CN110523438A - A kind of ferrous metals organic framework material, preparation method and the application of modification - Google Patents
A kind of ferrous metals organic framework material, preparation method and the application of modification Download PDFInfo
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- CN110523438A CN110523438A CN201910823378.4A CN201910823378A CN110523438A CN 110523438 A CN110523438 A CN 110523438A CN 201910823378 A CN201910823378 A CN 201910823378A CN 110523438 A CN110523438 A CN 110523438A
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- -1 ferrous metals Chemical class 0.000 title claims abstract description 55
- 239000013384 organic framework Substances 0.000 title claims abstract description 48
- 230000004048 modification Effects 0.000 title claims abstract description 40
- 238000012986 modification Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 86
- 239000011651 chromium Substances 0.000 claims abstract description 72
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 46
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 44
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 31
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 28
- 230000005855 radiation Effects 0.000 claims abstract description 26
- PSVSZBOMJGAVRS-UHFFFAOYSA-N 2,3-diaminoterephthalic acid Chemical compound NC1=C(N)C(C(O)=O)=CC=C1C(O)=O PSVSZBOMJGAVRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 78
- 239000011259 mixed solution Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 12
- 239000012621 metal-organic framework Substances 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003672 processing method Methods 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 23
- 239000007864 aqueous solution Substances 0.000 abstract description 16
- 239000002351 wastewater Substances 0.000 abstract description 5
- 229910002549 Fe–Cu Inorganic materials 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 55
- 239000013082 iron-based metal-organic framework Substances 0.000 description 37
- 238000006731 degradation reaction Methods 0.000 description 35
- 230000015556 catabolic process Effects 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 25
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000010586 diagram Methods 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction 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
- 239000008213 purified water Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
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- 238000004088 simulation Methods 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical group [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
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- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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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]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J2531/842—Iron
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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)
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- Organic Chemistry (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)
- Catalysts (AREA)
Abstract
The present invention relates to technical field of waste water processing more particularly to a kind of ferrous metals organic framework materials of modification, preparation method and application.The ferrous metals organic framework material of the modification, is prepared by the raw material comprising following parts by weight of component: 800~900 parts of Iron trichloride hexahydrate powder；500~600 parts of diamino terephthalic acid (TPA)；6~30 parts of molybdenum disulfide.Modified ferrous metals organic framework material can quickly adsorb the Cr VI in aqueous solution on the surface of the material, and under the radiation of visible light, the amino in modified ferrous metals organic backbone generates light induced electron and hole after absorbing the radiation of visible light.Light induced electron transits to Fe-Cu deposits at first, and because of the introducing of molybdenum disulfide, extends the service life of light induced electron, light induced electron is enabled rapidly and effectively to move to surface from composite inner, and reacted with the Cr VI for being adsorbed on surface, it is translated into trivalent chromium, thus chromium of effectively degrading.
Description
Technical field
The present invention relates to technical field of waste water processing more particularly to a kind of ferrous metals organic framework materials of modification, system
Preparation Method and application.
Background technique
Chromium (Cr) is sugar in humans and animals body, one of required microelement in protein and fat metabolism.In nature
In, chromium mainly exists in the form of trivalent and sexavalence, and Cr (VI) has stronger toxicity, Excess free enthalpy meeting to most of biologies
Lead to the intracorporal cancer of biology, mutagenicity and death.However, current whole world pollution of chromium situation very severe, many natural waters
The Cr (VI) of high concentration is all detected in body.The concern of many researchers is gradually caused in water body the problem of pollution of chromium.Most often
The processing method seen is to convert Cr (VI) to nontoxic Cr (III), traditional restoring method such as biological and chemical reduction method by
In time-consuming, at high cost and easily cause secondary pollution without being favored by people.Compared with above two method, photocatalysis technology tool
There is very big advantage, without generating secondary pollution while may be implemented faster rate of reduction.But high-performance optical is catalyzed
The preparation of agent material is the major obstacle that the technology realizes large-scale practical application.
Metal organic framework (MOF) be used as a kind of novel porous crystalline material, in the past few decades always in occupation of
Research hotspot.Since it has flexible regulatable bandgap structure, MOF can provide excellent photo-catalysis capability.Numerous metals
In base organic framework material, ferrous metals organic backbone (Fe-MOF) due to be able to achieve preferable stability in aqueous solution and by
Concerned, organic linker or metal-oxygen cluster in structure can produce light induced electron under the induction of light, via in structure
Portion reaches material surface, can restore the Cr (VI) in aqueous solution.Meanwhile itself large surface area and pore structure also can be
The process provides a large amount of absorption and active sites.Unfortunately, some intrinsic defects still limit Fe-MOF in light
The application of catalytic field, such as electronic conductivity difference and carrier separation low efficiency.Currently, mitigating the main means of these defects
It is to couple Fe-MOF with other semiconductors.
