CN109126885A - A kind of copper cobalt dual-metal organic frame/nano-fiber composite material and its preparation method and application - Google Patents
A kind of copper cobalt dual-metal organic frame/nano-fiber composite material and its preparation method and application Download PDFInfo
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- CN109126885A CN109126885A CN201811070248.XA CN201811070248A CN109126885A CN 109126885 A CN109126885 A CN 109126885A CN 201811070248 A CN201811070248 A CN 201811070248A CN 109126885 A CN109126885 A CN 109126885A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 59
- 239000002184 metal Substances 0.000 title claims abstract description 58
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002121 nanofiber Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 91
- 230000003197 catalytic effect Effects 0.000 claims abstract description 34
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 19
- 230000015556 catabolic process Effects 0.000 claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 68
- 238000001523 electrospinning Methods 0.000 claims description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 15
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 37
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 28
- 229940043267 rhodamine b Drugs 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 21
- 239000000987 azo dye Substances 0.000 abstract description 8
- 239000000975 dye Substances 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 5
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 80
- 239000002245 particle Substances 0.000 description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 19
- 238000006555 catalytic reaction Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 13
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 239000013084 copper-based metal-organic framework Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- -1 hydroxyl free radical Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 210000001170 unmyelinated nerve fiber Anatomy 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 239000002023 wood Substances 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/16—Copper
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
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- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of copper cobalt dual-metal organic frame/nano-fiber composite material (CuCo-MOF@NF), copper cobalt dual-metal organic framework is prepared using solvent-thermal method first, it is mixed with high molecular polymer then, copper cobalt dual-metal organic frame/nano-fiber composite material is prepared by the method for electrostatic spinning.The composite material all has good catalytic effect to the azo dyes such as rhodamine B (dye of positive ion) and azogeramine (anionic dye) at normal temperatures and pressures；The preparation method that the composite material is related to is simple, catalyst operates conveniently, high catalytic efficiency, stability are good, catalyst amount is few, recycling is convenient, is easy to be mass produced, and has a good application prospect in terms of the catalytic degradation of azo dyes and other pollution controls in industrial wastewater.
Description
Technical field
The invention belongs to environment functional material fields, and in particular to a kind of copper cobalt dual-metal organic frame/nanofiber is multiple
Condensation material and its preparation method and application.
Background technique
With the fast development of modernization and the extensive use of industry and agrochemicals, soil is related to the pollution of water
Problem is increasingly sharpened, therefore developing the effective catalyst for capableing of quick catalysis degradation water pollutant, there is important reality to anticipate
Justice.Transition-metal catalyst is a kind of efficient and cheap catalyst by wide coverage, can be used for catalytic degradation organic contamination
Object.For example, (Zeolitic Imidazole Framework-67 (ZIF-67) the as a heterogeneous such as Lin KYA
catalyst to activate peroxymonosulfate for degradation of Rhodamine B in
water[J].Journal ofthe Taiwan Institute of Chemical Engineers,2015,53:40-45)
Co-MOF (ZIF-67) is activated into potassium hydrogen peroxymonosulfate (PMS) catalytic degradation rhodamine B (RhB) as a kind of particle catalyst,
Although its catalytic performance is preferable, MOFs catalyst still remains many disadvantages.General this catalyst is powder or particle
Shape is dispersed in the suspension system of substrate solution formation in catalytic process, therefore catalyst particle is difficult to separate, and is recycled very tired
Difficulty limits the application and industrialized production of this MOFs catalyst.And MOFs particle catalyst is generally nano particle, table
Face can be larger, is easy to reunite in catalytic process, reduces its catalytic performance.There is research to fix MOFs material at present
On graphene, such as patent CN107760261A " graphene-metal organic frame laminated film and preparation method thereof ", the method
MOFs material can be reduced in the agglomeration for being catalyzed or participating in other reaction process, but the two-dimensional structure of this substrate limits
The diffusion for having made material electronics transfer and reactant, affects catalytic effect.
