CN115382577B - Application of covalent organic framework material in photodegradation of mustard gas and simulative substance thereof - Google Patents
Application of covalent organic framework material in photodegradation of mustard gas and simulative substance thereof Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 74
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000001782 photodegradation Methods 0.000 title claims abstract description 7
- 239000000126 substance Substances 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 16
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 13
- 150000003462 sulfoxides Chemical class 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 7
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 6
- 238000000862 absorption spectrum Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- -1 sulfone compounds Chemical class 0.000 abstract description 2
- GBNVXYXIRHSYEG-UHFFFAOYSA-N 1-chloro-2-ethylsulfanylethane Chemical compound CCSCCCl GBNVXYXIRHSYEG-UHFFFAOYSA-N 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 150000004032 porphyrins Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- QCWPXJXDPFRUGF-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 QCWPXJXDPFRUGF-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- LIPRCTSGLFLUNJ-UHFFFAOYSA-N 1-chloro-2-ethylsulfinylethane Chemical compound CCS(=O)CCCl LIPRCTSGLFLUNJ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002272 high-resolution X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000003278 mimic effect Effects 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FUQCKESKNZBNOG-UHFFFAOYSA-N 2-[4-(cyanomethyl)phenyl]acetonitrile Chemical compound N#CCC1=CC=C(CC#N)C=C1 FUQCKESKNZBNOG-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002575 chemical warfare agent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000002604 ultrasonography Methods 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/00—Sources of waste gases
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- B01D2258/0225—Other waste gases from chemical or biological warfare
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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
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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Abstract
The invention discloses an application of a covalent organic framework material in photodegradation of mustard gas and simulants thereof. In the application, the adopted covalent organic framework material can selectively and rapidly catalyze molecular oxygen to oxidize mustard gas and simulants thereof to generate sulfoxide, so that further oxidization into virulent sulfone compounds is avoided; the covalent organic framework material has excellent photocatalytic stability and recycling capability, and can keep high reactivity in the recycling process; and has the advantages of simple preparation method, wide and strong absorption spectrum in ultraviolet-visible light region, and the like. In addition, in the application method provided by the invention, the reaction condition is mild, and the application method can be realized by irradiation of visible light or sunlight at room temperature. The whole process is simple and efficient, and the reaction condition is mild.
Description
Technical Field
The invention relates to the field of degradation of mustard gas and simulants thereof. More particularly, to the use of a covalent organic framework material in the photodegradation of mustard gas and its mimics.
Background
Chemical warfare agents such as mustard gas and the like have great threat to human social safety due to the characteristics of great killing power, quick toxicity, easy preparation and release and the like. At present, the traditional thermochemical method aiming at the degradation of mustard gas has the defects of high energy consumption, low efficiency, secondary pollution and the like. In contrast, photocatalysis is a milder and environmentally friendly way to achieve degradation of mustard gas and its mimics (Ma, l.; liu, y.; jiang, s.; li, p.; hao, y.; shao, p.; yin, a.; feng, x.; wang, b.; angel. Chem. Int. Ed. Engl.2019,58 (13), 4221-4226). Wherein, the photocatalytic molecular oxygen is utilized to oxidize the mustard gas and the simulative thereof to generate sulfoxide, so that the toxic degradation of the mustard gas and the simulative thereof has the advantages of mild reaction conditions, high reaction efficiency and the like. Therefore, it is important to design a novel catalytic system which has high conversion rate, is environment-friendly and can realize degradation by oxidizing mustard gas with molecular oxygen and simulants thereof.
Covalent organic frameworks (Covalent organic framework, COF) are a class of crystalline organic porous polymers. In 2005, the Yaghi group reported Covalent Organic Frameworks (COFs) for the first time, and the Covalent Organic Frameworks (COFs) as novel porous crystalline polymers have been attracting attentionA.p.; benin, a.i.; ockwig, N.W.; o' keeffect, m.; matzger, A.J.; yaghi, o.m., science 2005,310,1166). COFs have been favored in various fields (such as gas adsorption and separation, sensing light emitting diodes, photo (electro) catalysis, and energy storage, etc.) because of their unique porous and periodic structures possessing a range of excellent properties (e.g., high surface area, efficient (photo) electronic properties, and excellent chemical stability) (Ashford, d.l.; gish, m.k.; vannucci, a.k.; brennaman, m.k.; sampleton, j.l.; papanikolas, j.m.; meyer, T.J., chem.Rev.2015,115 (23), 13006-49).