MoS2, one kind have extremely narrow direct band gap (1.2eV) semiconductor, can fast implement photon-electron conversion, then
In addition itself excellent conductivity, these characteristics make MoS2As laser emitter, photodetector and solar battery etc.
The ideal material of application.Nevertheless, being also due to narrow band gap, the recombination rate of carrier is very fast, will lead to light induced electron without
Method is utilized, i.e., catalyst effect is deteriorated, therefore MoS2Seldom catalysis material is used alone as to be used.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of ferrous metals organic backbone material of modification
Material, preparation method and application, the ferrous metals organic framework material of modification provided by the invention can be effectively treated in water body
Chromium.
The present invention provides a kind of ferrous metals organic framework materials of modification, by the raw material comprising following parts by weight of component
It is prepared:
800~900 parts of Iron trichloride hexahydrate powder；
500~600 parts of diamino terephthalic acid (TPA)；
6~30 parts of molybdenum disulfide.
Preferably, the partial size of the Iron trichloride hexahydrate powder is 10~50 μm.
Preferably, it is made in a solvent by the raw material comprising Iron trichloride hexahydrate powder, diamino terephthalic acid (TPA) and molybdenum disulfide
It is standby to obtain；
The solvent is N,N-dimethylformamide；
The amount ratio of the Iron trichloride hexahydrate powder and the N,N-dimethylformamide is 800~900mg:55~75mL.
The present invention also provides a kind of preparation methods of the ferrous metals organic framework material of modification, comprising the following steps:
First mixed solution and the second mixed solution are mixed, 24~26h is reacted at 140~160 DEG C, obtains modification
Ferrous metals organic framework material；
First mixed solution is by Iron trichloride hexahydrate powder, diamino terephthalic acid (TPA) and a part of N, N- dimethyl formyl
Amine is mixed to get；
Second mixed solution is mixed to get by molybdenum disulfide and remaining N,N-dimethylformamide.
Preferably, the Iron trichloride hexahydrate powder and the amount ratio of a part of n,N-Dimethylformamide are 800~900mg:
50~60mL；
First mixed solution is by Iron trichloride hexahydrate powder and diamino terephthalic acid (TPA) in a part of N, N- dimethyl methyl
15~20min of ultrasonic disperse is obtained in amide.
Preferably, the molybdenum disulfide and the amount ratio of remaining n,N-Dimethylformamide are 6~30mg:5~15mL；
Second mixed solution, 15~20min of ultrasonic disperse in remaining N,N-dimethylformamide by molybdenum disulfide
It obtains.
Preferably, after the reaction, further includes:
Product after the reaction is centrifuged 15~20min at 8~12 DEG C；
The revolving speed of the centrifugation is 7500~8500rpm.
Preferably, after the centrifugation, further includes:
Then product after being centrifuged described in washes of absolute alcohol dries 12~15h at 145~155 DEG C.
The present invention also provides a kind of processing methods of chromium in water body, comprising the following steps:
Water body containing chromium is mixed with modified ferrous metals organic framework material, after visible optical radiation, after being purified
Water body.
Preferably, the intensity of the radiation is 80~120mWcm-2, the wavelength of radiation is not less than 420nm.
The present invention provides a kind of ferrous metals organic framework materials of modification, by the raw material comprising following parts by weight of component
It is prepared: 800~900 parts of Iron trichloride hexahydrate powder；500~600 parts of diamino terephthalic acid (TPA)；6~30 parts of molybdenum disulfide.This
The ferrous metals organic framework material for the modification that invention is prepared by the above raw material can be quickly by the sexavalence in aqueous solution
Chromium adsorbs on the surface of the material, and then, under the radiation of visible light, the amino in the ferrous metals organic backbone of composite material is being inhaled
After the radiation for having received visible light, carrier separation phenomenon occurs, generates light induced electron and hole.Wherein light induced electron transition at first
To Fe-Cu deposits, and because molybdenum disulfide introducing, hetero-junctions bonding between iron sulphur, it is suppressed that carrier it is compound, extend photoproduction
The service life of electronics, meanwhile, molybdenum disulfide can enable light induced electron rapidly and effectively to move to from composite inner
Surface, and reacted with the Cr VI for being adsorbed on surface, it is translated into trivalent chromium.Therefore, modification provided by the invention is iron-based
Metal-organic framework materials can effectively degrade the Cr (VI) in water body.
