CN109603910A - A kind of nano core-shell compound of photo-thermal enhancing degradation chemical warfare agent analogies and its preparation method and application of composite cellulosic membrane - Google Patents
A kind of nano core-shell compound of photo-thermal enhancing degradation chemical warfare agent analogies and its preparation method and application of composite cellulosic membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 57
- 230000015556 catabolic process Effects 0.000 title claims abstract description 55
- 150000001875 compounds Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000011258 core-shell material Substances 0.000 title claims abstract description 42
- 239000002575 chemical warfare agent Substances 0.000 title claims abstract description 31
- 230000002708 enhancing effect Effects 0.000 title claims description 17
- 239000000843 powder Substances 0.000 claims abstract description 42
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 claims abstract description 32
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 229960003638 dopamine Drugs 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 238000009987 spinning Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 244000025254 Cannabis sativa Species 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000013110 organic ligand Substances 0.000 claims description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 7
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 239000012221 photothermal agent Substances 0.000 claims 1
- 230000001965 increasing effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 19
- 230000005855 radiation Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000009928 pasteurization Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- -1 Alkene nitrile Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Chemical compound [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/23—
-
- B01J35/30—
-
- B01J35/39—
-
- B01J35/51—
-
- B01J35/59—
-
- B01J35/615—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- 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
- B01J2531/02—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
-
- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Enhance the nano core-shell compound of degradation chemical warfare agent analogies and its preparation method and application of composite cellulosic membrane the present invention relates to a kind of photo-thermal.It is core, MOFs for shell that nano core-shell compound in the present invention, which is using light thermit powder, wherein light thermit powder is dopamine melanin nano particle, and the diameter of particle is 150~400nm, MOFs UiO-66-NH2, nano core-shell compound is Dpa@UiO-66-NH2, the diameter of compound is 300~500nm.Composite cellulosic membrane in the present invention is above-mentioned nano core-shell compound and spinning-aid agent mixes the composite cellulosic membrane obtained by electrostatic spinning process, which is Dpa@UiO-66-NH2/ PAN, the diameter of fiber are 0.5~3 μm.Nano core-shell compound and composite cellulosic membrane all present the catalytic efficiency increased substantially to the degradation of CWAs analogies under NIR laser irradiation.
Description
Technical field
The present invention relates to nano core-shell compounds and its composite fibre that a kind of photo-thermal enhances degradation chemical warfare agent analogies
The preparation method and application of film, belong to field of catalytic chemistry.
Background technique
In the world today, chemical warfare agent (Chemical Warfare Agents, CWAs) still has a large amount of inventory, and
It is likely to be used in various conflicts, the mankind and environment is caused with lasting threat, therefore, finds and develop environmental sound
Chemical warfare agent purification techniques has important social effect.Currently, people do various types of adsorbents and filter
Extensive research, such as: Chinese patent literature CN 107584824A disclose a kind of multifunctional ventilating type frog suit fabric and
Preparation method, the frog suit fabric use multilayered structure, are followed successively by Multifunctional layered, adhesive layer, adsorption layer, adhesive layer, comfortable
Layer, wherein adsorption layer is mainly made of active carbon fiber fabrics or felt, adsorbable toxic gas.However, active carbon and adsorbate it
Between interaction it is weaker, removal efficiency is low, and will cause secondary murder by poisoning, and in contrast, people prefer to obtain and can catch
Obtain and destroy CWAs from pasteurization material.
Metal oxide be widely studied for remove chemical warfare agent from pasteurization material, for example, Chinese patent
Document CN101622195A discloses a kind of preparation method of metal-oxide fiber, for the chemical warfare agent that absorbs and degrade.It should
Method by metal oxide supported on polymer nanofiber, by heat treatment by metal oxide nanofibres functionalization,
Promote the degradation rate to CWAs.However the structural property of metal oxide itself include lower adsorbance, it is fewer number of
Active site and poor configuration flexibility limit a possibility that further increasing its degradation chemical warfare agent efficiency.More metals
Oxygen hydrochlorate has molecule abundant and electronic structure, can be used as oxidation, reduction and hydrolyst, has attracted researcher recently
It is applied to the analogies of degradation chemical warfare agent.Such as: Chinese patent literature CN 107626201A discloses a kind of amphipathic
More niobium oxygen cluster lotions are synthesized using the hydration raw materials such as six niobates and organic ammonium by anion exchange methods, in normal temperature and pressure
Under can simultaneous oxidation degradation mustard gas analogies and hydrolysis never poison analogies；Chinese patent literature CN 108559100A is public
The preparation method of metal ion species guidance Carboxylic acid ligand functionalization polyacid compound is opened and its in catalytic degradation chemical warfare agent
Application in terms of analogies, oxidative degradation mustard gas analogies that can be more efficient, highly selective and hydrolysis never poison simulation
Object.Although the rate of degradation chemical warfare agent analogies is greatly improved by the modification to polyoxometallate, according to
The degradation rate in people's ideal is not reached so, and powder catalytic has centainly restricted in terms of practical application.
