CN108905976A - Manganese ion doping metal-organic framework materials and its preparation method and application - Google Patents
Manganese ion doping metal-organic framework materials and its preparation method and application Download PDFInfo
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- CN108905976A CN108905976A CN201810820329.0A CN201810820329A CN108905976A CN 108905976 A CN108905976 A CN 108905976A CN 201810820329 A CN201810820329 A CN 201810820329A CN 108905976 A CN108905976 A CN 108905976A
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- Prior art keywords
- manganese ion
- organic framework
- ion doping
- framework materials
- metal
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- 239000000463 material Substances 0.000 title claims abstract description 127
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910001437 manganese ion Inorganic materials 0.000 title claims abstract description 118
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002351 wastewater Substances 0.000 claims abstract description 58
- 239000013207 UiO-66 Substances 0.000 claims abstract description 48
- 230000003115 biocidal effect Effects 0.000 claims abstract description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000010521 absorption reaction Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 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 32
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 12
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 claims abstract description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 5
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 claims description 44
- 230000010355 oscillation Effects 0.000 claims description 17
- 238000005119 centrifugation Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical class O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 210000000988 bone and bone Anatomy 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 53
- 230000000694 effects Effects 0.000 abstract description 26
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 61
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000013078 crystal Substances 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 239000004098 Tetracycline Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000013384 organic framework Substances 0.000 description 7
- 229960002180 tetracycline Drugs 0.000 description 7
- 229930101283 tetracycline Natural products 0.000 description 7
- 235000019364 tetracycline Nutrition 0.000 description 7
- 150000003522 tetracyclines Chemical class 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- -1 deposit Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000013110 organic ligand Substances 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
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
-
- 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
Abstract
The invention discloses a kind of manganese ion doping metal-organic framework materials and its preparation method and application, which includes UiO-66（Zr）, doped with manganese ion.Preparation method includes：Zirconium chloride, terephthalic acid (TPA), four chloride hydrate manganese and n,N dimethylformamide are mixed and carry out solvent thermal reaction, obtains manganese ion doping metal-organic framework materials.The advantages that manganese ion doping metal-organic framework materials adsorption capacity of the present invention is big, absorption property is good, stability is good, and synthesis is simple, can be widely adopted, can efficient absorption removal water body in pollutant, it is a kind of new adsorbent, preparation method has many advantages, such as that easy to operate, preparation is convenient, raw material type is few, yield is high, at low cost.Material of the present invention can be widely used in handling antibiotic waste water and/or heavy metal wastewater thereby, have the advantages that easy to operate, equipment is simple, processing cost is cheap, treatment effeciency is high, removal effect is good, there is good application value and application prospect.
Description
Technical field
The invention belongs to field of compound material, it is related to a kind of manganese ion doping metal-organic framework materials and preparation method thereof
And application.
Background technique
Antibiotic is widely used in the mankind and veterinary treatment, animal husbandry and aquaculture.Such as, tetracycline is that a kind of wide spectrum is anti-
Raw element, annual output is thousands of tons of.However, tetracycline is seldom biodegradable and is metabolized, it is most of（About 30%-90%）Tetracycline is logical
It crosses excrement or unprocessed urine is excreted in environment.It can in soil, deposit, surface water, underground water even drinking water
Detect tetracycline residue object.In addition to antibiotic pollution, heavy metal pollution also endangers environment.Such as, in most cases, water ring
In border in the form of positive sexavalence existing for chromium be considered as a kind of having substance toxic and carcinogenic.Therefore, effectively from water environment
Except antibiotic, heavy metal are extremely urgent.
Currently, various technologies are used to remove antibiotic and heavy metal in aquatic environment, such as biodegrade, film
There are certain deficiencies for separation, photocatalytic degradation, electrochemistry, but the above method, are not widely deployed for tetracycline and positive sexavalence
The removal of chromium.And adsorption method have it is inexpensive, easy to operate and without secondary pollution, have been considered to be one kind have very much competition
The method of power, thus develop, to prepare efficient adsorbent particularly important.Recently, metal organic framework（MOFs）It is more as one kind
The functional material in hole, mainly passes through central metallic ions and organic ligand is formed by chemical bonds, due to its superelevation
Porosity, biggish specific surface area, adjustable port size and shape and easy functionalization, it has also become research hotspot.However, metal has
Machine framework material lacks functional group and adsorption site, causes it not high to the absorption property of pollutant in water body.Therefore, how entirely
Face improves the performance of existing metal-organic framework materials, obtains the metal organic framework material that a kind of stability is good, absorption property is good
Expect and obtain it is a kind of it is easy to operate, raw material type is few, the preparation method of metal-organic framework materials at low cost, for height
Effect, the antibiotic in inexpensive adsorbed water body and heavy metal have great importance.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide that a kind of stability is good, adsorptivity
Can good manganese ion doping metal-organic framework materials, additionally provide that a kind for the treatment of process is simple, raw material type is few, at low cost
The preparation method of manganese ion doping metal-organic framework materials and the manganese ion doping metal-organic framework materials are going to remove water
Application in body in antibiotic and/or heavy metal, in the application method manganese ion doping metal-organic framework materials can efficiently,
Antibiotic and heavy metal in the Adsorption water body of low cost.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of manganese ion doping metal-organic framework materials, including UiO-66（Zr）；The UiO-66（Zr）In doped with manganese from
Son.