Therefore, the ferrous metals organic framework material of modification provided by the invention is under visible light in catalytic degradation aqueous solution
0.0095~0.0552min may be implemented in the degradation rate constant of Cr (VI)-1。
Detailed description of the invention
Fig. 1 is MoS prepared by the embodiment of the present invention 12@Fe-MOF、MoS2And the scanning electron microscope (SEM) photograph of Fe-MOF and transmission electricity
Mirror figure；
Fig. 2 is MoS prepared by the embodiment of the present invention 12@Fe-MOF、MoS2And the XRD spectra of Fe-MOF；
Fig. 3 is MoS in the embodiment of the present invention 22@Fe-MOF、MoS2And Fe-MOF catalytic degradation aqueous solution under visible light
Degradation amount-time diagram of middle Cr (VI)；
Fig. 4 is MoS in the embodiment of the present invention 22@Fe-MOF、MoS2And Fe-MOF catalytic degradation aqueous solution under visible light
The rate constant fitted figure of middle Cr (VI)；
Fig. 5 is the MoS in the embodiment of the present invention 22Zeta potential characterization of the@Fe-MOF and Fe-MOF under acid system
Figure；
Fig. 6 is the MoS of the embodiment of the present invention 22@Fe-MOF、MoS2And the 2p of the element sulphur and ferro element in Fe-MOF
X-ray photoelectron spectroscopy (XPS) figure of track；
Fig. 7 is the MoS of the embodiment of the present invention 22@Fe-MOF、MoS2And the electrochemical impedance spectrogram of Fe-MOF；
Fig. 8 is MoS prepared by the embodiment of the present invention 12The repeatable phenogram of@Fe-MOF；
Fig. 9 is MoS prepared by the embodiment of the present invention 12The stability phenogram of@Fe-MOF；
Figure 10 is the different MoS of embodiment 42The composite material MoS of doping2@Fe-MOF is catalyzed drop under visible optical radiation
Degradation amount-time diagram of Xie Shuizhong Cr (VI)；
Figure 11 is ferrous metals organic framework material modified in embodiment 5 under visible optical radiation in catalytic degradation water
Degradation amount-the time diagram and degradation rate dynamics fitted figure of Cr (VI).
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of ferrous metals organic framework materials of modification, by the raw material comprising following parts by weight of component
It is prepared:
800~900 parts of Iron trichloride hexahydrate powder；
500~600 parts of diamino terephthalic acid (TPA)；
6~30 parts of molybdenum disulfide.
The raw material for preparing of the ferrous metals organic framework material of modification provided by the invention includes Iron trichloride hexahydrate powder.It is described
The parts by weight of Iron trichloride hexahydrate powder are 800~900 parts.In certain embodiments of the present invention, the Iron trichloride hexahydrate powder
Parts by weight are 810.9 parts.
In certain embodiments of the present invention, the partial size of the Iron trichloride hexahydrate powder is 10~50 μm.
The raw material for preparing of the ferrous metals organic framework material of modification provided by the invention further includes diamino terephthaldehyde
Acid.The parts by weight of the diamino terephthalic acid (TPA) are 500~600 parts.In certain embodiments of the present invention, the diamino
The parts by weight of base terephthalic acid (TPA) are 543.5 parts.
The raw material for preparing of the ferrous metals organic framework material of modification provided by the invention further includes molybdenum disulfide.Described two
The parts by weight of molybdenum sulfide are 6~30 parts.In certain embodiments of the present invention, the parts by weight of the molybdenum disulfide are
20.32 parts, 6.8 parts, 13.54 parts or 27.09 parts.
In an embodiment of the present invention, the ferrous metals organic framework material of the modification by comprising Iron trichloride hexahydrate powder,
The raw material of diamino terephthalic acid (TPA) and molybdenum disulfide is prepared in a solvent.
In certain embodiments of the present invention, the solvent is n,N-Dimethylformamide.In certain implementations of the invention
In example, the amount ratio of the Iron trichloride hexahydrate powder and the n,N-Dimethylformamide is 800~900mg:55~75mL.At certain
In a little embodiments, the amount ratio of the Iron trichloride hexahydrate powder and the n,N-Dimethylformamide is 810.9mg:67mL.
The ferrous metals organic framework material for the modification that the present invention is prepared by the above raw material can quickly will be water-soluble
Cr VI in liquid adsorbs on the surface of the material, then, under the radiation of visible light, in the ferrous metals organic backbone of composite material
Amino after absorbing the radiation of visible light, carrier separation phenomenon occurs, generates light induced electron and hole.Wherein photoproduction electricity
Son transits to Fe-Cu deposits at first, and because molybdenum disulfide introducing, hetero-junctions bonding between iron sulphur, it is suppressed that carrier it is compound,
The service life of light induced electron is extended, meanwhile, molybdenum disulfide can enable light induced electron rapidly and effectively from composite material
Internal migration is reacted to surface, and with the Cr VI for being adsorbed on surface, is translated into trivalent chromium.On the other hand, hole can shell
Take the electronics in the sacrifice agent methanol in aqueous solution by force, to realize circulation.Therefore, the ferrous metals of modification provided by the invention have
Machine framework material can effectively degrade the Cr (VI) in water body.