Metal organic framework compound (Metal-Organic Frameworks, MOFs) is one kind by metal node and has
Machine ligand assembles the porous material for the highly crystalline to be formed, as removing CWAs adsorbent and catalyst show nothing
The potentiality of limit.Chinese patent literature CN 107362832A discloses a kind of preparation method of mustard gas (HD) degradable material, passes through
LBL self-assembly is by the TiO with light degradation HD ability2Both combine with the MOFs with hydrolytic degradation HD ability, play
Synergistic effect, improve the degradation effect to mustard gas material, but LBL self-assembly process is time-consuming and complex steps, and most
The catalyst of the powder type obtained eventually is unfavorable for actually using.Chinese patent literature CN 108310982A discloses a kind ofization
Learn war agent disinfection MOFs fibrous filter membrane and preparation method thereof certainly, the metal oxide that will be obtained by spinning process and calcination process
Film carries out hydro-thermal reaction with corresponding organic ligand and activated acid solution mixing, obtains the MOFs tunica fibrosa of self-supporting, maintains
The specific surface area of MOFs itself super large, brilliant adsorption capacity and catalytic property.However the preparation method of the tunica fibrosa is relatively multiple
Miscellaneous harshness, it is difficult to realize scale, limit its practical application.In conclusion the novel general means of exploitation are significantly to mention
High disinfection fabric certainly is to the huge challenge that the degradation property of CWAs is still that current people face.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of nano core-shell of photo-thermal enhancing degradation chemical warfare agent analogies
The preparation method and application of compound and its composite cellulosic membrane, it is characterised in that be grown in light thermit powder by MOFs, form nanometer
Nucleocapsid compound, and be further coupled in polymer fiber film by electrostatic spinning.The nano core-shell compound and its compound
Tunica fibrosa effectively improves the temperature of reaction system by the photo-thermal effect generated under near-infrared laser, greatly increases
To promote the progress of degradation reaction MOFs degradation has been greatly enhanced in the chance that the substance that is degraded is contacted with active site
The rate of never poison analogies, and this method has the scalability of height.
Term explanation:
Room temperature: 25 ± 2 DEG C；
MOFs: metal organic framework compound (Metal-Organic Frameworks), one kind is by metal node and has
Machine ligand assembles the porous material for the highly crystalline to be formed.
Technical scheme is as follows:
A kind of nano core-shell compound of photo-thermal enhancing degradation chemical warfare agent analogies, the nano core-shell compound is with light
Thermit powder is core, MOFs is shell；
Wherein, the light thermit powder is dopamine melanin nano particle, is abbreviated as Dpa NPs, the diameter of particle is 150~
400nm, the MOFs are UiO-66-NH2, the nano core-shell compound is Dpa@UiO-66-NH2, the diameter of compound is
300~500nm.
A kind of composite cellulosic membrane of photo-thermal enhancing degradation chemical warfare agent analogies, the composite cellulosic membrane is above-mentioned nanometer core
Shell compound and spinning-aid agent mix the composite cellulosic membrane obtained by electrostatic spinning process；
Wherein, the composite cellulosic membrane is Dpa@UiO-66-NH2/ PAN, the diameter of fiber are 0.5~3 μm.
Preferred according to the present invention, the spinning-aid agent is polyacrylonitrile, and weight average molecular weight is 150000~200000.
A kind of preparation method of the nano core-shell compound of photo-thermal enhancing degradation chemical warfare agent analogies, steps are as follows:
(1) preparation of light thermit powder
Water, ethyl alcohol and ammonium hydroxide obtain mixed solution after 20~50min is mixed, and weigh Dopamine hydrochloride addition soluble in water
Into mixed solution, persistently stir 20~30h solid is collected by centrifugation after reaction, be washed with deionized three times to get
Light thermit powder dopamine melanin nano particle；
(2) preparation of nano core-shell compound
The dopamine melanin nano particle in step (1) is weighed to disperse in a solvent, zirconium chloride to be added, stirs at room temperature
4~6h obtains disperse system, it is therefore an objective to adsorb zirconium ion on dopamine melanin nano particle；It weighs organic ligand and is added to dispersion
In system, after stirring 1h at room temperature, disperse system is put into reaction kettle and carries out hydro-thermal reaction, after hydro-thermal reaction, is collected by centrifugation
Solid, with solvent wash three times, by obtained solid be placed in baking oven dry to get using dopamine melanin nano particle as core,
With UiO-66-NH2For the nano core-shell compound of shell.