Above-mentioned manganese ion doping metal-organic framework materials, further improved, the manganese ion and UiO-66（Zr）
Molar ratio be 1: 1.
Above-mentioned manganese ion doping metal-organic framework materials, further improved, the manganese ion doping metal is organic
Framework material passes through solvent thermal reaction using zirconium chloride, terephthalic acid (TPA), four chloride hydrate manganese and n,N dimethylformamide as raw material
It is prepared.
As a general technical idea, the present invention also provides a kind of systems of manganese ion doping metal-organic framework materials
Preparation Method includes the following steps：Zirconium chloride, terephthalic acid (TPA), four chloride hydrate manganese and n,N dimethylformamide are mixed and carried out
Solvent thermal reaction obtains manganese ion doping metal-organic framework materials.
Above-mentioned preparation method, further improved, the four chloride hydrates manganese, zirconium chloride, terephthalic acid (TPA) and N, N bis-
The molar ratio of methylformamide is 1: 1: 1: 162.
Above-mentioned preparation method, further improved, the mixing carries out under agitation；The revolving speed of the stirring is
The r/min of 300 r/min~500；The time of the stirring is 1h~3h；The solvent thermal reaction is 120 DEG C~150 in temperature
It is carried out at DEG C；The time of the solvent thermal reaction is h for 24 hours~36.
Above-mentioned preparation method, it is further improved, it is further comprising the steps of：It is anti-to being obtained after the completion of solvent thermal reaction
It answers product to be centrifuged, washed and is dried；The revolving speed of the centrifugation is the r/min of 5000 r/min~6000；The washing uses
Be n,N dimethylformamide and ethyl alcohol, each washing is 3 times~5 times；It is described to be dried to be done under vacuum conditions
It is dry；The temperature of the drying is 60 DEG C~80 DEG C；The time of the drying is the h of 8 h~12.
As a general technical idea, the present invention also provides a kind of above-mentioned manganese ion doping metal organic framework materials
Manganese ion doping metal-organic framework materials made from material or above-mentioned preparation method antibiotic and/or huge sum of money in removal water body
Application in category.
Above-mentioned application, it is further improved, include the following steps：By manganese ion doping metal-organic framework materials, resist
Raw element waste water and/or heavy metal wastewater thereby mixing carry out oscillation absorption, complete the processing to antibiotic in water body and/or heavy metal；
The ratio of the manganese ion doping metal-organic framework materials and the antibiotic waste water and/or heavy metal wastewater thereby be 0.3g~
0.5g∶1L。
Above-mentioned application, further improved, antibiotic is quadracycline in the antibiotic waste water；The antibiotic
The concentration of antibiotic is the mg/L of 5 mg/L~70 in waste water；The pH of the antibiotic waste water is 2~12；The heavy metal wastewater thereby
Middle heavy metal is Cr (VI)；The concentration of heavy metal is the mg/L of 1 mg/L~30 in the heavy metal wastewater thereby；The heavy metal wastewater thereby
PH be 2~12.
Above-mentioned application, further improved, it is to carry out under 150r/min~300r/min that the oscillation, which is adsorbed on revolving speed,；
The time of the oscillation absorption is 12h~for 24 hours.
Compared with the prior art, the advantages of the present invention are as follows：
（1）The present invention provides a kind of manganese ion doping metal-organic framework materials, including UiO-66（Zr）And manganese ion doping
UiO-66（Zr）.In the present invention, the doping of manganese ion can be to UiO-66（Zr）Crystal structure impacts, make its specific surface area with
And pore structure changes, wherein manganese ion doping UiO-66（Zr）The specific surface area of crystal and aperture are respectively 797.18 m2
g-1With 1.68 nm, biggish specific surface area and aperture are shown, this is conducive to improve UiO-66（Zr）The adsorption capacity of crystal,
And UiO-66（Zr）The specific surface area of crystal and aperture are respectively 582.34 m2 g-1With 1.35 nm.Meanwhile manganese ion doping into
UiO-66（Zr）Valence-band electrons can be contributed in the lattice of crystal and generate more adsorption sites.Compared to other metal organic frameworks
The advantages that material, manganese ion doping metal-organic framework materials adsorption capacity of the present invention is big, absorption property is good, stability is good, and
Synthesis is simple, can be widely adopted, can pollutant in efficient absorption removal water body, be a kind of new adsorbent.
