CN108675460A - A kind of ZIF-8/ mycelia composite material and preparation method and application - Google Patents
A kind of ZIF-8/ mycelia composite material and preparation method and application Download PDFInfo
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- CN108675460A CN108675460A CN201810293881.9A CN201810293881A CN108675460A CN 108675460 A CN108675460 A CN 108675460A CN 201810293881 A CN201810293881 A CN 201810293881A CN 108675460 A CN108675460 A CN 108675460A
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- mycelia
- zif
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- composite material
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/14—Fungi; Culture media therefor
-
- 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
Abstract
The invention belongs to field of material synthesis technology, and in particular to a kind of 8/ mycelia composite material and preparation methods of ZIF and application.The present invention is dissolved separately in after solvent and is uniformly mixed, the mycelia film of drying is added using 2 methylimidazoles and zinc nitrate hexahydrate as raw material, is put into ultrasonic synthesizer and is stirred and ultrasound, clean after reaction, dry after obtain material.The 8/ mycelia composite material and preparation method thereofs of ZIF are easy to operate, and at low cost, the reaction time is short, synthetic product has preferable mechanical performance, is easily recycled, transports and preserves, and can be applied to water treatment field, pollutant superior performance in adsorbed water body, has a extensive future.
Description
Technical field
The invention belongs to materials synthesis fields, and in particular to a kind of composite material by biomass and metal organic framework
Preparation method and applications.
Background technology
ZIF-8 is a kind of material of novel practical, has very high thermal stability (N2In 550 DEG C) and chemical stability,
Big surface area (BET：~1700m2/ g), it can be used as absorption, sensing, catalysis, energy storage and gas separation.However ZIF-8 is direct
Using due to size it is excessively small, do not simply fail to play its application effect, can also it be caused largely to waste, so in order to make ZIF-
8 preferably apply, and macroscopical ZIF-8 composite materials become research hotspot.
Currently, the application field of macroscopic view ZIF-8 composite materials includes：Mixed-matrix membrane material applied to gas absorption separation
Material adulterates other metal oxide composites applied to the Zn for forming catalysis and sensing, is applied to water body Dye Adsorption or shape
At ZIF-8/GO, ZIF-8/CNT composite material etc. of NF membrane.However, since the matrixes such as oxidation film, GO, CNT are very high
It is expensive, it is difficult to extensive use in actual production, and the preparation process of these composite materials is complicated, it is difficult to carry out large-scale production fortune
With.Therefore, develop a kind of low cost, be readily produced, be pollution-free, ZIF-8 composite materials that application prospect is good it is significant.
Invention content
It is an object of the present invention to for current ZIF-8 composite material preparations it is complicated, it is of high cost, be difficult on a large scale
Production is used, recyclability is poor, and the problems such as be not easy to transport, preserve, provide a kind of new ZIF-8/ mycelia composite material and
Preparation method and application.This method step is simple, of low cost, the new material good mechanical property prepared, is easily recycled, nothing
Pollution, transport and preservation are convenient, and application prospect is good, water pollutant removal can be used for, especially in terms of removal of heavy metal ions
There is remarkable result.
The purpose of the present invention is what is be accomplished by the following way.
A kind of ZIF-8/ mycelia composite material has ZIF-8 in hyphal surface load, preferably negative in filamentous fungi hyphal surface
It is loaded with ZIF-8.
The preparation method of the ZIF-8/ mycelia composite materials is added Filamentous true in the reaction system for preparing ZIF-8
Bacterium mycelia, product cleaning after reaction are dried to get to ZIF-8/ mycelia composite materials.
The preparation method of the ZIF-8/ mycelia composite materials, mixes after being dissolved in solvent respectively, adds mycelia；It is added
Dry mycelial weight：Zinc salt：Zinc salt solvent：2-methylimidazole：The mass volume ratio of the solvent of 2-methylimidazole be (20mg~
100mg):(0.8000g~1.000g):(25mL~35mL)：(0.9000g~1.100g)：(8mL~12mL).It is preferred that 50mg:
0.8925g:30mL：0.9852g：10mL can preferably synthesize ZIF-8/ mycelia composite materials, using 50mg with this condition
Material thin degree prepared by dry mycelial weight is lucky, and blocked up internal layer mycelia can not play a role, destructible when excessively thin synthesis.
The preparation method of the ZIF-8/ mycelia composite materials, the zinc salt include：Zinc nitrate, zinc chloride, acetic acid
Zinc, preferably zinc nitrate, three can synthesize, but zinc nitrate is commonplace；The filamentous fungi mycelia includes：It is Mucor, black
One or more of aspergillus, head mold, mould, preferably Mucor.
The preparation method of the ZIF-8/ mycelia composite materials, the solvent packet of the zinc salt solvent and 2-methylimidazole
Include methanol.It is not ZIF-8 that other solvents such as water, ethyl alcohol, which are combined to out,.
The preparation method of the ZIF-8/ mycelia composite materials is reacted for ultrasonic reaction, and the power of ultrasonic reaction is 100
~1000w, preferably 800w；The temperature of ultrasonic reaction is no more than 40 DEG C, preferably 20 DEG C；1~2h of ultrasonic reaction time, preferably 2h.