In recent years COF has been shown to be effective in activating triplet molecular oxygen. However, there is currently no report on the photocatalytic oxidation of mustard gas and its mimetic degradation by covalent organic frameworks. Therefore, how to utilize covalent organic frameworks to photo-catalyze and oxidize the degradation research of the mustard gas has important significance and prospect.
Disclosure of Invention
The invention aims to provide an application of a covalent organic framework material in photodegradation of mustard gas and mimics thereof. The application method well realizes that the photocatalytic mustard gas and the simulant thereof generate sulfoxide.
In order to achieve the above purpose, the invention adopts the following technical scheme:
use of a covalent organic framework material in the photodegradation of mustard gas and its analogues.
Further, the covalent organic framework material is a porphyrin covalent organic framework material.
Further, the porphyrin covalent organic framework material is hydrogen or metal coordination porphyrin organic covalent framework material.
Further, the metal in the hydrogen or metal coordination porphyrin organic covalent framework material is selected from one of Cu, zn, ni and Co.
Further, in the structure of the hydrogen or metal coordination porphyrin organic covalent framework material, phenyl porphyrin or metal phenyl porphyrin is used as a repeating unit A, and 1, 4-benzene diacetonitrile (PDAN) or 2, 5-diethoxy benzene-1, 4-bis (formylhydrazine) (DETH) is used as a repeating unit B, and the phenyl porphyrin or metal phenyl porphyrin is repeatedly and alternately connected to form a framework structure. The invention is described by optimizing literature [ Chen, r.; shi, j.; ma, y; lin, G.; lang, X.; wang, c., angel chem. Int. Ed. Engl.,2019,58 (19), 6430-6434]The synthesis strategy realizes the synthesis of PDAN series hydrogen and metal coordination porphyrin organic covalent frameworks, and is named as H 2 Por-sp 2 c-COF and MPor-sp 2 c-COF, optimized literature [ Chen, r.; wang, y; ma, y; mal, A.; gao, x.y.; gao, l.; qiao, l.; li, X.B.; wu, l.z.; wang, c., nat Commun 2021,12 (1), 1354.]The synthesis strategy realizes the synthesis of DETH series hydrogen and metal coordination porphyrin organic covalent frames, and is named as H 2 Port-DETH-COF and MPor-DETH-COF, which make it possible to produce sulfoxide by mild and efficient photocatalytic molecular oxygen oxidation of mustard gas and its mimic compounds. Wherein M is equal to Cu, zn, ni, co, etc.
Further, the structural formula of the phenylporphyrin is shown as the following formula I-1, and the structural formula of the metalloporphyrin is shown as the following formula I-2:
wherein M is a metal, preferably Cu, zn, co or Ni.
Further, the structural formula of the covalent organic framework material is one or more of the structural formulas shown in the following formulas II-1 to II-4:
wherein M is a metal.
Compounds represented by the above formulas II-1 to II-4 can be respectively designated as H 2 Por-sp 2 c-COF、MPor-sp 2 c-COF、H 2 The compounds represented by the formula (II-1), the formula (II-2), the formula (III-1) or the formula (III-2) can be prepared by the above-exemplified preparation methods unless otherwise specified.
Further, in the application, the degradation reaction is performed under aerobic conditions. The aerobic condition may be, for example, a pure oxygen atmosphere or air.
Further, preferably, in the application, the degradation reaction is performed at room temperature.
Further, in the photocatalytic process, the light source wavelength of the illumination is in the ultraviolet-visible range. Further, the light source may be sunlight, or may be provided by an LED, a xenon lamp, or the like.