MOFs particle catalyst is fixed on nanofiber, a kind of nanometer of one-dimentional structure can be obtained by electrostatic spinning
Fiber catalyst.Its aspect ratio with higher and biggish specific surface area, and in catalytic process, active site sufficiently exposes
In nanofiber surface, electron transfer rate is higher between nanofiber, excellent catalytic effect.After catalysis reaction is completed, receive
Rice fiber catalyst also can be recycled easier.(the Metal-organic framework one-dimensional such as Wang C
fibers as efficient catalysts for activating peroxymonosulfate[J].Chemical
Engineering Journal, 2017,330:262-271) polyacrylonitrile (PAN) is added in the dispersion liquid of ZIF-67 particle,
ZIF/PAN fiber film catalyst is prepared using electrostatic spinning technique.Such catalyst effect is preferable, solves to a certain degree
Stability of having determined and recycling problem.But this catalyst, there are some disadvantages, catalytic effect is undesirable under room temperature, and be catalyzed
PH value condition is 3.2 or so, and this greatly limits the practical applications of the catalyst material.Therefore, further exploitation is based on gold
Belong to organic frame/nanofibrous structures, and with the mild composite catalyst of good stability, operating condition with important
Realistic meaning.
Summary of the invention
It is a primary object of the present invention in view of the deficienciess of the prior art, providing a kind of copper cobalt dual-metal has machine frame
Frame/nano-fiber composite material, it is to prepare obtained nanofiber, and metallic copper using copper cobalt dual-metal organic framework
Be distributed in the oxide of metallic cobalt and the two in the nanofiber, make gained composite material have stronger stability,
Higher catalytic activity and recycling degree.And the preparation method being related to is simple, has in fields such as catalysis, pollution controls important
Application prospect.
To realize above scheme, the technical solution adopted by the present invention are as follows:
A kind of copper cobalt dual-metal organic frame/nano-fiber composite material, it is to utilize copper cobalt dual-metal organic framework
Obtained nanofiber is prepared, and metallic copper and metallic cobalt and the oxide of the two are distributed in the nanofiber.
A kind of preparation method of above-mentioned copper cobalt dual-metal organic frame/nano-fiber composite material, it includes the following steps:
1) mantoquita, cobalt salt, ligand, organic solvent are uniformly mixed, obtain precursor solution, then carry out solvent thermal reaction,
Washing, drying, obtain copper cobalt dual-metal organic framework；
2) gained copper cobalt dual-metal organic framework and high molecular polymer are added in organic solvent, are stirred
It is even, obtain electrospinning precursor solution；
3) electrospinning precursor solution is subjected to electrostatic spinning to get copper cobalt dual-metal organic frame/nanofiber composite wood
Material.
In above scheme, any one of the mantoquita in copper nitrate, copper chloride, copper sulphate, copper acetate；Cobalt salt choosing
From any one in cobalt nitrate, cobalt chloride, cobaltous sulfate, cobalt acetate.
In above scheme, the ligand is one of 2-methylimidazole, terephthalic acid (TPA), trimesic acid.
In above scheme, the organic solvent is dimethylformamide or dimethyl acetamide.
In above scheme, the high molecular polymer is one of polyacrylonitrile, polyaniline, polystyrene, polylactic acid
Or it is several.
In above scheme, the molar ratio of the mantoquita and cobalt salt is 1:(1~4).
In above scheme, the molar ratio of the mantoquita and cobalt salt integral molar quantity and ligand is 1:(2~4).
In above scheme, the mass ratio of the mantoquita and cobalt salt gross mass and high molecular polymer is 1:(1~4)；High score
Sub- polymer accounts for the 10~15% of electrospinning precursor solution quality.
In above scheme, the solvent thermal reaction temperature is 100-160 DEG C, time 18-24h.
In above scheme, in the electrostatic spinning process, spinning voltage 12-15kV, receiving distance is 10-15cm, quiet
The driving velocity of Electrospun is 0.8-1.0mL/h.
Copper cobalt dual-metal organic frame/nano-fiber composite material obtained by above scheme, which is applied to catalytic degradation water body, to be had
Machine pollutant all has preferable catalytic to cation azobenzene dyes such as the anionic azo dyes such as azogeramine, rhodamine Bs
Effect, and required catalytic condition is mild, catalytic stability is good, has potential application prospect in fields such as catalysis, pollution controls.