Ultrasonic power is too small can not to be synthesized, and excessive noise is too big, and power is excessively high, and ZIF-8 is likely to be broken.
The preparation method of the ZIF-8/ mycelia composite materials, after reaction mycelia directly take out, reuse clear water
Clean and dried at 50~80 DEG C 2~6h, preferably 60 DEG C drying 6h.
The preparation method of the ZIF-8/ mycelia composite materials, the mycelia after culture filters, drying obtains mycelia film use
In reaction；It is preferred that mycelia drying temperature is 50~80 DEG C, the time is 1min~3min.It is inadequate not dry or dry degree, super
Mycelia can shake scattered during phonoresponse, can be destroyed.
The ZIF-8/ mycelia composite materials are removed for water pollutant.
The ZIF-8/ mycelia composite materials are applied to water body removing heavy metals, preferably remove lead.
Beneficial effects of the present invention：
(1) present invention provides one kind using filamentous fungi thalline as matrix, and it is macro that zinc nitrate and 2-methylimidazole are prepared by raw material
ZIF-8/ mycelia composite materials are seen, preparation method is simple, at low cost, pollution-free, there is higher application prospect.Filamentous fungi can be big
Scale fast and low-cost culture, ultrasonic wave with extremely low Power operation can synthetic material, and by-product be it is unsupported up
ZIF-8 has great application value.
(2) ZIF-8/ mycelia composite material of the invention can at least be effectively removed water body by Preliminary Experiment confirmation
Middle pollutant, especially heavy metal ion, large amount of adsorption, removal rate is high, and by taking Pb ions as an example, theoretical adsorbance reaches
380mg/g, the removal rate of waste water containing Pb for handling 100mg/L are up to 99.5%, and equilibration time 2h, application process is simple, absorption
Rate is fast, easily operated, can carry out wide popularization and application.
(3) better mechanical property, main cause are that ZIF-8 is supported on to ZIF-8/ mycelia composite material of the invention in water
On mycelia so that mycelia mechanical strength improves, and possible cause is equivalent to and strengthens often after ZIF-8 is supported on hyphal surface
The intensity of root fungus silk, and ZIF-8 is not hydrophilic, can completely cut off contact of the mycelia with water so that and mycelia mechanical strength improves, and is not easy
It scatters, and can effectively be recycled by simple filtration.The material of preparation stirs not cracky in water, and it is reachable to bear stirring rotor speed
1000rpm。
(4) even if the ZIF-8/ mycelia composite materials of the present invention are crushed to 1~5mm and are adsorbed for water pollutant
When, settling property is also very superior.
(5) existing other mycelia composite materials are such as：PmPD/ mycelia, generated time do not include follow-up probably in 6h
Oxidant need to be uninterruptedly added in cleaning, when synthesis；For another example：A kind of biological composite membrane materials of CN201610036944-, modified suction
Attached the effect is unsatisfactory, and modifying process is complicated；The ZIF-8/ mycelia composite material preparation process of the present invention is simple, at low cost,
Speed is fast.Existing other mycelia composite materials mainly utilize the characteristic that can disperse in water of mycelia, and when use need to keep mycelia
The finished product of moisture state, preparation can not be dried, and otherwise can influence dispersion performance, therefore the shipping storage of product is very inconvenient.This
The ZIF-8/ mycelia composite materials of invention, using the characteristic of its microscopic fibers shape, are not stranded above using dry mycelia as carrier
It disturbs.Product of the present invention need to only be applied in the liquid phase, and product itself is drying regime, and when use is put into solution, and without using
The dispersibility of mycelia, reaction terminate also to be still sheet, are easy to transport, the recycling separation after preserving and reacting.
The filamentous fungi mycelia that the present invention selects includes Mucor, aspergillus niger, head mold, mould, not necessarily emphasizes it is certain
The special bacterial strain of kind, the conventional bacterial strain of the filamentous fungi of these types.
Description of the drawings：
Fig. 1 is the photo of ZIF-8/ mycelia composite materials prepared by the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of ZIF-8/ mycelia composite materials prepared by the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of ZIF-8/ mycelia composite materials prepared by the embodiment of the present invention 2；It is followed successively by from left to right
Mould, head mold, aspergillus niger；
Fig. 4 is the scanning electron microscope (SEM) photograph of ZIF-8/ mycelia composite materials prepared by the embodiment of the present invention 3；
Fig. 5 is the scanning electron microscope (SEM) photograph of ZIF-8/ mycelia composite materials prepared by the embodiment of the present invention 4.
Specific implementation mode：
With specific embodiment, the invention will be further described below, but can't form limitation of the present invention.