Further, the application comprises the steps of:
under the aerobic condition, the covalent organic framework material is dispersed in an organic solvent, and then a reaction substrate is added, and the mixture is irradiated under the airtight condition.
Wherein the reaction substrate is mustard gas and its mimic. By the method, the oxidation of the mustard gas and the simulants thereof to generate sulfoxide can be catalyzed.
Further, in the above application, the temperature is maintained at room temperature during degradation. The amount of the covalent organic framework material added to the organic solvent is not limited and may be not more than the saturation concentration thereof.
Further, the organic solvent includes, but is not limited to, one or more selected from methanol, ethanol, acetonitrile.
The beneficial effects of the invention are as follows:
in the application method provided by the invention, the adopted covalent organic framework material can selectively and rapidly catalyze molecular oxygen to oxidize mustard gas and mimics thereof to generate sulfoxide, so that further oxidization into virulent sulfone compounds is avoided; the covalent organic framework material has excellent photocatalytic stability and recycling capability, and can keep high reactivity in the recycling process; and has the advantages of simple preparation method, wide and strong absorption spectrum in ultraviolet-visible light region, and the like.
Meanwhile, in the application method provided by the invention, the reaction condition is mild, and the application method can be realized by irradiation of visible light or sunlight at room temperature. The whole process is simple and efficient, and the reaction condition is mild.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 shows CuPor-sp in the present invention 2 Structure of c-COF.
FIG. 2 shows CuPor-sp in the present invention 2 High resolution transmission electron microscopy of c-COF.
FIG. 3 shows CuPor-sp in the present invention 2 c-COF and Por-sp 2 X-ray diffraction (XRD) pattern of c-COF.
FIG. 4 shows CuPor-sp in the present invention 2 X-ray photoelectron Spectrometry (XPS) Spectrometry for c-COF
FIG. 5 shows CuPor-sp in the present invention 2 High resolution X-ray photoelectron Spectroscopy (HR-XPS) of the Cu 2p orbital of c-COF.
FIG. 6 shows CuPor-sp in the present invention 2 c-COF and H 2 Por-sp 2 Kinetics of conversion of the 2-chloroethyl ethyl sulfide (CEES) substrate by the photocatalytic molecular oxygen oxidation of C-COF, wherein C/C is the ordinate 0 Representing the raw material remaining concentration/raw material initial concentration.
FIG. 7 shows CuPor-sp in the present invention 2 c-COF and H 2 Por-sp 2 Kinetics of c-COF photocatalytic CEES formation of product sulfoxide.
FIG. 8 shows CuPor-sp in the present invention 2 catalytic reaction recycling capability of c-COF.
FIG. 9 shows the yield of the product sulfoxide from CEES photocatalytic reaction using a portion of the catalyst of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
The preparation of covalent organic frameworks in the present invention is according to literature [ Chen, r.; shi, j.; ma, y; lin, G.; lang, X.; wang, c., angel chem. Int. Ed. Engl.,2019,58 (19), 6430-6434] and modified, the specific experimental steps include:
preparation of p-CuPor-CHO: 200mg of p-Por-CHO (0.27 mmol) and 100mg of CuCl were weighed out separately 2 ·2H 2 O (0.58 mmol) was placed in a 100mL round bottom flask and 50mL DMF was added thereto, followed by refluxing under nitrogen at 120℃for 4-5 h, after the reaction system cooled to room temperature, it was poured into a beaker with 100mL distilled water, left to stand for 2h and suction filtered, the crude product was washed with ethanol to give 210mg of red solid in about 97% yield.