The principle of the present invention are as follows:
1) present invention prepares the metal-organic framework material of copper cobalt dual-metal using solvent-thermal method first, and internal distribution is big
Metering-orifice road, large specific surface area.On the basis of Co metallic catalyst, the introducing of Cu metallic element plays a significant role, copper metal
As secondary active site, helper activity is played to cobalt metal, so that the catalytic action of cobalt metal is enhanced: from structural point
See, Cu and Co and its oxide (active material) on carrier interaction and active material and carrier between effective phase
Interaction can improve the dispersibility and adhesive force of the transition metal such as Cu, Co, to be conducive to the activity and stability of catalyst；
In terms of reaction angle, Cu activates PMS etc. to generate SO4 ·-(potentiometric titrations) and OH (hydroxyl free radical) promotes Co ion
(Co2+、Co3+) reaction generation O4 ·-And OH, wherein to promoting generation OH effect prominent.And Cu and Co can mutually promote
In catalytic processThe metal ion reaction cycle of (M=Cu or Co).
Electrostatic spinning film is first prepared under common situation at present, then MOF material is grown in film surface again, is prepared
Load has the composite film material of MOFs particle.But the method for usually preparing MOFs particle is solvent-thermal method, reaction temperature is higher,
And the time is longer, if preparing and growing MOFs particle on film again, the structure of film may be destroyed under hot conditions.And
Solvent-thermal method uncontrollable factor is more, and the stability and load capacity of MOFs particle load may be poor and more difficult to control.Therefore,
The present invention first prepares MOFs particle and recycles electrostatic spinning that MOFs particle is fixed on nano fibrous membrane.This preparation method obtains
The composite material arrived, MOFs particle is more stable in the load of nanofiber, and load capacity is more, active site can more fully with have
The contact of machine pollutant, catalytic effect are enhanced.And its reaction condition milder, the scope of application are wider.
2) copper cobalt dual-metal organic frame/nano-fiber catalyst is prepared by electrostatic spinning technique in the present invention.It should
The nanofibrous structures energy increasing specific surface area of catalyst promotes the suction-operated to substrate, and can more effectively show activity
The exposure in site.MOFs particle is fixed on nano fibrous membrane, the cellular structure of nano fibrous membrane and MOFs particle can be held
Perhaps the organic pollutant in substrate comes into full contact with MOFs active material, promotes the absorption to substrate, to improve catalytic effect.
The copper cobalt dual-metal organic frame/nano-fiber catalyst being prepared, copper cobalt dual-metal organic framework materials are fixed on
On nanofiber, not only contribute to the exposure in MOF particle activated centre, and solve MOF particle suspension system difficulty separate,
The givey problem of MOF structural instability, therefore catalytic effect is more stable in practical applications, recycling is easier.
Compared with prior art, the invention has the following beneficial effects:
1) it is excellent to have that catalytic condition is mild, stability is good, be easy recycling, catalytic effect is obvious etc. for present invention gained catalyst
Point.
2) preparation process of the present invention is simple, and catalytic condition needed for catalyst is mild and catalytic stability is good, and grasps
Facilitate, can effectively solve MOF particle the problems such as the separation of suspension system difficulty, MOF structural instability easily collapse, suitable popularization is answered
With.
3) present invention gained copper cobalt dual-metal organic frame/nano-fiber composite material is to the anion azo such as azogeramine
The cation azobenzene dyes such as dyestuff, rhodamine B all have preferable catalytic effect, have in fields such as catalysis, pollution controls
Potential application prospect.
Detailed description of the invention
Fig. 1 (a) is copper cobalt dual-metal organic frame/nano-fiber material CuCo-MOF@prepared by the embodiment of the present invention 1
NF*SEM figure, Fig. 1 (b) be comparative example 1 of the present invention prepare copper cobalt dual-metal spread film CuCo-MOF*SEM figure；
Fig. 2 is copper cobalt dual-metal organic frame/nano-fiber material CuCo-MOF@NF prepared by the embodiment of the present invention 2
XRD diagram；
Fig. 3 is that nitrogen adsorption-desorption isothermal of embodiment 2 gained CuCo-MOF@NF and 2 gained CuCo-MOF of comparative example are bent
Line.