Preferred according to the present invention, the volume ratio of step (1) water, ethyl alcohol and ammonium hydroxide is (40~50): (15~25):
1。
Preferred according to the present invention, step (1) Dopamine hydrochloride mass concentration soluble in water is 0.04~0.1g/
mL。
Preferred according to the present invention, the temperature of step (1) described reaction is 20~40 DEG C；It is further preferred that described anti-
The temperature answered is 30 DEG C.
Preferred according to the present invention, step (2) solvent is n,N-Dimethylformamide, and the organic ligand is 2- ammonia
Base terephthalic acid (TPA).
Preferred according to the present invention, the mass concentration of step (2) the dopamine melanin nano particle in a solvent is
0.1~0.2mg/mL；The mass ratio of the dopamine melanin nano particle and zirconium chloride is 1:(30~60)；The zirconium chloride
Molar ratio with organic ligand is 1:1.
Preferred according to the present invention, the reaction temperature of step (2) described hydro-thermal reaction is 130~150 DEG C, and the reaction time is
20~30h.
A kind of preparation method of the composite cellulosic membrane of photo-thermal enhancing degradation chemical warfare agent analogies, steps are as follows:
(1) preparation of spinning solution
The nano core-shell compound of above-mentioned preparation is uniformly dispersed in n,N-Dimethylformamide solution, adds poly- third
Alkene nitrile is uniformly mixed and obtains spinning solution；
(2) preparation of composite cellulosic membrane
The spinning solution that step (1) is obtained carries out electrostatic spinning to get composite cellulosic membrane.
It is preferred according to the present invention, step (1) the nano core-shell compound, polyacrylonitrile and n,N-Dimethylformamide
Mass ratio be (0.011~1.5): 1:9, wherein the weight average molecular weight of polyacrylonitrile be 150000~200000.
It is preferred according to the present invention, the condition of step (2) described electrostatic spinning are as follows: 10~20kV of spinning voltage, electrode spacing
From 150~200mm, 25~30 DEG C of temperature, relative humidity 10~15%.
The nano core-shell compound or composite cellulosic membrane of above-mentioned photo-thermal enhancing degradation chemical warfare agent analogies are in catalytic degradation
Application in chemical warfare agent analogies diformazan grass ether (DMNP), steps are as follows:
The composite cellulosic membrane that nano core-shell compound is added into reaction vessel or shreds, and alkaline aqueous solution is added, it is acute
Strong stirring 30min, container is placed in the camera bellows with light source, and then DMNP is added in above-mentioned mixed liquor and is persistently stirred
It mixes, reacts 20~30min, complete the degradation of DMNP.
Preferred according to the present invention, the mass ratio of the nano core-shell compound and DMNP are (1.1~1.4): 1, it is described
The mass ratio of composite cellulosic membrane and DMNP are (2.1~2.4): 1.
Preferred according to the present invention, the alkaline aqueous solution is N-ethylmorpholine aqueous solution, and concentration is 0.1~0.5M.
Preferred according to the present invention, the light source is ultraviolet source, visible light source or near-infrared light source；Further preferably
, the light source is near-infrared light source.
Preferred according to the present invention, the temperature of the reaction is 25 DEG C.
The principle of the present invention:
Nano core-shell compound Dpa@UiO-66-NH prepared by the present invention2And its composite cellulosic membrane utilizes light thermit powder core Dpa
Photothermal conversion efficiency NPs excellent in ultraviolet-visible-near infrared region can effectively transfer heat to UiO-66-NH2Shell increases
The contact area being degraded between object and active catalyst sites greatly improves degradation efficiency.
It technical characterstic of the invention and has the beneficial effect that:
1, the nano core-shell compound Dpa@UiO-66- that the present invention is rationally designed out using light thermit powder core and micropore catalysis shell
NH2Heterojunction structure, either powder morphology or fibre morphology all open up the degradation of CWAs analogies under NIR laser irradiation
The catalytic efficiency increased substantially is showed.
2, composite cellulosic membrane Dpa@UiO-66-NH prepared by the present invention2/ PAN provides another and improves CWAs simulation
The method of object degradation efficiency, even in the case that the fine catalyst being present in tunica fibrosa has aggregation to a certain degree, nanometer
Nucleocapsid compound Dpa@UiO-66-NH2Heterojunction structure still can effectively transfer heat to Catalytic Layer by photo-thermal effect, improve and pass
Matter efficiency promotes reaction to carry out, increases substantially degradation efficiency.