CuPor-sp 2 Preparation of c-COF is shown in FIG. 1: 4mL of 1, 2-dichlorobenzene followed by 0.4mL of 6mol/L DBU in water was added to an amp tube weighed with terephthalonitrile (30.0 mg,0.192 mmol) and p-CuPor-CHO (75.7 mg,0.096 mmol), and the amp tube was placed in ultrasound for 10 minutes to disperse the system uniformly; then placing the ampere tube in liquid nitrogen for freezing, circularly vacuumizing and introducing nitrogen for three times, and sealing the ampere tube by a flame gun under a vacuum condition; after the ampere tube returns to room temperatureThe mixture was put into an oven at 80℃for 3 days, after the reaction was completed and cooled to room temperature, the solid was collected by filtration, and was extracted with tetrahydrofuran and methylene chloride for 24 hours, respectively, and dried to obtain 75.9mg of a bluish-black solid with a yield of about 78%. CuPor-sp prepared by TEM, XRD, XPS, IR pair 2 c-COF. FIG. 1 is CuPor-sp 2 Transmission Electron Microscope (TEM) image of c-COF, as can be seen from FIG. 2, the CuPor-sp 2 c-COF presents a two-dimensional sheet shape; FIG. 3 is CuPor-sp 2 An X-ray diffraction pattern (XRD) of c-COF, wherein each absorption peak corresponds to each crystal plane of the material; FIG. 4 is CuPor-sp 2 XPS pattern of c-COF, XPS full spectrum (FIG. 4) shows prepared CuPor-sp 2 The C-COF is composed of four elements of C, N, O and Cu, and the peaks at 934.48eV and 954.38eV of the Cu 2p high-resolution XPS spectrum (figure 5) correspond to Cu 2p respectively 3/2 Cu 2p 1/2 。
Example 2
Firstly, the prepared catalyst CuPor-sp is weighed 2 C-COF 0.5mg was placed in 5mL light, and 1mL CH was added 3 CN is used as a solvent, and sealing and ultrasonic treatment are carried out for 20min. Then, oxygen is introduced into the system for 5min to make the system under the oxygen atmosphere. Subsequently, 5. Mu.L of substrate 2-chloroethyl ethyl sulfide (CEES) (0.043 mmol) was injected therein, wax sealed. Finally, the reaction system was irradiated under a 300W Xe lamp equipped with a 400nm filter. The feasibility of the experiment under different reaction conditions was controlled.
Conclusion: experimental results show that under the condition that the variables of the catalyst, the substrate, the light source and the oxygen are controlled to be single, the system can not efficiently catalyze CEES to oxidize to generate 2-chloroethyl ethyl sulfoxide (CEESO). Indicating that all conditions play an irreplaceable role in the reaction process.
Table 1 control of single variable experiments to investigate the effect of different components on the photocatalytic reaction
| Sequence number | Catalyst | Substrate(s) | Reaction time | Light source | Atmosphere of | Nuclear magnetic conversion (%) | Nuclear magnetic productivity (%) |
| 1 | CuPor-sp 2 c-COF | CEES | 1h | ≥400nm | O 2 | 96.68 | 95.23 |
| 2 | CuPor-sp 2 c-COF | CEES | 1h | ≥400nm | Ar | 0 | 0 |
| 3 | CuPor-sp 2 c-COF | CEES | 1h | Dark | O 2 | 0 | 0 |
| 4 | CuPor-sp 2 c-COF | -- | 1h | ≥400nm | O 2 | 0 | 0 |
| 5 | -- | CEES | 1h | ≥400nm | O 2 | Trace amount of | Trace amount of |
Example 3
Firstly, the prepared catalyst CuPor-sp is weighed 2 C-COF 0.5mg was placed in 5mL light, and 1mL CH was added 3 CN is used as a solvent, and sealing and ultrasonic treatment are carried out for 20min. Then, oxygen is introduced into the system for 5min to make the system under the oxygen atmosphere. Subsequently, 5. Mu.L of substrate CEES (0.043 mmol) was injected therein, wax-sealed. Finally, the reaction system was irradiated under 300W Xe with 400nm filter. The system products of different reaction times were tested.