Fig. 4 is the pore size distribution curve of embodiment 2 gained CuCo-MOF@NF and 2 gained CuCo-MOF of comparative example.
Fig. 5 is 2 gained CuCo-MOF@NF of embodiment, 2 gained CuCo-MOF of comparative example, 3 gained Cu-MOF@NF of comparative example
The ultraviolet curve graph changed over time with 4 gained Co-MOF@NF of comparative example catalysis azogeramine, wherein C0For azogeramine solution
Initial concentration, CtFor the azogeramine solution concentration value after time t, t is the time；
Fig. 6 is CuCo-MOF@NF, 3 gained Cu-MOF@NF of comparative example and 4 gained Co-MOF@NF of comparative example in embodiment 2
The ultraviolet curve graph that catalysis rhodamine B changes over time, wherein C0For the initial concentration of rhodamine B solution, CtTo pass through time t
Rhodamine B solution concentration value afterwards, t are the time；
Fig. 7 is the ultraviolet curve graph that 3 gained 2-CuCo-MOF@NF of embodiment is catalyzed that azogeramine absorbance changes over time；
Fig. 8 is the ultraviolet curve graph that 4 gained 3-CuCo-MOF@NF rhodamine B absorbance of embodiment changes over time.
Fig. 9 is the datagram of 2 gained CuCo-MOF@NF catalytic stability of embodiment experiment.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
A kind of copper cobalt dual-metal organic frame/nano-fiber composite material, preparation method includes the following steps:
1) 2-methylimidazole of the copper nitrate of 1.5mmol, the cobalt nitrate of 1.5mmol, 6.0mmol are added to 50mL N,
In dinethylformamide (DMF) solution, after dissolution is sufficiently stirred, it is transferred in autoclave, is warming up to 120 DEG C, confined reaction
For 24 hours, water, ethanol washing then are used three times and be centrifuged, obtain copper cobalt dual-metal MOF particle；
2) 9.45g N,N-dimethylformamide is added in 0.50g copper cobalt dual-metal MOF particle and 1.36g polyacrylonitrile
(DMF) it in solution, stirs evenly, obtains electrospinning precursor solution；
3) gained electrospinning precursor solution is placed in 10mL with electrostatic spinning is carried out in the plastic injector of syringe needle, be arranged
Operating voltage be 12kV DC high-voltage, syringe needle is 15cm at a distance from receiver board, and in electro-spinning process, the humidity of environment is
30-50% is 1.0mL/h by the flow velocity that syringe pump controls electrospinning precursor solution, obtains the double gold of copper cobalt by electrostatic spinning
Belong to organic frame/nanofiber and (is named as CuCo-MOF@NF*)。
Copper cobalt dual-metal organic frame/nanofiber SEM figure obtained by the present embodiment is shown in Fig. 1, it can be seen that bimetallic
MOF uniform particle is supported on nano fibrous membrane, and the diameter of nanofiber is in 300~400nm or so.
Embodiment 2
A kind of copper cobalt dual-metal organic frame/nano-fiber composite material, preparation method includes the following steps:
1) terephthalic acid (TPA) of the copper nitrate of 1.5mmol, the cobalt nitrate of 1.5mmol, 6.0mmol are added to 50mL N,
In dinethylformamide (DMF) solution, after dissolution is sufficiently stirred, it is transferred in autoclave, is warming up to 120 DEG C, confined reaction
For 24 hours, water, ethanol washing then are used three times and is centrifuged, dries, obtain copper cobalt dual-metal MOF particle；
2) 9.45g N,N-dimethylformamide is added in 0.50g copper cobalt dual-metal MOF particle and 1.36g polyacrylonitrile
(DMF) it in solution, stirs evenly, obtains electrospinning precursor solution；
3) gained electrospinning precursor solution is placed in 10mL with electrostatic spinning is carried out in the plastic injector of syringe needle, be arranged
Operating voltage be 12kV DC high-voltage, syringe needle is 15cm at a distance from receiver board, and in electro-spinning process, the humidity of environment is
30-50% is 1.0mL/h by the flow velocity that syringe pump controls electrospinning precursor solution, obtains the double gold of copper cobalt by electrostatic spinning
Belong to organic frame/nanofiber (being named as CuCo-MOF@NF).The present invention is during the experiment by using different ligands (miaow
Azole or carboxylic acids ligand) preparation MOF discovery particle both topographically have certain difference, but performance no significant difference, now with carboxylic acid
For class ligand, a series of experiment and characterization are carried out.