（2）A kind of preparation method of manganese ion doping metal-organic framework materials is provided in the present invention, with zirconium chloride, right
Phthalic acid, four chloride hydrate manganese and n,N dimethylformamide be raw material by solvent thermal reaction synthesized for the first time stability it is good,
The good manganese ion doping metal-organic framework materials of absorption property, with easy to operate, preparation is convenient, raw material type is few, yield
The advantages that high, at low cost, it is suitable for large scale preparation, is conducive to industrialized utilization.
（3）The present invention provides a kind of manganese ion doping metal-organic framework materials removal water body in antibiotic and/or
Application in heavy metal, by by manganese ion doping metal-organic framework materials and antibiotic waste water and/or heavy metal wastewater thereby into
The removal to antibiotic in waste water and heavy metal is completed in row oscillation absorption.The present invention utilizes manganese ion doping metal organic framework material
Material antibiotic and/or heavy metal in removal water body, with easy to operate, equipment is simple, processing cost is cheap, treatment effeciency
Advantage high, removal effect is good may be widely used for processing antibiotic waste water and/or heavy metal wastewater thereby, have and answer well
With value and application prospect.
Detailed description of the invention
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical scheme in the embodiment of the invention is clearly and completely described.
Fig. 1 is manganese ion doping metal-organic framework materials obtained in the embodiment of the present invention 1（MnUiO-66（Zr））With
Metal-organic framework materials obtained in comparative example 1（UiO-66（Zr））Scanning electron microscope (SEM) photograph, wherein（a）For UiO-66（Zr）,
（b）For MnUiO-66（Zr）.
Fig. 2 is manganese ion doping metal-organic framework materials obtained in the embodiment of the present invention 1（MnUiO-66（Zr））, it is real
Apply the manganese ion doping metal-organic framework materials obtained for being adsorbed with quadracycline in example 2（MnUiO-66（Zr）+TC）With
It is adsorbed with the manganese ion doping metal-organic framework materials of Cr (VI)（MnUiO-66（Zr）+Cr(Ⅵ)）, it is obtained in comparative example 1
Metal-organic framework materials（UiO-66（Zr））XRD diagram.
Fig. 3 is manganese ion doping metal-organic framework materials obtained in the embodiment of the present invention 1（MnUiO-66（Zr））With
Metal-organic framework materials obtained in comparative example 1（UiO-66（Zr））FTIR spectrum figure.
Fig. 4 is manganese ion doping metal-organic framework materials obtained in the embodiment of the present invention 1（MnUiO-66（Zr））With
Metal-organic framework materials obtained in comparative example 1（UiO-66（Zr））Thermogravimetric analysis map.
Fig. 5 is manganese ion doping metal-organic framework materials in the embodiment of the present invention 2（MnUiO-66（Zr））To hydrochloric acid four
The adsorption effect figure of ring element and Cr (VI), wherein（a）For TC,（b）For Cr (VI).
Fig. 6 is manganese ion doping metal-organic framework materials in the embodiment of the present invention 3（MnUiO-66（Zr））It is total in difference
The quadracycline of ionic conditions pair and the adsorption effect figure of Cr (VI) are deposited, wherein（a）For TC,（b）For Cr (VI).
Fig. 7 is manganese ion doping metal-organic framework materials in the embodiment of the present invention 4（MnUiO-66（Zr））To different pH
Quadracycline waste water and containing Cr (VI) waste water the adsorption effect figure and corresponding zeta potential diagram, wherein（a）For TC,（b）
For Cr (VI).
Manganese ion doping metal-organic framework materials in Fig. 8 embodiment of the present invention 5（MnUiO-66（Zr））To various concentration
Quadracycline waste water and the adsorption effect figure for containing Cr (VI) waste water, wherein（a）For TC,（b）For Cr (VI).
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Raw material employed in following embodiment and instrument are commercially available.In following embodiment, unless otherwise noted, gained
Data are the average value for repeating experiment more than three times.
Embodiment 1
A kind of manganese ion doping metal-organic framework materials, including UiO-66（Zr）, wherein UiO-66（Zr）In doped with manganese from
Son.
In the present embodiment, manganese ion and UiO-66（Zr）Molar ratio be 1: 1.
A kind of preparation method of manganese ion doping metal-organic framework materials in above-mentioned the present embodiment, including following step
Suddenly：
（1）It weighs zirconium chloride, terephthalic acid (TPA), four chloride hydrate manganese and is scattered in n,N dimethylformamide（DMF）In, in revolving speed
To stir 1h under 150r/min, mixed solution is obtained；Wherein, zirconium chloride, four chloride hydrate manganese, terephthalic acid (TPA) and N, N diformazan
The molar ratio of base formamide is 1: 1: 1: 162.