The present invention also provides a kind of preparation methods of the ferrous metals organic framework material of modification described above, including
Following steps:
First mixed solution and the second mixed solution are mixed, 24~26h is reacted at 140~160 DEG C, obtains modification
Ferrous metals organic framework material；
First mixed solution is by Iron trichloride hexahydrate powder, diamino terephthalic acid (TPA) and a part of N, N- dimethyl formyl
Amine is mixed to get；
Second mixed solution is mixed to get by molybdenum disulfide and remaining N,N-dimethylformamide.
In the preparation method of the ferrous metals organic framework material of modification provided by the invention, the component of the raw material and match
Than ibid, details are not described herein.
In the present invention, first mixed solution is by Iron trichloride hexahydrate powder, diamino terephthalic acid (TPA) and a part of N,
Dinethylformamide (DMF) is mixed to get.Specifically, can be with are as follows: first mixed solution is by Iron trichloride hexahydrate powder and two
Amino terephthalic acid (TPA) ultrasonic disperse in a part of N,N-dimethylformamide obtains.
In certain embodiments of the present invention, the time of the ultrasonic disperse is 15~20min.In certain embodiments,
The time of the ultrasonic disperse is 15min.
In certain embodiments of the present invention, the dosage of the Iron trichloride hexahydrate powder and a part of n,N-Dimethylformamide
Than for 800~900mg:50~60mL.In certain embodiments, the Iron trichloride hexahydrate powder and a part of N, N- dimethyl formyl
The amount ratio of amine is 810.9mg:57mL.
In the present invention, second mixed solution is mixed by molybdenum disulfide with remaining n,N-Dimethylformamide
It arrives.Specifically, can be with are as follows: second mixed solution ultrasonic disperse in remaining n,N-Dimethylformamide by molybdenum disulfide
It obtains.
In certain embodiments of the present invention, the time of the ultrasonic disperse is 15~20min.In certain embodiments,
The time of the ultrasonic disperse is 15min.
In certain embodiments of the present invention, the molybdenum disulfide and the amount ratio of remaining n,N-Dimethylformamide are
6~30mg:5~15mL.
After obtaining the first mixed solution and the second mixed solution, the first mixed solution and the second mixed solution are mixed, In
24~26h is reacted at 140~160 DEG C, obtains modified ferrous metals organic framework material.
It in certain embodiments of the present invention, further include ultrasonic disperse after the mixing.In certain embodiments of the present invention
In, the time of the ultrasonic disperse is 5~20min.In certain embodiments, the time of the ultrasonic disperse is 15min.
The temperature of the reaction is 140~160 DEG C.In certain embodiments of the present invention, the temperature of the reaction is 150
℃.The time of the reaction is 24~26h.In certain embodiments of the present invention, the time of the reaction is for 24 hours.In this hair
In bright some embodiments, the reaction carries out in the autoclave containing polytetrafluoroethylliner liner.
In certain embodiments of the present invention, after the reaction, further includes: be centrifuged the product after the reaction.
Reactant of the centrifugation for removing solvent N,N-dimethylformamide and having neither part nor lot in reaction.
In certain embodiments of the present invention, the temperature of the centrifugation is 8~12 DEG C.In certain embodiments, it is described from
The temperature of the heart is 10 DEG C.In certain embodiments of the present invention, the time of the centrifugation is 15~20min.In some embodiments
In, the time of the centrifugation is 15min.In certain embodiments of the present invention, the revolving speed of the centrifugation be 7500~
8500rpm.In certain embodiments, the revolving speed of the centrifugation is 8000rpm.
It in certain embodiments of the present invention, further include cooling down the product after the reaction before the centrifugation.This
Invention has no special limitation to the method and rate of the cooling, in certain embodiments of the present invention, after the reaction
Product cooled to room temperature.
In certain embodiments of the present invention, after the centrifugation, further includes:
Product after being centrifuged described in washes of absolute alcohol, is then dried.
In certain embodiments of the present invention, the temperature of the drying is 145~155 DEG C.In certain embodiments, described
Dry temperature is 150 DEG C.In certain embodiments of the present invention, the time of the drying is 12~15h.In some embodiments
In, the time of the drying is 13h.