The XRD diagram of the present embodiment products therefrom is shown in Fig. 2, the results showed that in the CuCo-MOFs material of hydro-thermal method preparation, point
It is furnished with the oxide of Cu, Co metal and the two, the two metal simple-substance and its oxide all have catalytic activity；And it is aoxidized in metal
In system existing for object, the active force between active metal is stronger, and catalyst is more stable.
The nitrogen adsorption of the present embodiment products therefrom-desorption isothermal curve and pore size distribution curve are shown in Fig. 3 and Fig. 4 respectively,
The result shows that the specific surface area of gained CuCo-MOF@NF is 102.204m2/ g, most of pore-size distribution is in 20nm hereinafter, aperture
Smaller and distribution uniform.
Embodiment 3
A kind of copper cobalt dual-metal organic frame/nano-fiber composite material, preparation method includes the following steps:
1) terephthalic acid (TPA) of the copper nitrate of 1.0mmol, the cobalt nitrate of 2.0mmol, 6.0mmol are added to 50mL N,
In dinethylformamide (DMF) solution, after dissolution is sufficiently stirred, it is transferred in autoclave, is warming up to 120 DEG C, confined reaction
For 24 hours, water, ethanol washing then are used three times and is centrifuged, dries, obtain copper cobalt dual-metal MOF particle；
2) 9.45g N,N-dimethylformamide is added in 0.50g copper cobalt dual-metal MOF particle and 1.36g polyacrylonitrile
(DMF) it in solution, stirs evenly, obtains electrospinning precursor solution；
3) gained electrospinning precursor solution is placed in 10mL with electrostatic spinning is carried out in the plastic injector of syringe needle, be arranged
Operating voltage be 12kV DC high-voltage, syringe needle is 15cm at a distance from receiver board, and in electro-spinning process, the humidity of environment is
30-50% is 1.0mL/h by the flow velocity that syringe pump controls electrospinning precursor solution, obtains the double gold of copper cobalt by electrostatic spinning
Belong to organic frame/nanofiber (being named as 2-CuCo-MOF@NF).
Embodiment 4
A kind of copper cobalt dual-metal organic frame/nano-fiber composite material, preparation method includes the following steps:
1) trimesic acid of the copper nitrate of 1.0mmol, the cobalt nitrate of 2.0mmol, 6.0mmol are added to 50mL N,
In dinethylformamide (DMF) solution, after dissolution is sufficiently stirred, it is transferred in autoclave, is warming up to 120 DEG C, confined reaction
For 24 hours, water, ethanol washing then are used three times and be centrifuged, obtain copper cobalt dual-metal MOF particle after dry；
2) 9.45g N,N-dimethylformamide is added in 0.50g copper cobalt dual-metal MOF particle and 1.36g polyacrylonitrile
(DMF) it in solution, stirs evenly, obtains electrospinning precursor solution；
3) gained electrospinning precursor solution is placed in 10mL with electrostatic spinning is carried out in the plastic injector of syringe needle, be arranged
Operating voltage be 12kV DC high-voltage, syringe needle is 15cm at a distance from receiver board, and in electro-spinning process, the humidity of environment is
30-50% is 1.0mL/h by the flow velocity that syringe pump controls electrospinning precursor solution, obtains the double gold of copper cobalt by electrostatic spinning
Belong to organic frame/nanofiber (being named as 3-CuCo-MOF@NF).