（2）By step（1）Mixed solution obtained is placed in the reaction kettle containing polytetrafluoroethyllining lining, is 120 in temperature
Solvent thermal reaction is carried out at DEG C, the time of reaction is for 24 hours.
（3）Step（2）In the reaction product natural cooling that obtains after the reaction was completed, carried out in the case where revolving speed is 5000 r/min
Centrifugation is respectively washed centrifugation obtained solid 3 times using n,N dimethylformamide and ethyl alcohol, in 60 DEG C of vacuum drying 12h, is obtained
Manganese ion doping metal-organic framework materials, be named as MnUiO-66（Zr）.
Comparative example 1
A kind of metal-organic framework materials（UiO-66（Zr））Preparation method, it is essentially identical with the preparation method in embodiment 1,
Difference is only that：Step（1）In do not add four chloride hydrate manganese.
Embodiment 2
A kind of application of manganese ion doping metal-organic framework materials in removal water body in antibiotic or heavy metal, is specially adopted
With the quadracycline and Cr (VI) in manganese ion doping metal-organic framework materials Adsorption water body, include the following steps：
Weigh manganese ion doping metal-organic framework materials obtained in embodiment 1（MnUiO-66（Zr））It is made in comparative example 1
The metal-organic framework materials obtained（UiO-66（Zr））, each 30mg is respectively added to 100mL, concentration is that 20 mg/L, pH are
5.74 quadracycline waste water in, carry out oscillation absorption in the case where revolving speed is 150 r/min, complete to quadracycline in water body
Removal.It vibrates in adsorption process, takes 4mL sample at regular intervals, and sample is centrifuged.Take centrifugation gained upper layer clear
Liquid measures absorbance by ultraviolet-uisible spectrophotometer, determines quadracycline concentration after absorption, mixes to obtain manganese ion
Adsorption effect of the miscellaneous metal-organic framework materials to quadracycline.After completing to the absorption of quadracycline, solid-liquid point is carried out
From obtained solid substance is the manganese ion doping metal-organic framework materials for being adsorbed with quadracycline, is named as MnUiO-66
（Zr）+TC.
Weigh manganese ion doping metal-organic framework materials obtained in embodiment 1（MnUiO-66（Zr））With comparative example 1
In metal-organic framework materials obtained（UiO-66（Zr））, each 30mg is respectively added to 100mL, concentration is 20 mg/L, pH
For 7.0 containing in Cr (VI) waste water, oscillation absorption is carried out in the case where revolving speed is 150 r/min, Cr in water body (VI) is removed in completion
It removes.It vibrates in adsorption process, takes 3mL sample at regular intervals, and sample is centrifuged.Centrifugation gained supernatant liquor is taken,
By diphenyl carbazide spectrophotometry, Cr (VI) concentration after absorption is determined, so that the metal for obtaining manganese ion doping is organic
Adsorption effect of the framework material to Cr (VI).It after completing to the absorption of Cr (VI), is separated by solid-liquid separation, obtained solid substance is to inhale
With the manganese ion doping metal-organic framework materials of Cr (VI), it is named as MnUiO-66（Zr）+Cr(Ⅵ).
Fig. 1 is manganese ion doping metal-organic framework materials obtained in the embodiment of the present invention 1（MnUiO-66（Zr））With
Metal-organic framework materials obtained in comparative example 1（UiO-66（Zr））Scanning electron microscope (SEM) photograph, wherein（a）For UiO-66（Zr）,
（b）For MnUiO-66（Zr）.It will be seen from figure 1 that metal-organic framework materials（UiO-66（Zr））Reunion form is showed, point
It is poor to dissipate property, and manganese ion doping metal-organic framework materials of the invention（MnUiO-66（Zr））In occur it is cube shaped
Looks, it is more dispersed.
By manganese ion doping metal-organic framework materials obtained in embodiment 1（MnUiO-66（Zr））, make in embodiment 2
The manganese ion doping metal-organic framework materials for being adsorbed with quadracycline obtained（MnUiO-66（Zr）+TC）Be adsorbed with Cr
(VI) manganese ion doping metal-organic framework materials（MnUiO-66（Zr）+ Cr(Ⅵ)）, metal obtained has in comparative example 1
Machine framework material（UiO-66（Zr））XRD analysis is carried out, as a result as shown in Figure 2.Fig. 2 is manganese obtained in the embodiment of the present invention 1
Ion doping metal-organic framework materials（MnUiO-66（Zr））, in embodiment 2 manganese obtained for being adsorbed with quadracycline from
Sub- doping metals organic framework material（MnUiO-66（Zr）+TC）With the manganese ion doping metal organic framework for being adsorbed with Cr (VI)
Material（MnUiO-66（Zr）+Cr(Ⅵ)）, metal-organic framework materials obtained in comparative example 1（UiO-66（Zr））XRD diagram.