3, composite cellulosic membrane Dpa@UiO-66-NH prepared by the present invention2/ PAN overcomes by increasing catalyst loadings
Degradation efficiency is improved to reduce the problem of tunica fibrosa mechanical strength, solves the long-term of MOFs tunica fibrosa catalytic performance reduction
Challenge, this novel photo-thermal enhancing catalysis removing toxic substances strategy can be extended other catalytic degradation fields.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram piece of Dpa NPs made from embodiment 1.
Fig. 2 is Dpa@UiO-66-NH made from embodiment 12Scanning electron microscope diagram piece.
Fig. 3 is Dpa NPs made from embodiment 1, Dpa@UiO-66-NH2With UiO-66-NH made from comparative example 12Powder
X-ray diffracting spectrum.
Fig. 4 is Dpa NPs made from embodiment 1, Dpa@UiO-66-NH2With UiO-66-NH made from comparative example 12Powder
Fourier transform infrared spectroscopy figure.
Fig. 5 is Dpa NPs made from embodiment 1, Dpa@UiO-66-NH2With UiO-66-NH made from comparative example 12Powder
Thermogravimetric analysis figure.
Fig. 6 is Dpa NPs made from embodiment 1, Dpa@UiO-66-NH2With UiO-66-NH made from comparative example 12Powder
N2Adsorption desorption curve.
Fig. 7 is Dpa NPs made from embodiment 1, Dpa@UiO-66-NH2With UiO-66-NH made from comparative example 12Powder
Ultraviolet-visible-near-infrared spectrum figure.
Fig. 8 is Dpa NPs made from embodiment 1, Dpa@UiO-66-NH2With UiO-66-NH made from comparative example 12Powder
And the temperature under near-infrared laser irradiation of deionized water changes with time figure.
Fig. 9 is composite cellulosic membrane Dpa@UiO-66-NH made from embodiment 22The scanning electron microscope diagram piece of/PAN.
Figure 10 is composite cellulosic membrane Dpa@UiO-66-NH made from embodiment 22The X-ray diffracting spectrum of/PAN.
Figure 11 is composite cellulosic membrane Dpa@UiO-66-NH made from embodiment 22The Fourier transform infrared spectroscopy of/PAN
Figure.
Figure 12 is composite cellulosic membrane Dpa@UiO-66-NH made from embodiment 22The thermogravimetric analysis figure of/PAN.
Figure 13 is composite cellulosic membrane Dpa@UiO-66-NH made from embodiment 22The N of/PAN2Adsorption desorption curve graph.
Figure 14 is composite cellulosic membrane Dpa@UiO-66-NH made from embodiment 22The stress-strain curve diagram of/PAN.
Figure 15 is composite cellulosic membrane Dpa@UiO-66-NH made from embodiment 22The optical photograph of/PAN.
Figure 16 is UiO-66-NH made from comparative example 12Powder is right in unglazed source radiation and under adding near-infrared laser to radiate
The conversion ratio figure of DMNP degradation.
Figure 17 is UiO-66-NH made from comparative example 22In unglazed source radiation and add near-infrared with the mixture of Dpa NPs
To the conversion ratio figure of DMNP degradation under laser emission.
Figure 18 is Dpa@UiO-66-NH made from embodiment 12Powder is in unglazed source radiation and under adding near-infrared laser to radiate
To the conversion ratio figure of DMNP degradation.
Figure 19 is UiO-66-NH made from comparative example 32/ PAN fiber film is in unglazed source radiation and plus near-infrared laser radiation
Under to DMNP degradation conversion ratio figure.
Figure 20 is UiO-66-NH made from comparative example 42With Dpa mixture/PAN fiber film in unglazed source radiation and plus closely
To the conversion ratio figure of DMNP degradation under IR laser radiation.
Figure 21 is Dpa@UiO-66-NH made from embodiment 22/ PAN fiber film is in unglazed source radiation and plus near-infrared laser
To the conversion ratio figure of DMNP degradation under radiation.
Specific embodiment
The present invention will be further explained with reference to the examples below, but not limited to this.
Raw materials used in embodiment is conventional products, and device therefor is conventional equipment.
Room temperature in embodiment is 25 ± 2 DEG C.
