with oxygen (or air), target is urged
Change substrate CEES to be added, with white LED lamp illumination, monitor catalysis process with nuclear magnetic resonance spectroscopy (shown in Fig. 4).Catalysis knot
Beam is centrifugated catalyst, i.e., recycling, circulation for several times after, the X-ray powder diffraction of material there is no any variation,
Illustrate that material is able to maintain excellent stability for a long time, in multiple circulation catalysis.
Required illumination wavelength range includes whole wave bands of ultraviolet light and visible light, i.e. 10nm~760nm；Required aerobic conditions
Oxygen content is air and purity oxygen；Required catalyst loading is mustard gas analogies 2- chloroethylethyl thioether mole
0.2%~5%.
The invention has the advantages that prepared novel porous cluster polymerization of olefin using catalyst polymer material being capable of quick catalysis degradation mustard gas mould
Quasi- object: under oxygen atmosphere, half-life period 1.5 minutes；Under air environment, half-life period 4 minutes (shown in Fig. 5).The materials synthesis
Method simple possible, can scale of mass production.Mild condition required by the material catalytic degradation mustard gas analogies, in air ring
Under border.The material is that production takes precautions against mustard gas poison gas device and handles the safe and reliable of degradation mustard gas poison gas great potential
Material.
Detailed description of the invention
Fig. 1 is the structural unit figure of catalytic degradation mustard gas analogies material of the present invention.
Fig. 2 is the packed structures schematic diagram of catalytic degradation mustard gas analogies material of the present invention.
Fig. 3 is the X-ray powder diffraction figure of catalytic degradation mustard gas analogies material of the present invention, in figure, 1- material of the present invention
Material, 2- simulation.
Fig. 4 is the nuclear magnetic resonance wave that catalytic degradation mustard gas analogies material of the present invention carries out photocatalytic degradation CEES experiment
Compose monitoring figure.
Fig. 5 is catalytic degradation mustard gas analogies material of the present invention photocatalytic degradation CEES under oxygen or air environment
When m- conversion ratio figure.
Specific embodiment
Below by example, the present invention is described further:
Embodiment 1: synthesis catalytic degradation mustard gas analogies material
By 0.02g (0.1mmol) tert-butyl sulphur silver (tBuSAg) it is placed in the mixing of 3mL acetonitrile and 3mL 1,4- dioxane
In solution, quickly stir；0.022g (0.1mmol) silver trifluoroacetate (CF is added3COOAg), stirring to solution is clarified；It is added
0.01ml (0.6mmol) trifluoroacetic acid (CF3COOH), finally by 0.001g (0.0032mmol) four (4- pyridyl group) porphyrin
(TPyP) it is dissolved in 1ml chloroformic solution and reaction system is added, continue stirring 5 minutes.After reaction, solution is kept away at room temperature
Photoablation, after 2 days darkviolet bulk crystals, yield 71.65%, filtering are washed with methanol and acetonitrile, must be urged after room temperature is dried
Change degradation mustard gas analogies material.
Embodiment 2: material catalytic degradation mustard gas analogies CEES of the present invention is utilized
Capacity be 7ml vial in be added embodiment 1 made from degradation mustard gas analogies material sample 1.5mg and
1ml deuterated methanol, is passed through oxygen or air is bubbled 15 minutes, and 5.6uL CEES is added, irradiates under white LED lamp, carries out light
Catalysis reaction, is monitored with nuclear-magnetism method and is reacted.As shown in Figure 4, under photocatalysis, the material is by toxic mustard gas analogies
CEES selective oxidation is nontoxic 2- chloroethylethyl sulfoxide (CEESO), the compound 2- chloroethyl second without generating severe toxicity
Base sulfone (CEESOO).As shown in Figure 5, material energy quick catalysis degradation mustard gas analogies.
Material of the present invention is centrifuged, and is washed three times, is dried with 2ml methanol, i.e., reusable.Repeatedly recycled in catalysis
Still it is able to maintain excellent stability.
Catalytic degradation mustard gas analogies material made from Example 1 further characterizes, and process is as follows:
(1) crystal structure determination
The X-ray single crystal diffraction data of Inventive polymers are turned with sizeable single crystal samples in Rigaku XtaLAB Pro
It is measured on target monocrystalline instrument.Data are with through graphite monochromatised Cu-K alpha rayIt is scanned for radiographic source by ω
Mode is collected at room temperature, and passes through Lp factor correction and semiempirical absorption correction.Structure elucidation is to first pass through SHELXT-2015
Program obtains just structure, then uses the complete matrix least square method refine of SHELXL-2015 program.All non-hydrogen atoms are adopted
With anisotropic thermal parametric method refine.Detailed axonometry data are shown in Table 1.