As shown in Figure 2, the crystallinity of all samples is preferable, the MnUiO-66 after adulterating manganese ion（Zr）With pure UiO-66（Zr）XRD
Diffracting spectrum is similar, and no other miscellaneous peaks occur, and illustrates that the doping of manganese ion does not cause UiO-66（Zr）Topological structure change.
Meanwhile not occurring the characteristic peak of manganese or Mn oxide in XRD diffracting spectrum, illustrate that manganese element is mixed in the form of manganese ion
It is miscellaneous into UiO-66（Zr）Lattice.It is analyzed by ICP-AES it is found that manganese ion doping metal-organic framework materials（MnUiO-66
（Zr））The manganese ion content of middle doping is only 1.06%.Since metal ion is difficult to be doped into lattice, it is doped into UiO-66（Zr）
Manganese ion content in crystal is low and high degree of dispersion, thus does not occur the characteristic peak of manganese in XRD spectrum.Have in XRD spectrum
7.3 °, 8.5 ° and 25.8 ° three main peaks occur, and respectively correspond UiO-66（Zr）(111), (200) and (442) crystal face.
In addition, MnUiO-66（Zr）Peak shape does not change afterwards by absorption quadracycline and Cr (VI), illustrates that adsorption reaction will not destroy
Peak shape.
By manganese ion doping metal-organic framework materials obtained in embodiment 1（MnUiO-66（Zr））In comparative example 1
Metal-organic framework materials obtained（UiO-66（Zr））Fourier's infrared analysis is carried out, as a result as shown in Figure 3.Fig. 3 is this hair
Manganese ion doping metal-organic framework materials obtained in bright embodiment（MnUiO-66（Zr））With metal obtained in comparative example 1
Organic framework material（UiO-66（Zr））FTIR spectrum figure.As seen from Figure 3, metal-organic framework materials
（UiO-66（Zr））Peak type it is almost unchanged, and after adulterating manganese ion, manganese ion doping metal organic framework material of the present invention
Material（MnUiO-66（Zr））In 3450 cm-1Place's peak shape broadens, and peak intensity becomes strong, illustrates after manganese ion doping object in crystal duct
Hydrone content increases.Meanwhile the doping of manganese ion may cause aperture and become larger, so that more object hydrones are concentrated in duct
In.
By manganese ion doping metal-organic framework materials obtained in embodiment 1（MnUiO-66（Zr））In comparative example 1
Metal-organic framework materials obtained（UiO-66（Zr））Thermogravimetric analysis analysis is carried out, as a result as shown in Figure 4.Fig. 4 is the present invention
Manganese ion doping metal-organic framework materials obtained in embodiment 1（MnUiO-66（Zr））With metal obtained in comparative example 1
Organic framework material（UiO-66（Zr））Thermogravimetric analysis map.As shown in Figure 4, thermogravimetric weight loss is divided into two stages, first stage
It is 25 DEG C~400 DEG C, is the loss of object hydrone, in this stage, UiO-66（Zr）And MnUiO-66（Zr）Thermogravimetric weight loss
Respectively 29.69% and 41.42%, this illustrates the doping of manganese ion so that UiO-66（Zr）Object hydrone content in crystal duct
Increase.Second stage is 400 DEG C~800 DEG C, is the collapsing of skeleton structure, ultimately generates metal oxide（ZrO2Or ZrO2With
The mixture of MnO）, in this stage, UiO-66（Zr）And MnUiO-66（Zr）Thermogravimetric weight loss be respectively 35.83% and 26.82%,
MnUiO-66（Zr）There is less residual quantity, illustrates that manganese ion is successfully doped into UiO-66（Zr）In crystal.In addition, can by Fig. 4
Know, manganese ion doping UiO-66（Zr）Crystal has good thermal stability, can keep within the temperature range of within 400 DEG C
Stable structure.
Fig. 5 is manganese ion doping metal-organic framework materials in the embodiment of the present invention 2（MnUiO-66（Zr））To hydrochloric acid four
The adsorption effect figure of ring element and Cr (VI), wherein（a）For TC,（b）For Cr (VI).As shown in Figure 5,10min is before oscillation is adsorbed
Then quick adsorption slowly adsorbs until balance.In 60min, UiO-66（Zr）And MnUiO-66（Zr）Reach adsorption equilibrium.
In 1440 min, UiO-66（Zr）Adsorbance to TC and Cr (VI) is respectively 12.2 mg/g and 8.1 mg/g, and
MnUiO-6（Zr）Adsorption capacity to TC and Cr (VI) is respectively 72.5 mg/g and 25.1 mg/g, this illustrates mixing for manganese ion
It is miscellaneous to greatly improve UiO-66（Zr）Adsorption capacity.