Comparative example 1
A kind of copper cobalt dual-metal organic frame/polyacrylonitrile composite material, preparation method include the following steps:
1) 2-methylimidazole of the copper nitrate of 1.5mmol, the cobalt nitrate of 1.5mmol, 6.0mmol are added to 50mL N,
In dinethylformamide (DMF) solution, after dissolution is sufficiently stirred, it is transferred in autoclave, is warming up to 120 DEG C, confined reaction
For 24 hours, water, ethanol washing then are used three times and be centrifuged, obtain copper cobalt dual-metal MOF particle；
2) 9.45g N,N-dimethylformamide is added in 0.50g copper cobalt dual-metal MOF particle and 1.36g polyacrylonitrile
(DMF) it in solution, stirs evenly, obtains mixed solution；
3) gained mixed solution being spread in surface plate, cap upper surface ware lid, is stood, solution to be mixed spontaneously dries,
The spread film for obtaining copper cobalt dual-metal (is named as CuCo-MOF*)。
The scanning electron microscope (SEM) photograph of this comparative example products therefrom is shown in Fig. 1 (b), it can be seen that spread film CuCo-MOF*Film it is endless
It is whole, and surface, without obvious MOFs particle, fold breakage is more.
Comparative example 2
A kind of copper cobalt dual-metal organic frame/polyacrylonitrile composite material, preparation method include the following steps:
1) terephthalic acid (TPA) of the copper nitrate of 1.5mmol, the cobalt nitrate of 1.5mmol, 6.0mmol are added to 50mL N,
In dinethylformamide (DMF) solution, after dissolution is sufficiently stirred, it is transferred in autoclave, is warming up to 120 DEG C, confined reaction
For 24 hours, water, ethanol washing then are used three times and be centrifuged, obtain copper cobalt dual-metal MOF particle；
2) 9.45g N,N-dimethylformamide is added in 0.50g copper cobalt dual-metal MOF particle and 1.36g polyacrylonitrile
(DMF) it in solution, stirs evenly, obtains mixed solution；
3) gained mixed solution being spread in surface plate, cap upper surface ware lid, is stood, solution to be mixed spontaneously dries,
Obtain the spread film (being named as CuCo-MOF) of copper cobalt dual-metal.
The nitrogen adsorption of this comparative example products therefrom-desorption isothermal curve and pore size distribution curve are shown in Fig. 3 and Fig. 4 respectively,
The result shows that the specific surface area of spread film only has 15.712m2/ g, and pore-size distribution is uneven.
Comparative example 3
A kind of copper metal organic frame/nanofiber, preparation method include the following steps:
1) 50mL N,N-dimethylformamide (DMF) solution is added in 3.0mmol copper nitrate, 6.0mmol terephthalic acid (TPA)
In, it after dissolution is sufficiently stirred, is transferred in autoclave, is warming up to 120 DEG C, confined reaction is for 24 hours；Then pass through water, ethyl alcohol respectively
It washs three times and is centrifuged, obtain copper metal MOF particle；
2) 9.45g N,N-dimethylformamide (DMF) is added in 0.50g copper metal MOF particle and 1.36g polyacrylonitrile
In solution.It stirs evenly, obtains electrospinning precursor solution；
3) gained electrospinning precursor solution is placed in 10mL in the plastic injector of syringe needle, operating voltage is 12kV's
DC high-voltage, syringe needle is 15cm at a distance from receiver board, and in electro-spinning process, the humidity of environment is 30%-50%, passes through injection
The flow velocity of pump control electrospinning precursor solution is 1.0mL/h, obtains copper metal organic frame/nanofiber by electrostatic spinning,
It is named as Cu-MOF@NF.
Comparative example 4
A kind of cobalt metal organic frame/nanofiber, preparation method include the following steps:
1) 50mL N,N-dimethylformamide (DMF) is added in the terephthalic acid (TPA) of the cobalt nitrate of 3.0mmol, 6.0mmol
It in solution, after dissolution is sufficiently stirred, is transferred in autoclave, is warming up to 120 DEG C, confined reaction is for 24 hours；Then respectively by water,
Ethanol washing three times and is centrifuged, and obtains cobalt metal MOF particle；
2) 9.45g N,N-dimethylformamide (DMF) is added in 0.50g cobalt metal MOF particle and 1.36g polyacrylonitrile
It in solution, stirs evenly, obtains electrospinning precursor solution；
3) acquired electrospinning precursor solution is placed in 10mL to have in the plastic injector of syringe needle, operating voltage 12kV
DC high-voltage, syringe needle is 15cm at a distance from receiver board, and in electro-spinning process, the humidity of environment is 30%-50%, passes through note
The flow velocity for penetrating pump control electrospinning precursor solution is 1.0mL/h, obtains cobalt metal organic frame/Nanowire by electrostatic spinning
Dimension, is named as Co-MOF@NF.