Conclusion: the results are shown in FIG. 6, cuPor-sp 2 c-COF and H 2 Por-sp 2 The c-COF can efficiently realize the conversion of a substrate CEES, and CuPor-sp 2 c-COF compared to H 2 Por-sp 2c COF possesses higher catalytic CEES conversion efficiency. H, especially when the reaction is carried out for 20min 2 Por-sp 2 The conversion rate of the substrate of the c-COF system is only 25.8%, while the conversion rate of the substrate of the CuPor-sp is only 25.8% 2 The substrate conversion rate of the c-COF system reaches 78.7 percent and is Port-sp 2 Three times more c-COF and the corresponding CEESO yields (fig. 7) also have a similar trend, with similar conversion rates and yields, indicating highly selective oxidation of CEES to CEESO.
Example 4
Firstly, the prepared catalyst CuPor-sp is weighed 2 C-COF 0.5mg was placed in 5mL light, and 1mL CH was added 3 CN is used as a solvent, and sealing and ultrasonic treatment are carried out for 20min. Then, oxygen is introduced into the system for 5min to make the system under the oxygen atmosphere. Subsequently, 5. Mu.L of substrate CEES (0.043 mmol) was injected therein, wax-sealed. Finally, the reaction system was irradiated under 300W Xe with 400nm filter. The photocatalytic substrate yields were measured for the same catalyst reuse.
For CuPor-sp 2 The c-COF was subjected to recycling experiments (fig. 8), and the results showed that the catalyst had good photocatalytic CEES conversion capacity in all three cycles, indicating that the material had good stability and recycling capacity.
Example 5
Firstly, 0.5mg of the catalyst prepared in the part is weighed and placed in 5mL of a light pipe, and 1mL of CH is added 3 CN is used as a solvent, and sealing and ultrasonic treatment are carried out for 20min. Then, oxygen is introduced into the system for 5min to make the system under the oxygen atmosphere. Subsequently, 5. Mu.L of substrate CEES (0.043 mmol) was injected therein, wax-sealed. Finally, the reaction system was irradiated under 300W Xe with 400nm filter for 1h. The photo-catalytic substrate yields of the different catalyst systems were examined.
All catalysts achieved high selectivity photocatalytic conversion of mustard gas and its simulants to sulfoxide (fig. 9). Wherein H is 2 Por-sp 2 c-COF、CuPor-sp 2 c-COF、H 2 The yields of Por-DETH-COF and ZnPor-DETH-COF were 86.55%, 95.23%, 90.42% and 93.51%, respectively.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (5)
1. The application of the covalent organic framework material in the photodegradation of mustard gas is characterized in that the structural formula of the covalent organic framework material is one or more of the structural formulas shown in the following formulas II-1 to II-4:
II-1；/>II-2；
II-3；/>II-4；
wherein M is a metal selected from one of Cu, zn, ni and Co.
2. The use according to claim 1, wherein in the use the degradation reaction is carried out under aerobic conditions.
3. The use according to claim 1, wherein in the use the degradation reaction is carried out at room temperature.
4. Use according to claim 1, characterized in that the light source wavelength of the illumination is in the uv-visible range during the photocatalysis.
5. The application according to claim 1, characterized in that it comprises the steps of:
under the aerobic condition, the covalent organic framework material is dispersed in an organic solvent, and then the reaction substrate mustard gas is added, and the mixture is irradiated under the closed condition.
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| CN108117643A (en) * | 2016-11-30 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of porous polymer containing porphyrin group and preparation method thereof |
| CN110437459A (en) * | 2019-08-01 | 2019-11-12 | 郑州大学 | A kind of catalytic degradation mustard gas analogies material and preparation method thereof |
| WO2021097324A1 (en) * | 2019-11-15 | 2021-05-20 | University Of South Florida | Covalent organic frameworks and applications as photocatalysts |
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| CN108117643A (en) * | 2016-11-30 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of porous polymer containing porphyrin group and preparation method thereof |
| CN110437459A (en) * | 2019-08-01 | 2019-11-12 | 郑州大学 | A kind of catalytic degradation mustard gas analogies material and preparation method thereof |
| WO2021097324A1 (en) * | 2019-11-15 | 2021-05-20 | University Of South Florida | Covalent organic frameworks and applications as photocatalysts |
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