Embodiment 3
A kind of application of manganese ion doping metal-organic framework materials in removal water body in antibiotic or heavy metal, is specially adopted
With the quadracycline and Cr (VI) in manganese ion doping metal-organic framework materials Adsorption water body, include the following steps：
Weigh manganese ion doping metal-organic framework materials obtained in 9 parts of embodiments 1（MnUiO-66（Zr））, each 30mg, point
Be not added to 9 parts of 100mL, concentration is in quadracycline waste water that 20 mg/L, pH are 5.74, while at this 9 parts of hydrochloric acid Fourth Rings
NaCl, Na are separately added into plain waste water2SO4、Na3PO4, and control NaCl, Na2SO4、Na3PO4Concentration in the solution is respectively 5
Mmol/L, 10 mmol/L, 15 mmol/L carry out oscillation absorption for 24 hours in the case where revolving speed is 150 r/min, complete to salt in water body
The removal of sour tetracycline.It vibrates in adsorption process, takes 4mL sample at regular intervals, and sample is centrifuged.Take centrifugation institute
It obtains supernatant liquor and passes through ultraviolet-uisible spectrophotometer measurement absorbance, quadracycline concentration after absorption is determined, to obtain
Adsorption effect of the manganese ion doping metal-organic framework materials to quadracycline.
Weigh manganese ion doping metal-organic framework materials obtained in 9 parts of embodiments 1（MnUiO-66（Zr））, respectively
30mg is respectively added to 9 parts of 100mL, concentration is that 20 mg/L, pH are 7.0 containing in Cr (VI) waste water, while containing Cr at this 9 parts
(VI) NaCl, Na are separately added into waste water2SO4、Na3PO4, and control NaCl, Na2SO4、Na3PO4Concentration difference in the solution
For 5 mmol/L, 10 mmol/L, 15 mmol/L, oscillation absorption is carried out for 24 hours in the case where revolving speed is 150 r/min, is completed to water body
The removal of middle Cr (VI).It vibrates in adsorption process, takes 3mL sample at regular intervals, and sample is centrifuged.Take centrifugation institute
Supernatant liquor is obtained, by diphenyl carbazide spectrophotometry, Cr (VI) concentration after absorption is determined, to obtain manganese ion doping
Adsorption effect of the metal-organic framework materials to Cr (VI).
Fig. 6 is manganese ion doping metal-organic framework materials in the embodiment of the present invention 3（MnUiO-66（Zr））It is total in difference
The quadracycline of ionic conditions pair and the adsorption effect figure of Cr (VI) are deposited, wherein（a）For TC,（b）For Cr (VI).It can by Fig. 6
Know, different coexisting ions are to MnUiO-66（Zr）The influence of adsorption effect be it is different, e.g., be added NaCl after to MnUiO-66
（Zr）Adsorption effect influence less, and Na to be added2SO4、Na3PO4MnUiO-66 can be substantially reduced（Zr）Adsorption effect.Separately
Outside, with the increase of coexisting ion concentration, MnUiO-66（Zr）Adsorption effect further decrease, this is because excessive coexists
Anion can be with contaminant molecule competitive Adsorption active site, thus removal rate declines.Meanwhile anion valence state is higher,
MnUiO-66（Zr）It is lower to the removal rate of pollutant.
Embodiment 4
A kind of application of manganese ion doping metal-organic framework materials in removal water body in antibiotic or heavy metal, is specially adopted
With the quadracycline and Cr (VI) in manganese ion doping metal-organic framework materials Adsorption water body, include the following steps：
Weigh manganese ion doping metal-organic framework materials obtained in 6 parts of embodiments 1（MnUiO-66（Zr））, each 30mg, point
It is not added to the quadracycline waste water that pH is 2,4,6,8,10,12（The volume of these waste water is that 100mL, concentration are
20mg/L）In, oscillation absorption is carried out for 24 hours in the case where revolving speed is 150 r/min, completes the removal to quadracycline in water body.Vibration
It swings in adsorption process, takes 4mL sample at regular intervals, and sample is centrifuged.Centrifugation gained supernatant liquor is taken to pass through purple
Outer visible spectrophotometer measures absorbance, quadracycline concentration after absorption is determined, so that obtaining manganese ion doping metal has
Adsorption effect of the machine framework material to different pH quadracycline waste water.
Weigh manganese ion doping metal-organic framework materials obtained in 6 parts of embodiments 1（MnUiO-66（Zr））, respectively
30mg, being respectively added to pH is 2,4,6,8,10,12 containing Cr (VI) waste water（The volume of these waste water is that 100mL, concentration are equal
For 10mg/L）In, oscillation absorption is carried out for 24 hours in the case where revolving speed is 150 r/min, completes the removal to Cr in water body (VI).Oscillation
In adsorption process, 3mL sample is taken at regular intervals, and sample is centrifuged.Centrifugation gained supernatant liquor is taken, hexichol is passed through
Two hydrazine spectrophotometry of phosphinylidyne determines Cr (VI) concentration after absorption, to obtain manganese ion doping metal-organic framework materials pair
Different pH contain the adsorption effect of Cr (VI) waste water.