Application examples 1
Respectively by 2 gained CuCo-MOF@NF of embodiment, 2 gained CuCo-MOF of comparative example, 3 gained Cu-MOF@of comparative example
NF, 4 gained Co-MOF@NF of comparative example, are applied to catalysis azogeramine (anionic dye), and specific steps include:
1) the azogeramine solution for preparing 25mg/L, takes the azogeramine solution of 20mL into vial, is then added
The potassium hydrogen peroxymonosulfate (PMS) of 0.15g/L；
2) it is separately added into the CuCo-MOF@of 0.5g/L after potassium hydrogen peroxymonosulfate (PMS) dissolution in red 1 solution of oxytropism again
NF,CuCo-MOF,Cu-MOF@NF,Co-MOF@NF；At interval of feature of the 2min sampling and measuring azogeramine solution at 530nm
Absorption peak, until azo dyes azogeramine solution becomes colourless from red.
Fig. 2 is the ultraviolet curve graph that azogeramine solution changes over time, the results showed that, it is catalyzed using obtained by the present embodiment 2
Azogeramine solution fast degradation can be colourless in 4min by agent.
Application examples 2
Respectively by 2 gained CuCo-MOF@NF of embodiment, 3 gained Cu-MOF@NF of comparative example, 4 gained Co-MOF@of comparative example
NF, is applied to catalysis rhodamine B (dye of positive ion), and specific steps include:
1) rhodamine B solution for preparing 25mg/L, takes the rhodamine B solution of 20mL into vial, is then added
The potassium hydrogen peroxymonosulfate (PMS) of 0.15g/L；
2) it is separately added into the CuCo-MOF@of 0.5g/L after potassium hydrogen peroxymonosulfate (PMS) dissolution into rhodamine B solution again
NF,Cu-MOF@NF,Co-MOF@NF；At interval of characteristic absorption peak of the 2min sampling and measuring rhodamine B solution at 530nm, directly
It becomes colorless to azo dyes rhodamine B solution from orange red.
When Fig. 3 is using different catalysts, ultraviolet curve graph that rhodamine B solution changes over time, the results showed that, use
Rhodamine B solution fast degradation can be colourless in 6min by gained catalyst CuCo-MOF@NF of the invention.
Application examples 3
3 gained catalyst 2-CuCo-MOF@NF of embodiment is applied to catalysis azogeramine solution, specific steps include:
1) the azogeramine solution for preparing 25mg/L, takes the azogeramine solution of 20mL into vial, is then added
The potassium hydrogen peroxymonosulfate (PMS) of 0.15g/L；
2) the 2-CuCo-MOF NF of 0.5g/L is added after potassium hydrogen peroxymonosulfate (PMS) dissolution into azogeramine solution；Often
Be spaced full spectrum of the 2min sampling and measuring rhodamine B solution between 400nm to 600nm, until azo dyes azogeramine solution from
Red becomes colorless.
Fig. 7 is the ultraviolet curve graph that 3 gained 2-CuCo-MOF@NF of embodiment is catalyzed that rhodamine B absorbance changes over time；
The result shows that azogeramine solution degradation is colourless in 4min or so by catalyst.
Application examples 4
4 gained catalyst 3-CuCo-MOF@NF of embodiment is applied to catalysis rhodamine B solution, specific steps include:
1) rhodamine B solution for preparing 25mg/L, takes the rhodamine B solution of 20mL into vial, is then added
The potassium hydrogen peroxymonosulfate (PMS) of 0.15g/L；
2) the 3-CuCo-MOF NF of 0.5g/L is added after potassium hydrogen peroxymonosulfate (PMS) dissolution into rhodamine B solution；Often
Every full spectrum of the 2min sampling and measuring rhodamine B solution between 400nm to 600nm, until azo dyes rhodamine B solution is from orange
Red becomes colorless.