Embodiment 1
A kind of preparation method of the nano core-shell compound of photo-thermal enhancing degradation chemical warfare agent analogies, steps are as follows:
(1) preparation of light thermit powder
90mL water, 40mL ethyl alcohol and 2mL ammonium hydroxide obtain mixed solution after 30min is mixed, and weigh 0.5g Dopamine hydrochloride
Be dissolved in 10mL water and being added in mixed solution, persistently stirred at 30 DEG C for 24 hours, after reaction, solid is collected by centrifugation, spend from
Sub- water washing is three times to get light thermit powder dopamine melanin nano particle (Dpa NPs)；
(2) preparation of nano core-shell compound
The Dpa NPs weighed in 7mg step (1) is dispersed in 50mL n,N-Dimethylformamide, and 1.3mmol chlorine is added
Change zirconium, stirs 5h at room temperature and obtain disperse system, it is therefore an objective to the zirconium ion on Dpa NPs adsorption；By 1.3mmol 2- amino pair
Phthalic acid is added in disperse system, after stirring 1h at room temperature, disperse system is put into reaction kettle, hydro-thermal reaction at 140 DEG C
For 24 hours, after reaction, solid is collected by centrifugation, is washed three times with n,N-Dimethylformamide, obtained solid is placed in 110 DEG C very
In empty drying box dry to get using Dpa NPs as core, with UiO-66-NH2For the nano core-shell compound of shell, i.e. Dpa@UiO-
66-NH2。
The SEM photograph of Dpa NPs made from the present embodiment is as shown in Figure 1, Dpa NPs manufactured in the present embodiment has relatively
Smooth surface, the diameter of particle are 150~400nm, average diameter 200nm.
Dpa@UiO-66-NH made from the present embodiment2SEM photograph as shown in Fig. 2, Dpa@UiO- manufactured in the present embodiment
66-NH2Surface is by UiO-66-NH2Nanocrystalline composition, Dpa@UiO-66-NH2Diameter be 300~500nm, average diameter is
400nm。
Dpa NPs made from the present embodiment, Dpa@UiO-66-NH2X-ray diffraction spectrogram as shown in figure 3, can by Fig. 3
Know, the X-ray diffraction data of Dpa NPs manufactured in the present embodiment shows a wide diffraction relevant to its undefined structure
Peak, Dpa@UiO-66-NH2And UiO-66-NH2It coincide with the data of simulation preferable, it was demonstrated that the present embodiment is successfully prepared Dpa@
UiO-66-NH2。
Dpa NPs made from the present embodiment, Dpa@UiO-66-NH2Fourier transform infrared spectroscopy figure as shown in figure 4,
As shown in Figure 4, the present embodiment is successfully prepared Dpa NPs, Dpa@UiO-66-NH2。
Dpa NPs made from the present embodiment, Dpa@UiO-66-NH2Thermogravimetric analysis figure as shown in figure 5, by Dpa NPs,
Dpa@UiO-66-NH2And UiO-66-NH2Thermogravimetric curve analyze it is found that UiO-66-NH2In Dpa@UiO-66-NH2In it is shared
Mass fraction be 82%.
Dpa NPs made from the present embodiment, Dpa@UiO-66-NH2N2Adsorption desorption curve as shown in fig. 6, it will be appreciated from fig. 6 that
Dpa NPs、Dpa@UiO-66-NH2And UiO-66-NH2The BET of powder is respectively 21,730 and 736m2g-1。
Dpa NPs made from the present embodiment, Dpa@UiO-66-NH2Ultraviolet-visible-near-infrared spectrum figure such as Fig. 7 institute
Show, as shown in Figure 7, Dpa@UiO-66-NH made from the present embodiment2Maintain the good optical absorption property of Dpa itself, explanation
Dpa@UiO-66-NH2There are the potentiality as optothermal material.
Dpa NPs made from the present embodiment, Dpa@UiO-66-NH2Temperature under near-infrared laser irradiation is at any time
Variation is as shown in figure 8, as shown in Figure 8, Dpa@UiO-66-NH made from the present embodiment2Temperature gradient variation than Dpa is said greatly
Bright Dpa@UiO-66-NH2With good photothermal conversion efficiency, optothermal material can be used as.
Embodiment 2
A kind of preparation method of the composite cellulosic membrane of photo-thermal enhancing degradation chemical warfare agent analogies, steps are as follows:
(1) preparation of spinning solution
Dpa@UiO-66-NH prepared by 0.6g embodiment 12Disperse in 3.6g N,N-dimethylformamide solution equal
It is even, 0.4g polyacrylonitrile stirring 12h is added, is uniformly mixed and obtains spinning solution；Wherein the weight average molecular weight of polyacrylonitrile is
150000；
(2) preparation of composite cellulosic membrane
The spinning solution that step (1) is obtained carries out electrostatic spinning, spinning condition are as follows: spinning voltage 16kV, electrode distance
180mm, 30 DEG C of temperature, relative humidity 10% is to get composite cellulosic membrane, i.e. Dpa@UiO-66-NH2/PAN。
Composite cellulosic membrane Dpa@UiO-66-NH made from the present embodiment2The SEM of/PAN schemes as shown in figure 9, the fiber
Diameter is 0.5~3 μm.
Composite cellulosic membrane Dpa@UiO-66-NH made from the present embodiment2The x-ray diffraction pattern of/PAN is as shown in Figure 10, by
Figure 10 is it is found that composite cellulosic membrane Dpa@UiO-66-NH made from the present embodiment2/ PAN has still maintained UiO-66-NH2Crystal
Structure.