The predominant crystal data of the catalytic degradation mustard gas analogies material of the present invention of table 1
1 predominant crystal data of table
R1=∑ | | Fo|-|Fc||/∑|Fo|.wR2=[∑ w (Fo 2-Fc 2)2/∑w(Fo 2)2]1/2
The X-ray powder diffraction (XRD) of catalytic degradation mustard gas analogies material of the present invention characterizes
The PXRD figure of catalytic degradation mustard gas analogies material of the present invention is shown in Fig. 3.Institute is simulated with the single crystal structural data of the material
The surveyed XRD data mapping of the XRD data and experiment obtained, instrument model: Rigaku XtaLAB Pro diffractometer (Cu-K α, ), as a result unanimously.
Claims (6)
1. a kind of catalytic degradation mustard gas analogies material, it is characterised in that: the chemical formula of the material are as follows: [Ag12(StBu)6
(CF3COO)6(TPyP)4]n, belong to anorthic system；Space group is P-1, α=61.4520 (10) °, β=68.2290 (10) °, γ=67.3880 (10) °,Its structural unit is as follows:
Wherein TPyP is 5,10,15,20- tetra- (4- pyridyl group) porphyrins, and skeleton symbol is as follows:
2. catalytic degradation mustard gas analogies material as described in claim 1, it is characterised in that: the material is sulfydryl silver cluster
Coordination polymer, the polymer are formed using 12 core sulfydryl silver clusters as node by four (4- pyridyl group) porphyrin tetradentate ligands bridgings
Two-dimensional layered structure；It is accumulated in the form of ABAB between layer and layer.
3. the method for preparing catalytic degradation mustard gas analogies material as described in claim 1, which is characterized in that by following
Step is realized: tert-butyl sulphur silver being added in acetonitrile and 1,4- dioxane mixed solution and is stirred；Silver trifluoroacetate is added, stirs
It mixes to solution and clarifies；Trifluoroacetic acid is added, 5,10,15,20- tetra- (4- pyridyl group) porphyrin TPyP are finally dissolved in chloroform
And be added in reaction system, continue to be stirred to react；After reaction, it filters, filtrate is protected from light to volatilization at room temperature, is obtained brilliant
Body, filtering, it is washed, dry after catalytic degradation mustard gas analogies material.
4. the preparation method of catalytic degradation mustard gas analogies material as claimed in claim 3, which is characterized in that each group centimorgan
You are than range: tert-butyl sulphur silver: silver trifluoroacetate: trifluoroacetic acid: TPyP is 0.05~0.15:0.05~0.15:0.3~0.9:
0.001~0.006.
5. the application of catalytic degradation mustard gas analogies material as claimed in claim 1 or 2, it is characterised in that: meet illumination,
Under aerobic conditions, it is applied to catalytic degradation mustard gas analogies 2- chloroethylethyl thioether as catalyst.
6. the application of catalytic degradation mustard gas analogies material as claimed in claim 5, it is characterised in that: required illumination wavelength
Range 10nm~760nm；Required aerobic conditions are air and purity oxygen；Required catalyst loading is mustard gas analogies 2- chlorine
The 0.2%~5% of ethyl diethyldithiocarbamate thioether mole.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114835733A (en) * | 2022-05-27 | 2022-08-02 | 南昌大学 | Sp (sp) 2 Preparation method of-C metal organic framework and application of detoxified mustard gas simulant |
| CN114933704A (en) * | 2022-06-02 | 2022-08-23 | 南昌大学 | Preparation method of porous organic polymer connected by heteroatom and application of sulfur mustard simulant for photocatalytic detoxification |
| CN115382577A (en) * | 2021-05-24 | 2022-11-25 | 中国科学院理化技术研究所 | Application of covalent organic framework material in mustard gas and analogue photodegradation thereof |
| WO2023079111A1 (en) | 2021-11-05 | 2023-05-11 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Photocatalytic aerobic oxidation of yperite or an analog thereof |
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| CN106501230A (en) * | 2016-12-22 | 2017-03-15 | 郑州大学 | A kind of application of sulfydryl silver cluster coordination polymer in organic solvent detection |
| CN106589400A (en) * | 2016-12-22 | 2017-04-26 | 河南理工大学 | Application of mercapto silver cluster coordination polymer in detection of oxygen |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115382577A (en) * | 2021-05-24 | 2022-11-25 | 中国科学院理化技术研究所 | Application of covalent organic framework material in mustard gas and analogue photodegradation thereof |
| CN115382577B (en) * | 2021-05-24 | 2024-04-12 | 中国科学院理化技术研究所 | Application of covalent organic framework material in photodegradation of mustard gas and simulative substance thereof |
| WO2023079111A1 (en) | 2021-11-05 | 2023-05-11 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Photocatalytic aerobic oxidation of yperite or an analog thereof |
| CN114835733A (en) * | 2022-05-27 | 2022-08-02 | 南昌大学 | Sp (sp) 2 Preparation method of-C metal organic framework and application of detoxified mustard gas simulant |
| CN114835733B (en) * | 2022-05-27 | 2023-10-03 | 南昌大学 | Sp (sp) 2 Preparation method of-C metal organic framework and application of detoxified mustard gas simulator |
| CN114933704A (en) * | 2022-06-02 | 2022-08-23 | 南昌大学 | Preparation method of porous organic polymer connected by heteroatom and application of sulfur mustard simulant for photocatalytic detoxification |
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