Fig. 7 is manganese ion doping metal-organic framework materials in the embodiment of the present invention 4（MnUiO-66（Zr））To different pH
Quadracycline waste water and containing Cr (VI) waste water the adsorption effect figure and corresponding zeta potential diagram, wherein（a）For TC,（b）
For Cr (VI).From Fig. 7（a）In as can be seen that pH value from 2 increases to 8, MnUiO-66（Zr）To the adsorption capacity of quadracycline
Increase to 73.5 mg/g from 16.5 mg/g.It is worth noting that, pH value is in the range of 4 to 12, MnUiO-66（Zr）To salt
The adsorption capacity of sour tetracycline is almost unchanged, illustrates MnUiO-66（Zr）On the absorption of quadracycline by solution ph influenced compared with
Small, suction-operated is mainly by quadracycline and MnUiO-66（Zr）Pi-pi bond effect between middle organic ligand.In water
MnUiO-66（Zr）Zeta current potential isoelectric point be 9.85, and the MnUiO-66 in quadracycline solution（Zr）Zeta current potential
Isoelectric point is that the increase of 11.15, zeta current potential isoelectric point may be phenyl ring and MnUiO-66 because of quadracycline（Zr）In have
Machine ligand generates hydrogen bond.From 7（b）In as can be seen that MnUiO-66（Zr）The absorption of Cr (VI) is influenced very greatly, to say by pH value
Bright MnUiO-66（Zr）The absorption of Cr (VI) is mainly influenced by electrostatic interaction.When pH value is 6, MnUiO-66（Zr）To Cr
(VI) maximal absorptive capacity is 25.4 mg/g.The MnUiO-66 in Cr (VI) solution（Zr）Zeta current potential isoelectric point be 7.11,
Compared to MnUiO-66（Zr）Zeta current potential isoelectric point in water（9.85）, zeta current potential isoelectric point decline, this is because in Cr
(VI) reason of anions aggregation.
Embodiment 5
A kind of application of manganese ion doping metal-organic framework materials in removal water body in antibiotic or heavy metal, is specially adopted
With the quadracycline and Cr (VI) in manganese ion doping metal-organic framework materials Adsorption water body, include the following steps：
Weigh manganese ion doping metal-organic framework materials obtained in 5 parts of embodiments 1（MnUiO-66（Zr））, each 30mg, point
It is not added to the quadracycline waste water that concentration is 5 mg/L, 10 mg/L, 30 mg/L, 50 mg/L, 70 mg/L（The body of waste water
Product is 100mL, pH 5.74）In, oscillation absorption is carried out for 24 hours in the case where revolving speed is 150 r/min, is completed to hydrochloric acid four in water body
The removal of ring element.It vibrates in adsorption process, takes 4mL sample at regular intervals, and sample is centrifuged.It takes on centrifugation gained
Layer clear liquid measures absorbance by ultraviolet-uisible spectrophotometer, determines antibiotic concentration after absorption, mixes to obtain manganese ion
Adsorption effect of the miscellaneous metal-organic framework materials to various concentration quadracycline waste water.
Weigh manganese ion doping metal-organic framework materials obtained in 5 parts of embodiments 1（MnUiO-66（Zr））, respectively
30mg, be respectively added to concentration be 1 mg/L, 5 mg/L, 10 mg/L, 20 mg/L, 30 mg/L containing Cr (VI) waste water（Waste water
Volume be 100mL, pH 7.0）In, oscillation absorption is carried out for 24 hours in the case where revolving speed is 150 r/min, is completed to Cr in water body
(VI) removal.It vibrates in adsorption process, takes 3mL sample at regular intervals, and sample is centrifuged.It takes on centrifugation gained
Layer clear liquid determines Cr (VI) concentration after absorption, to obtain the gold of manganese ion doping by diphenyl carbazide spectrophotometry
Belong to organic framework material to the adsorption effect of Cr (VI).
Manganese ion doping metal-organic framework materials in Fig. 8 embodiment of the present invention 5（MnUiO-66（Zr））To various concentration
Quadracycline waste water and the adsorption effect figure for containing Cr (VI) waste water, wherein（a）For TC,（b）For Cr (VI).By Fig. 8（a）It can
Know, 5 mg/L of concentration of quadracycline waste water increases to 70 mg/L, manganese ion doping metal-organic framework materials（MnUiO-
66（Zr））184.49 mg/g are increased to from 19.39 mg/g to the adsorbance of quadracycline, this is because quadracycline is dense
The increase of degree will increase the motive force of concentration gradient, so that adsorption capacity be made to increase.Meanwhile with the increasing of quadracycline concentration
Add, MnUiO-66（Zr）On can be relatively fewer with adsorption site, removal rate reduce.By Fig. 8（b）It is found that containing Cr (VI) waste water
Concentration increases to 30 mg/L, manganese ion doping metal-organic framework materials from 1 mg/L（MnUiO-66（Zr））To Cr's (VI)
Adsorbance increases to 32.77 mg/g from 3.32 mg/g, this is because the increase of Cr (VI) concentration will increase pushing away for concentration gradient
Power, so that adsorption capacity be made to increase.Meanwhile with the increase of Cr (VI) concentration, MnUiO-66（Zr）On can use adsorption site
Relatively fewer, removal rate reduces.