The ferrous metals organic framework material for the modification that the present invention is prepared can be quickly by the sexavalence in aqueous solution
Chromium adsorbs on the surface of the material, and then, under the radiation of visible light, the amino in the ferrous metals organic backbone of composite material is being inhaled
After the radiation for having received visible light, carrier separation phenomenon occurs, generates light induced electron and hole.Wherein light induced electron transition at first
To Fe-Cu deposits, and because molybdenum disulfide introducing, hetero-junctions bonding between iron sulphur, it is suppressed that carrier it is compound, extend photoproduction
The service life of electronics, meanwhile, molybdenum disulfide can enable light induced electron rapidly and effectively to move to from composite inner
Surface, and reacted with the Cr VI for being adsorbed on surface, it is translated into trivalent chromium.On the other hand, hole can deprive in aqueous solution
Sacrifice agent methanol in electronics, to realize circulation.Therefore, the ferrous metals organic framework material of modification provided by the invention
The Cr (VI) that can effectively degrade in water body.
The present invention also provides a kind of processing methods of chromium in water body, comprising the following steps:
Water body containing chromium is mixed with modified ferrous metals organic framework material, after visible optical radiation, after being purified
Water body.
In certain embodiments of the present invention, the concentration of Cr VI is 15~25mg/L in the water body containing chromium.Certain
In embodiment, the concentration of Cr VI is 20mg/L in the water body containing chromium.
In certain embodiments of the present invention, the pH value of the water body containing chromium is 1.8~2.2.In certain embodiments, institute
The pH value for stating the water body containing chromium is 2.0.
In certain embodiments of the present invention, the dosage of the water body containing chromium and modified ferrous metals organic framework material
Than for 35~45mL:35~45mg.In certain embodiments, the water body containing chromium and modified ferrous metals organic framework material
Amount ratio be 40mL:40mg.
In certain embodiments of the present invention, the mixed material further includes methanol.The methanol is sacrifice agent.At this
In some embodiments of invention, the concentration of methanol is 0.3~0.8mol/L in the mixed solution.In some embodiments
In, the concentration of methanol is 0.5mol/L in the mixed solution.
In certain embodiments of the present invention, described be mixed into is stirred.In certain embodiments of the present invention, described
The mixed time is 3~5min.In certain embodiments, the mixed time is 3min.
In certain embodiments of the present invention, the intensity of the radiation is 80~120mWcm-2, the wavelength of radiation is small
In 420nm.In certain embodiments, the intensity of the radiation is 100mWcm-2, the wavelength of radiation is 420nm.
In certain embodiments of the present invention, the light source of the visible light is xenon source.
The present invention has no special limitation to the source of the raw material used above, can be general commercially available.
The ferrous metals organic framework material of modification provided by the invention Cr in catalytic degradation aqueous solution under visible light
(VI) 0.0095~0.0552min may be implemented in degradation rate constant-1。
In order to further illustrate the present invention, have below with reference to embodiment to a kind of ferrous metals of modification provided by the invention
Machine framework material, preparation method and application are described in detail, but they cannot be interpreted as to the scope of the present invention
Restriction.
Embodiment 1
0.8109g Iron trichloride hexahydrate, 0.5435g 2- amino terephthalic acid (TPA) are subjected to ultrasonic disperse in the DMF of 57mL
15min obtains the first mixed solution；
Weigh the MoS of 0.02032g2The ultrasonic disperse 15min in 10mL DMF, obtains the second mixed solution；
Second mixed solution is added in the first mixed solution, ultrasonic disperse 15min moves to finely dispersed mixed liquor
In the autoclave of the polytetrafluoroethylliner liner of 100mL, 24 h are reacted in 150 DEG C of baking ovens, after being cooled to room temperature, 10
DEG C, be centrifuged 15min under the revolving speed of 8000rpm, obtained brownish black material is used washes of absolute alcohol 5 times again, will finally have been cleaned
Material be placed in 150 DEG C of baking oven dry 13h, obtain modified ferrous metals organic framework material MoS2@Fe-MOF。
The present embodiment is to obtained MoS2@Fe-MOF、MoS2And Fe-MOF is scanned respectively and transmission electron microscope analysis,
As a result as shown in Figure 1.Fig. 1 is MoS prepared by the embodiment of the present invention 12@Fe-MOF、MoS2And the scanning electron microscope (SEM) photograph of Fe-MOF and
Transmission electron microscope picture.Wherein, the figure a in Fig. 1 is the MoS that embodiment 1 uses2Scanning electron microscope (SEM) photograph；Figure d in Fig. 1 is embodiment 1
The MoS used2Transmission electron microscope picture；Figure c in Fig. 1 is MoS prepared by embodiment 12The scanning electron microscope (SEM) photograph of@Fe-MOF；In Fig. 1
Figure f be embodiment 1 prepare MoS2The transmission electron microscope picture of@Fe-MOF；The scanning electricity that figure b in Fig. 1 is existing Fe-MOF
Mirror figure；The transmission electron microscope picture that figure e in Fig. 1 is existing Fe-MOF.