Composite cellulosic membrane Dpa@UiO-66-NH made from the present embodiment2The Fourier transform infrared spectroscopy figure of/PAN is as schemed
Shown in 11, as shown in Figure 11, composite cellulosic membrane Dpa@UiO-66-NH made from the present embodiment2/ PAN has still maintained UiO-66-
NH2Active function groups.
Composite cellulosic membrane Dpa@UiO-66-NH made from the present embodiment2The thermogravimetric analysis figure of/PAN is as shown in figure 12, by scheming
12 it is found that composite cellulosic membrane Dpa@UiO-66-NH made from the present embodiment2UiO-66-NH in/PAN2Content be 56%.
Dpa@UiO-66-NH made from the present embodiment2The N of/PAN composite cellulosic membrane2Adsorption desorption curve is as shown in figure 13, by
Figure 13 is it is found that Dpa@UiO-66-NH made from the present embodiment2The BET of/PAN composite cellulosic membrane is 254m2g-1。
Dpa@UiO-66-NH made from the present embodiment2The stress-strain diagram of/PAN composite cellulosic membrane is as shown in figure 14, by
Figure 14 is it is found that Dpa@UiO-66-NH made from the present embodiment2The tensile strength of/PAN composite cellulosic membrane is 1.61Mpa, illustrates this
Invent the Dpa@UiO-66-NH of preparation2/ PAN composite cellulosic membrane has good mechanical strength.
Composite cellulosic membrane Dpa@UiO-66-NH made from the present embodiment2The optical photograph of/PAN is as shown in figure 15, illustrates this
Invent the composite cellulosic membrane Dpa@UiO-66-NH of preparation2/ PAN has highly scalable.
Comparative example 1
A kind of organic metal framework compound UiO-66-NH2The preparation method of powder, steps are as follows:
1.3mmol zirconium chloride and 1.3mmol 2- amino terephthalic acid (TPA) are dissolved in 50mL n,N-Dimethylformamide, then
Solution is transferred in 100mL reaction kettle, after reacting for 24 hours under the conditions of 140 DEG C, solid is collected by centrifugation, with N, N- dimethyl formyl
Amine wash three times, at 110 DEG C be dried in vacuo to get.
Comparative example 2
A kind of metal organic framework compound UiO-66-NH2The preparation method of powder and light thermit powder Dpa NPs mixture,
Steps are as follows:
By 0.49g UiO-66-NH2Powder and 0.11g Dpa NPs are uniformly mixed to get UiO-66-NH2With Dpa NPs
Mixture.
Wherein, UiO-66-NH2The preparation method of powder is the same as comparative example 1, light thermit powder Dpa NPs and light thermit powder in embodiment 1
Preparation method it is identical.
Comparative example 3
A kind of composite cellulosic membrane UiO-66-NH2The preparation method of/PAN, as described in Example 2, except that:
In step (1), by 0.49g UiO-66-NH2Powder disperses in 3.6g N,N-dimethylformamide solution
It is even.
Wherein, UiO-66-NH2The preparation method of powder is the same as comparative example 1.
Comparative example 4
A kind of composite cellulosic membrane UiO-66-NH2With Dpa NPs mixture/PAN preparation method, as described in Example 2,
Except that:
In step (1), by 0.11g Dpa NPs and 0.49g UiO-66-NH2Powder is in 3.6g N, N- dimethyl formyl
It is uniformly dispersed in amine aqueous solution.
Wherein, UiO-66-NH2The preparation method of powder is the same as comparative example 1, light thermit powder Dpa NPs and light thermit powder in embodiment 1
Preparation method it is identical.
Experimental example 1
Near-infrared laser and plus near-infrared laser condition is being not added respectively in the product that embodiment 1 and comparative example 1-2 obtain
The lower degradation experiment carried out to chemical warfare agent analogies diformazan grass ether (DMNP), the specific steps are as follows: at room temperature, by 6.7-
The N-ethylmorpholine aqueous solution of the above-mentioned powder sample of 7.7mg and 1mL 0.45M are vigorously stirred 30min in 7mL quartz test tube, so
Test tube is respectively placed in the camera bellows with near-infrared laser and gauge without light source afterwards, and places recirculated water around it, by temperature
It is maintained at 25 DEG C.4 μ L DMNP are added in above-mentioned mixed liquor and continue to stir, take out the dilution of 20 μ L solution at regular intervals
In 0.15M N-ethylmorpholine aqueous solution, the absorbance of each sample is detected with ultraviolet-visible spectrophotometer, is obtained such as figure
The conversion rate curve of DMNP shown in 16-18.