Therefore, manganese ion doping metal-organic framework materials of the present invention（MnUiO-66（Zr））To quadracycline and Cr
(VI) there is good adsorption effect.Particularly, manganese ion doping metal-organic framework materials of the present invention（MnUiO-66（Zr））
Quadracycline antibiotic waste water to low concentration and there is better adsorption effect containing Cr (VI) waste water.In actual waste water
In, the content of quadracycline and Cr (VI) are often very low, manganese ion doping metal-organic framework materials（MnUiO-66
（Zr））The removal rate for improving the quadracycline and Cr (VI) in low concentration wastewater, illustrates manganese ion doping metal of the present invention
Organic framework material（MnUiO-66（Zr））Doping metals organic framework material（MnUiO-66（Zr））With very high business valence
Value and application prospect.
Above embodiments are only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned reality
Apply example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that being led for this technology
For the those of ordinary skill in domain, improvements and modifications without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of manganese ion doping metal-organic framework materials, which is characterized in that including UiO-66（Zr）；The UiO-66（Zr）
In doped with manganese ion；The manganese ion and UiO-66（Zr）Molar ratio be 1: 1.
2. manganese ion doping metal-organic framework materials according to claim 1, which is characterized in that the manganese ion doping
Metal-organic framework materials pass through molten using zirconium chloride, terephthalic acid (TPA), four chloride hydrate manganese and n,N dimethylformamide as raw material
Agent thermal response is prepared.
3. a kind of preparation method of manganese ion doping metal-organic framework materials, which is characterized in that include the following steps：By chlorination
Zirconium, terephthalic acid (TPA), four chloride hydrate manganese and n,N dimethylformamide mixing carry out solvent thermal reaction, obtain manganese ion doping
Metal-organic framework materials.
4. preparation method according to claim 3, which is characterized in that the four chloride hydrates manganese, zirconium chloride, terephthaldehyde
The molar ratio of acid and n,N dimethylformamide is 1: 1: 1: 162.
5. preparation method according to claim 3 or 4, which is characterized in that the mixing carries out under agitation；It is described
The revolving speed of stirring is the r/min of 300 r/min~500；The time of the stirring is 1h~3h；The solvent thermal reaction is in temperature
It is to be carried out at 120 DEG C~150 DEG C；The time of the solvent thermal reaction is h for 24 hours~36.
6. preparation method according to claim 3 or 4, which is characterized in that further comprising the steps of：It is complete to solvent thermal reaction
The reaction product obtained after is centrifuged, is washed and is dried；The revolving speed of the centrifugation is the r/min of 5000 r/min~6000；
The washing is 3 times~5 times using n,N dimethylformamide and ethyl alcohol, each washing；It is described to be dried as in vacuum item
It is dried under part；The temperature of the drying is 60 DEG C~80 DEG C；The time of the drying is the h of 8 h~12.
7. any in a kind of manganese ion doping metal-organic framework materials as claimed in claim 1 or 2 or claim 3~6
Manganese ion doping metal-organic framework materials made from preparation method described in antibiotic and/or heavy metal in removal water body
In application.
8. application according to claim 7, which is characterized in that include the following steps：By the organic bone of manganese ion doping metal
Frame material, antibiotic waste water and/or heavy metal wastewater thereby mixing carry out oscillation absorption, complete to antibiotic in water body and/or a huge sum of money
The processing of category；The ratio of the manganese ion doping metal-organic framework materials and the antibiotic waste water and/or heavy metal wastewater thereby
It is 0.3g~0.5g: 1L.
9. application according to claim 8, which is characterized in that antibiotic is quadracycline in the antibiotic waste water；
The concentration of antibiotic is the mg/L of 5 mg/L~70 in the antibiotic waste water；The pH of the antibiotic waste water is 2~12；It is described
Heavy metal is Cr (VI) in heavy metal wastewater thereby；The concentration of heavy metal is the mg/L of 1 mg/L~30 in the heavy metal wastewater thereby；It is described
The pH of heavy metal wastewater thereby is 2~12.
10. application according to claim 8 or claim 9, which is characterized in that it is described oscillation be adsorbed on revolving speed be 150r/min~
It is carried out under 300r/min；The time of the oscillation absorption is 12h~for 24 hours.
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