It can be seen that MoS from the figure a and figure d in Fig. 12For two-dimensional flake.It can from the figure b and figure e in Fig. 1
Out, it is about 3.5 μm that Fe-MOF, which shows length, the wide about three-dimensional spindle-shaped structure of 400nm.It can from the figure c and figure f in Fig. 1
To find out, it is being doped with MoS2Later, the pattern of material has greatly changed, and is changed by initial micron-sized fusiform and is received
Meter level it is octahedronlike, it is believed that this is because in the synthesis process of MOF, synthetic environment is required more harsh, works as MoS2
After being added in system, acting as " additive ", (a kind of substance often used in MOF synthesis process, helps to obtain spy
The MOF for the looks that shape) effect, on the one hand affect the nucleation process of MOF, on the other hand its a certain crystalline substance that may be attached to MOF
On face, to limit the growth of crystal.But material is conducive to its filling with visible light to nanoscale transformation by micron order
Tap touching, while also will the more absorption of exposure and reactivity site.
The present embodiment is to obtained MoS2@Fe-MOF、MoS2And Fe-MOF carries out the characterization of crystalline structure (XRD) respectively,
As shown in Figure 2.Fig. 2 is MoS prepared by the embodiment of the present invention 12@Fe-MOF、MoS2And the XRD spectra of Fe-MOF.From Fig. 2
As can be seen that in composite material MoS2It can clearly be found out in the XRD diagram of@Fe-MOF and MoS2And Fe-MOF is consistent
Crystallographic plane diffraction peak shows MoS2It is successfully doped in Fe-MOF, and passes through MoS2After doping, the basic object phase of Fe-MOF is not
Biggish change occurs.
Embodiment 2
The composite material MoS for taking 40mg embodiment 1 to be prepared2@Fe-MOF is added in 40mL simulation chromium waste water, described
Simulating Cr (VI) concentration in chromium waste water is 20mg/L, in addition, addition methanol (CH3OH it) is used as sacrifice agent, so that simulation chromium waste water
The concentration of middle methanol is 0.5mol/L, after quickly stirring 3min, applies the xenon lamp of an assembly 420nm filter to whole system
The radiation in source, the intensity of the radiation are 100mWcm-2.And start timing；About 15min takes 2mL reaction solution, is centrifuged, is filtered
Deng operation, supernatant liquor is obtained, and carried out to Cr (VI) concentration in solution with DPC method combination ultraviolet-visible spectrophotometer
Detection, as a result with absorbance AtIndicate, and repeat aforesaid operations, until system in Cr (VI) concentration removal rate to 99.9% with
On, according to degradation rate-time (At/A0- t) mapping, and the part of steepest in degradation curve is handled to obtain material most
Big degradation rate constant K；MoS is set simultaneously2And the experiment of Fe-MOF control group, and and MoS2@Fe-MOF is compared, as a result
As shown in Figure 3 and Figure 4.Fig. 3 is MoS in the embodiment of the present invention 22@Fe-MOF、MoS2And Fe-MOF is catalyzed drop under visible light
Solve degradation amount-time diagram of Cr (VI) in aqueous solution.Fig. 4 is MoS in the embodiment of the present invention 22@Fe-MOF、MoS2And Fe-MOF
Under visible light in catalytic degradation aqueous solution Cr (VI) rate constant fitted figure.
From figure 3, it can be seen that compared to MoS2For Fe-MOF, MoS2@Fe-MOF shows higher Cr (VI) drop
Solve rate.Degradation rate constant in Fig. 4 also shows MoS2@Fe-MOF possesses highest Cr (VI) degradation rate constant, is
0.0552min-1, which is MoS respectively2(0.008min-1) and Fe-MOF (0.0143min-1) 7 times and 4 times, the above results
Show the generation of synergistic effect.
To the MoS in embodiment 22@Fe-MOF and Fe-MOF carry out the characterization of practical degradation environment following table Surface charge distribution
(Zeta electric potential), as a result as shown in Figure 5.Fig. 5 is the MoS in the embodiment of the present invention 22@Fe-MOF and Fe-MOF are in acid system
Under Zeta potential phenogram.From fig. 5, it can be seen that through MoS2After modification, the positively charged amount of material surface institute increases, and because
Cr (VI) is in acid condition mainly with Cr2O7 2-Form exist, by positive and negative attracting, so MoS2@Fe-MOF is in aqueous solution
Cr (VI) there is stronger adsorption capacity, and degradation of the good adsorption capacity also for Cr (VI) provides basis.