By Figure 16-18 it is found that under no near-infrared laser radiation condition, UiO-66-NH2、UiO-66-NH2With Dpa NPs
Mixture, Dpa@UiO-66-NH2Three powder samples shown in the reaction in 30min almost the same degradation rate,
Dynamics, half-life period are respectively 2.6,2.8 and 2.7min.Under near-infrared laser irradiation, Dpa@UiO-66-NH2Catalytic degradation
The dynamics of DMNP dramatically increases, and half-life period is down to 0.7min, and conversion rate (TOF) increases 2.9 times, and UiO-66-NH2With
The degradation effect of the mixture of Dpa NPs under the same conditions is more weaker, UiO-66-NH2Degradation effect of the powder to DMNP
Substantially do not change.Illustrate the Dpa@UiO-66-NH of present invention design synthesis2Nano core-shell compound is imitated because of its good photo-thermal
The degradation efficiency to chemical warfare agent analogies should be greatly improved, and the superiority on core-shell structure causes photo-thermal to enhance
Catalytic efficiency be much higher than Dpa NPs and UiO-66-NH2Random mixture.
Experimental example 2
Near-infrared laser and plus near-infrared laser condition is being not added respectively in the product that embodiment 2 and comparative example 3-4 obtain
The lower Degrading experiment carried out to chemical warfare agent analogies diformazan grass ether (DMNP), the specific steps are as follows: at room temperature, 12mg is above-mentioned
The N-ethylmorpholine aqueous solution of the fiber membrane sample and 1mL 0.45M that have shredded is vigorously stirred 30min in 7mL quartz test tube.
Then test tube is respectively placed in the camera bellows with near-infrared laser and gauge without light source, and places recirculated water around it, it will be warm
Degree is maintained at 25 DEG C.4 μ L DMNP are added in above-mentioned mixed liquor and continue to stir, it is dilute to take out 20 μ L solution at regular intervals
Release in 0.15M N-ethylmorpholine aqueous solution, the absorbance of each sample detected with ultraviolet-visible spectrophotometer, obtain as
The conversion rate curve of DMNP shown in Figure 19-21.
By Figure 19-21 it is found that under no near-infrared laser radiation condition, UiO-66-NH2/PAN、UiO-66-NH2And Dpa
NPs mixture/PAN and Dpa@UiO-66-NH2Tri- kinds of tunica fibrosas of/PAN show similar inversion cuver to the degradation of DMNP,
80% DMNP degrades in 30min, and half-life period is about 14min.When being irradiated with near-infrared laser, Dpa@UiO-66-NH2/
PAN shows most fast degradation rate (t1/2=1.8min) and highest conversion ratio (100%), TOF increases 5.8 times, than making
Use UiO-66-NH2Powder (t1/2=1.8vs.2.6min) degradation rate faster.And UiO-66-NH2With Dpa NPs mixture/
The half-life period of PAN catalytic degradation DMNP is reduced to 6.7min, and conversion ratio increases to 97%.Illustrate Dpa@UiO- prepared by the present invention
66-NH2The photo-thermal enhancing catalysis of/PAN composite cellulosic membrane can significantly improve the detoxifying properties of tunica fibrosa, wherein photo-thermal effect
The catalyst function of the core-shell structure of material is more more effective than the random mixture of two kinds of components.
Claims (10)
1. a kind of nano core-shell compound of photo-thermal enhancing degradation chemical warfare agent analogies, which is characterized in that the nano core-shell
Compound is shell by core, MOFs of light thermit powder；
Wherein, the light thermit powder is dopamine melanin nano particle, and the diameter of particle is 150~400nm, and the MOFs is
UiO-66-NH2, the nano core-shell compound is Dpa@UiO-66-NH2, the diameter of compound is 300~500nm.
2. a kind of composite cellulosic membrane of photo-thermal enhancing degradation chemical warfare agent analogies, which is characterized in that the composite cellulosic membrane is
Nano core-shell compound and spinning-aid agent described in claim 1 mix the composite cellulosic membrane obtained by electrostatic spinning process；
Wherein, the composite cellulosic membrane is Dpa@UiO-66-NH2/ PAN, the diameter of fiber are 0.5~3 μm.
3. composite cellulosic membrane as claimed in claim 2, which is characterized in that the spinning-aid agent is polyacrylonitrile, Weight-average molecular
Amount is 150000~200000.