Fig. 8 is the ultraviolet curve that 4 gained 3-CuCo-MOF@NF of the present embodiment is catalyzed that rhodamine B absorbance changes over time
Figure；The result shows that catalyst rhodamine B solution is degraded in 6min it is colourless.
Application examples 5
By 2 gained catalyst CuCo-MOF@NF of embodiment, 5 repetitions are applied to azogeramine solution, specific steps packet
It includes:
1) the azogeramine solution for preparing 25mg/L, takes the azogeramine solution of 20mL into vial, is then added
The potassium hydrogen peroxymonosulfate (PMS) of 0.15g/L；
2) the CuCo-MOF NF of 0.5g/L is added after potassium hydrogen peroxymonosulfate (PMS) dissolution into azogeramine solution；Every
Every characteristic absorption peak of the 2min sampling and measuring azogeramine solution at 530nm, until azo dyes azogeramine solution is from red
Become colourless；
3) after Catalysis experiments, CuCo-MOF@NF tunica fibrosa is taken out, for several times with ethanol washing, other conditions after drying
The above-mentioned Catalysis experiments of constant repetition so repeat experiment 5 times, and record each Catalysis experiments data.
Fig. 9 is that catalyst CuCo-MOF@NF is applied to azogeramine in embodiment 2, is repeated 5 times the Catalytic data figure of experiment,
It can be seen that catalytic condition needed for present invention gained catalyst is mild and catalytic stability is good.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection scope of the invention.
Claims (10)
1. a kind of copper cobalt dual-metal organic frame/nano-fiber composite material, it is to utilize copper cobalt dual-metal organic framework system
Standby obtained nanofiber, the oxide of metallic copper, metallic cobalt and the two are distributed in the nanofiber.
2. a kind of preparation method of copper cobalt dual-metal organic frame/nano-fiber composite material, which is characterized in that including walking as follows
It is rapid:
1) mantoquita, cobalt salt, ligand, organic solvent are uniformly mixed, obtain precursor solution, then carry out solvent thermal reaction, wash,
It is dry, obtain copper cobalt dual-metal organic framework；
2) gained copper cobalt dual-metal organic framework and high molecular polymer are added in organic solvent, are uniformly mixed, obtain
Electrospinning precursor solution；
3) electrospinning precursor solution is subjected to electrostatic spinning to get copper cobalt dual-metal organic frame/nano-fiber composite material.
3. preparation method according to claim 2, which is characterized in that the mantoquita is selected from copper nitrate, copper chloride, sulfuric acid
One of copper, copper acetate；Cobalt salt is selected from one of cobalt nitrate, cobalt chloride, cobaltous sulfate, cobalt acetate.
4. preparation method according to claim 2, which is characterized in that the ligand be 2-methylimidazole, terephthalic acid (TPA),
One of trimesic acid.
5. preparation method according to claim 2, which is characterized in that the organic solvent is dimethylformamide or diformazan
Yl acetamide.
6. preparation method according to claim 2, which is characterized in that the high molecular polymer is polyacrylonitrile, polyphenyl
One or more of amine, polystyrene, polylactic acid.
7. preparation method according to claim 2, which is characterized in that the molar ratio of the mantoquita and cobalt salt be 1:(1~
4)；The molar ratio of the mantoquita and cobalt salt integral molar quantity and ligand is 1:(2~4).
8. preparation method according to claim 2, which is characterized in that the mantoquita and cobalt salt gross mass and high molecular polymerization
The mass ratio of object is 1:(1~4)；High molecular polymer accounts for the 10~15% of electrospinning precursor solution quality.
9. preparation method according to claim 2, which is characterized in that the solvent thermal reaction temperature is 100-160 DEG C, when
Between be 18-24h.
10. copper cobalt dual-metal organic frame/nanometer obtained by any one of described in claim 1 or claim 2~9 preparation method
Application of the fibrous composite in catalytic degradation organic pollutants in water body field.
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