To the MoS in embodiment 22@Fe-MOF、MoS2And the surrounding chemical of the element sulphur and ferro element in Fe-MOF
Environment is characterized (XPS), as a result as shown in Figure 6.Fig. 6 is the MoS of the embodiment of the present invention 22@Fe-MOF、MoS2And Fe-MOF
In element sulphur and ferro element 2p track x-ray photoelectron spectroscopy (XPS) figure.Wherein the figure a in Fig. 6 is that the present invention is real
Apply the Fe-MOF and MoS of example 32The XPS figure of the 2p track of ferro element in@Fe-MOF；Figure b in Fig. 6 is the embodiment of the present invention 3
MoS2And MoS2The XPS figure of the 2p track of element sulphur in@Fe-MOF.
The characteristic peak that can be seen that the Fe element compared with simple Fe-MOF, in composite material from the figure a in Fig. 6 has
One offset to low combination energy direction about 0.4eV.It can be seen that and simple MoS from the figure b in Fig. 62It compares, composite wood
Expect MoS2The characteristic peak of S element in@Fe-MOF has an offset to high combination energy direction about 0.4eV.Both connections, show
Composite material MoS2In the forming process of@Fe-MOF, MoS2In S element by part electronics transfer arrived the Fe in Fe-MOF member
On element, therefore the two bonding, heterojunction structure is formed.
To the MoS in embodiment 22@Fe-MOF、MoS2And Fe-MOF carries out the electrochemical impedance spectroscopy under three-electrode system
Characterization (EIS), as a result as shown in Figure 7.Fig. 7 is the MoS of the embodiment of the present invention 22@Fe-MOF、MoS2And the electrification of Fe-MOF
Learn impedance spectra.It can be seen from figure 7 that Fe-MOF and MoS2The reason of because of self structure, possesses worst and best respectively
Electron transfer capacity；But introducing MoS2Afterwards, MoS2The electric conductivity of@Fe-MOF be improved significantly.
Embodiment 3
Good repeatability and stability are to evaluate two important indicators of catalysis material actual application ability, I
Embodiment 1 is prepared immediately composite material MoS2The repeatability and stability of@Fe-MOF is detected, as a result
As shown in Figure 8 and Figure 9.Fig. 8 is MoS prepared by the embodiment of the present invention 12The repeatable phenogram [email protected]. 9 is this hair
MoS prepared by bright embodiment 12The stability phenogram of@Fe-MOF.
It can find out from Fig. 8 and Fig. 9, composite material MoS2@Fe-MOF degrades after continuous 4 Degrading experiments
Efficiency was still able to maintain in 93% (compared with for the first time, there are about 7% reductions) within a hour, while self structure is simultaneously
It does not substantially change.
Embodiment 4
In order to probe into MoS2Doping for composite material MoS2The influence of@Fe-MOF photocatalytic degradation Cr (VI) ability,
We are in composite material MoS2MoS is changed in the preparation process of@Fe-MOF2Dosage, prepared a series of difference MoS2
The composite material of doping, is denoted as 0.5%MoS respectively2@Fe-MOF (Iron trichloride hexahydrate powder 0.8109g, diamino pair in raw material
Phthalic acid 0.5435g, molybdenum disulfide 0.006800g), 1.0%MoS2@Fe-MOF (Iron trichloride hexahydrate powder in raw material
0.8109g, diamino terephthalic acid (TPA) 0.5435g, molybdenum disulfide 0.01354g), 1.5%MoS2@Fe-MOF (six water in raw material
Chlorination iron powder 0.8109g, diamino terephthalic acid (TPA) 0.5435g, molybdenum disulfide 0.02032g), 2.0%MoS2@Fe-MOF is (former
Iron trichloride hexahydrate powder 0.8109g, diamino terephthalic acid (TPA) 0.5435g, molybdenum disulfide 0.02709g in material), other the step of
With embodiment 2, and degradation experiment is carried out, the results are shown in Figure 10.Figure 10 is the different MoS of embodiment 42The composite wood of doping
Expect MoS2Degradation amount-time diagram of@Fe-MOF Cr (VI) in catalytic degradation water under visible optical radiation.
From fig. 10 it can be seen that in doping MoS2Later, photocatalytic degradation Cr (VI) ability of all composite materials is compared
In MoS2It is all improved with Fe-MOF, but the degradation capability and MoS of composite material2Doping simple line is not presented
Sexual intercourse, the electric conductivity that very few doping may cause composite material cannot get substantive promotion, and excessively high doping
It is likely to result in composite material again to lose to visible light-responded ability, and optimal doping as shown in the figure is 1.5%.