4. a kind of preparation side of the nano core-shell compound of photo-thermal enhancing degradation chemical warfare agent analogies described in claim 1
Method, which is characterized in that steps are as follows:
(1) preparation of light thermit powder
Mixed solution is mixed after 20~50min to obtain in water, ethyl alcohol and ammonium hydroxide, weigh Dopamine hydrochloride it is soluble in water be added to it is mixed
It closes in solution, persistently stirs 20~30h and solid is collected by centrifugation after reaction, be washed with deionized three times to get photo-thermal
Agent dopamine melanin nano particle；
(2) preparation of nano core-shell compound
Weigh in step (1) dopamine melanin nano particle dispersion in a solvent, be added zirconium chloride, at room temperature stir 4~
6h obtains disperse system, it is therefore an objective to adsorb zirconium ion on dopamine melanin nano particle；It weighs organic ligand and is added to disperse system
In, after stirring 1h at room temperature, disperse system is put into reaction kettle and carries out hydro-thermal reaction, after hydro-thermal reaction, is collected by centrifugation solid
Body, with solvent wash three times, by obtained solid be placed in baking oven dry to get using dopamine melanin nano particle as core, with
UiO-66-NH2For the nano core-shell compound of shell.
5. preparation method as claimed in claim 4, which is characterized in that meet one or more in the following conditions:
I. the volume ratio of step (1) water, ethyl alcohol and ammonium hydroxide is (40~50): (15~25): 1；
Ii. step (1) Dopamine hydrochloride mass concentration soluble in water is 0.04~0.1g/mL；
Iii. the temperature of step (1) described reaction is 20~40 DEG C；
Iv. step (2) solvent is n,N-Dimethylformamide, and the organic ligand is 2- amino terephthalic acid (TPA)；
V. the mass concentration of step (2) the dopamine melanin nano particle in a solvent is 0.1~0.2mg/mL；It is described more
The mass ratio of bar amine melanin nano particle and zirconium chloride is 1:(30~60)；The molar ratio of the zirconium chloride and organic ligand is
1:1；
Vi. the reaction temperature of step (2) described hydro-thermal reaction is 130~150 DEG C, and the reaction time is 20~30h.
6. a kind of preparation method of the composite cellulosic membrane of photo-thermal enhancing degradation chemical warfare agent analogies as claimed in claim 2,
It is characterized in that, steps are as follows:
(1) preparation of spinning solution
By the nano core-shell compound of the preparation of preparation method according to claim 4 in N,N-dimethylformamide solution
Be uniformly dispersed, add polyacrylonitrile be uniformly mixed obtain spinning solution；
(2) preparation of composite cellulosic membrane
The spinning solution that step (1) is obtained carries out electrostatic spinning to get composite cellulosic membrane.
7. preparation method as claimed in claim 6, which is characterized in that step (1) the nano core-shell compound, polyacrylonitrile
Mass ratio with n,N-Dimethylformamide is (0.011~1.5): 1:9, and wherein the weight average molecular weight of polyacrylonitrile is 150000
~200000.
8. preparation method as claimed in claim 6, which is characterized in that the condition of step (2) described electrostatic spinning are as follows: spinning electricity
Press 10~20kV, 150~200mm of electrode distance, 25~30 DEG C of temperature, relative humidity 10~15%.
9. nano core-shell compound or claim 2 institute of photo-thermal enhancing degradation chemical warfare agent analogies described in claim 1
Application of the composite cellulosic membrane stated in catalytic degradation chemical warfare agent analogies diformazan grass ether, which is characterized in that steps are as follows:
Nano core-shell compound described in claim 1 is added into reaction vessel or shreds as claimed in claim 2 compound
Tunica fibrosa, and alkaline aqueous solution is added, it is vigorously stirred 30min, container is placed in the camera bellows with light source, then by diformazan grass
Ether is added in above-mentioned mixed liquor and continues to stir, and reacts 20~30min, completes the degradation of diformazan grass ether.
10. application as claimed in claim 9, which is characterized in that meet one or more in the following conditions:
I. the mass ratio of the nano core-shell compound and diformazan grass ether is (1.1~1.4): 1, the composite cellulosic membrane and diformazan
The mass ratio of careless ether is (2.1~2.4): 1；
Ii. the alkaline aqueous solution is N-ethylmorpholine aqueous solution, and concentration is 0.1~0.5M；
Iii. the light source is ultraviolet source, visible light source or near-infrared light source；
Iv. the temperature of the reaction is 25 DEG C.
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| CN113502596A (en) * | 2021-06-28 | 2021-10-15 | 南通大学 | Self-supporting MgTiO3Nano fiber chemical warfare agent degradation material and preparation method thereof |
| CN113930859A (en) * | 2021-10-29 | 2022-01-14 | 中国海洋大学 | Multifunctional core-shell self-repairing electrostatic spinning material and synthesis method and application thereof |
| CN114307693A (en) * | 2022-01-04 | 2022-04-12 | 大连理工大学 | Preparation method of MOFs and polymer bicontinuous mixed matrix membrane |
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