Embodiment 5
Cr (VI) rate in water removal is gone for photocatalysis in order to probe into the dosage of modified ferrous metals organic framework material
Influence, we have done a series of conditions experiment, by the dosage of modified ferrous metals organic framework material from 0.2mg/mL by
It is cumulative to add to 1.0mg/mL (specifically including 0.2mg/mL, 0.5mg/mL, 0.8mg/mL, 1.0mg/mL), other the step of with real
Example 2 is applied, its influence for Cr (VI) removal rate is observed.Shown in experimental result Figure 11.Figure 11 is iron modified in embodiment 5
Base Metal organic framework material under visible optical radiation in catalytic degradation water degradation amount-time diagram of Cr (VI) and degradation speed
Rate dynamics fitted figure.Figure a in Figure 11 is the modified ferrous metals organic framework material of different amounts under visible optical radiation
Degradation amount-time diagram of Cr (VI) in catalytic degradation water.Figure b in Figure 11 is the modified ferrous metals organic backbone of different amounts
Material under visible light in catalytic degradation aqueous solution Cr (VI) degradation rate dynamics fitted figure.
As can be known from Fig. 11, with the increase of the dosage of modified ferrous metals organic framework material, under visible light
The rate of catalysis reduction Cr (VI) gradually increases, and degradation rate constant also gradually increases.Modified ferrous metals organic backbone material
When the dosage of material is 0.2mg/mL, 0.5mg/mL, 0.8mg/mL, 1.0mg/mL, corresponding Cr (VI) degradation rate constant difference
For 0.0095min-1、0.0169min-1、0.0279min-1And 0.0552min-1。
Therefore, the ferrous metals organic framework material of modification provided by the invention is under visible light in catalytic degradation aqueous solution
0.0095~0.0552min may be implemented in the degradation rate constant of Cr (VI)-1。
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of ferrous metals organic framework material of modification, which is characterized in that by the raw material system comprising following parts by weight of component
It is standby to obtain:
800~900 parts of Iron trichloride hexahydrate powder；
500~600 parts of diamino terephthalic acid (TPA)；
6~30 parts of molybdenum disulfide.
2. the ferrous metals organic framework material of modification according to claim 1, which is characterized in that the Iron trichloride hexahydrate
The partial size of powder is 10~50 μm.
3. the ferrous metals organic framework material of modification according to claim 1, which is characterized in that by including six water chlorinations
The raw material of iron powder, diamino terephthalic acid (TPA) and molybdenum disulfide is prepared in a solvent；
The solvent is N,N-dimethylformamide；
The amount ratio of the Iron trichloride hexahydrate powder and the N,N-dimethylformamide is 800~900mg:55~75mL.
4. a kind of preparation method of the ferrous metals organic framework material of modification, comprising the following steps:
First mixed solution and the second mixed solution are mixed, 24~26h is reacted at 140~160 DEG C, obtains the iron-based of modification
Metal-organic framework materials；
First mixed solution is mixed by Iron trichloride hexahydrate powder, diamino terephthalic acid (TPA) and a part of N,N-dimethylformamide
Conjunction obtains；
Second mixed solution is mixed to get by molybdenum disulfide and remaining N,N-dimethylformamide.
5. the preparation method of the ferrous metals organic framework material of modification according to claim 4, which is characterized in that described
The amount ratio of Iron trichloride hexahydrate powder and a part of N,N-dimethylformamide is 800~900mg:50~60mL；
First mixed solution is by Iron trichloride hexahydrate powder and diamino terephthalic acid (TPA) in a part of N,N-dimethylformamide
Middle 15~20min of ultrasonic disperse is obtained.
6. the preparation method of the ferrous metals organic framework material of modification according to claim 4, which is characterized in that described
The amount ratio of molybdenum disulfide and remaining N,N-dimethylformamide is 6~30mg:5~15mL；
By molybdenum disulfide, 15~20min of ultrasonic disperse in remaining N,N-dimethylformamide is obtained second mixed solution
It arrives.
7. the preparation method of the ferrous metals organic framework material of modification according to claim 4, which is characterized in that described
After reaction, further includes:
Product after the reaction is centrifuged 15~20min at 8~12 DEG C；
The revolving speed of the centrifugation is 7500~8500rpm.
8. the preparation method of the ferrous metals organic framework material of modification according to claim 4, which is characterized in that described
After centrifugation, further includes:
Then product after being centrifuged described in washes of absolute alcohol dries 12~15h at 145~155 DEG C.
9. the processing method of chromium in a kind of water body, comprising the following steps:
Water body containing chromium is mixed with modified ferrous metals organic framework material, the water after visible optical radiation, after being purified
Body.
10. the processing method of chromium in water body according to claim 9, which is characterized in that the intensity of the radiation be 80~
120mW·cm-2, the wavelength of radiation is not less than 420nm.
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Application publication date: 20191203 |