Embodiment 1
Potato culture medium is prepared, the potato for taking 200g to remove the peel, about 10min is boiled in chopping into the water, until glass bar can be used
It breaks, is poured into 1L measuring cups with filtered through gauze after slightly cold, and moisture in soil dynamic test is back-outed easily, 20g glucose, 0.5g is added
Magnesium sulfate and 1.0g potassium dihydrogen phosphates, are settled to 1L, 5 conical flasks are poured into after stirring evenly, each about 200mL, is used in combination sealed membrane
It seals, is put into 115 DEG C of autoclave, sterilize 15min, obtains fluid nutrient medium.With the inoculum concentration of culture volume 2% by concentration
106~107Mucor (Mucormucedo (Linnaeus) Fresenius, deposit number CCTCC AF 93229) bacterium solution of a/ml
It is seeded in fluid nutrient medium and cultivates, it is 30 DEG C to be subsequently placed in temperature, the constant temperature oscillation case culture that rotating speed is 160r/min 3 days；
5mL bacterium solutions (a concentration of 10g/L) volume is pipetted with 5mL liquid-transfering guns, vacuum filtration film forming is put into 60 DEG C of baking ovens and dries 2min, does
Weight is 50mg, weighs 0.9852g 2-methylimidazoles and is dissolved in 10mL methanol, 0.8925g zinc nitrates are dissolved in 30mL methanol, wait for that its is complete
It is mixed after fully dissolved, and the film and stirrer filtered is added, be put into ultrasound synthesis instrument, power is adjusted to 800w, stirring speed
Rate is 200rpm, and normal-temperature reaction 2h is obtained material and pressed from both sides out with tweezers, cleaned with clear water, and dries 6h at 60 DEG C, obtains ZIF-
8/ mycelia material, macroscopic view such as Fig. 1, microcosmic such as Fig. 2.
Embodiment 2
Mould, head mold, aspergillus niger are cultivated respectively in the cultural hypha method in embodiment 1, and 3mL is pipetted with 5mL liquid-transfering guns
Bacterium solution (a concentration of 10g/L) volume, vacuum filtration film forming are put into 60 DEG C of baking ovens and dry 1min, dry weight 30mg；It weighs
0.9803g 2-methylimidazoles are dissolved in 10mL methanol, and 0.8902g zinc nitrates are dissolved in 30mL methanol, are mixed after it is completely dissolved,
And the film and stirrer filtered is added, it is put into ultrasound synthesis instrument, power is adjusted to 800w, stir speed (S.S.) 200rpm, often
Temperature reaction 2h, obtain material and pressed from both sides out with tweezers, cleaned with clear water, and 6h is dried at 60 DEG C, obtain ZIF-8/ mycelia (mould,
Aspergillus niger or head mold) material, it is microcosmic such as Fig. 3.
Embodiment 3
10mL bacterium solutions (a concentration of 5g/L) volume is pipetted with 5mL liquid-transfering guns, vacuum filtration film forming is put into 60 DEG C of baking ovens and dries
2min, dry weight 50mg weigh 0.9704g 2-methylimidazoles and are dissolved in 10mL methanol, and 0.8925g zinc nitrates are dissolved in 30mL methanol, wait for
It is mixed after being completely dissolved, and the film filtered is added, and is not put stirrer, is put into ultrasound synthesis instrument, and power is adjusted to 100w,
Normal-temperature reaction 2h is obtained material and is pressed from both sides out with tweezers, cleaned with clear water, and is dried and dried 6h at 60 DEG C, and ZIF-8/ mycelia is obtained
Material, it is microcosmic such as Fig. 4.
Embodiment 4
10mL bacterium solutions (a concentration of 5g/L) volume is pipetted with 5mL liquid-transfering guns, vacuum filtration film forming is put into 60 DEG C of baking ovens and dries
3min, dry weight 50mg weigh 0.9852g 2-methylimidazoles and are dissolved in 10mL methanol, and 0.8925g zinc nitrates are dissolved in 30mL methanol,
It is mixed after it is completely dissolved, and the film filtered is added, stir speed (S.S.) 100rpm is put into ultrasound synthesis instrument, power
It is adjusted to 1000w, normal-temperature reaction 2h is obtained material and pressed from both sides out with tweezers, cleaned with clear water, and dries 6h at 60 DEG C, obtains ZIF-
8/ mycelia material, it is microcosmic such as Fig. 5.
Embodiment 5
Under room temperature, it is right that the ZIF-8/ Mucor composite materials prepared with embodiment 1 are crushed to tiny shape (sieving of 16 mesh)
Ion concentration containing Pb is that 100mg/L solution 20mL is adsorbed, and 0.0200g composite materials are added, and it is laggard that 4h is adsorbed at 30 DEG C
Row solution filters, and Pb ion concentrations are measured with inductively coupled plasma atomic emission spectrometry (ICP) in filtrate, filtered
Pb ion concentrations are 0.45mg/L, and filter liquor concentration is measured as 94.55mg/L before adsorbing, and Pb removal rates reach 99.52%.
Embodiment 6
Under room temperature, the ZIF-8/ aspergillus nigers composite material prepared with embodiment 1 is 500mg/L to containing Pb ion concentrations
Solution 20mL is adsorbed, and 0.0200g composite materials (not crushing) are added, and solution filtering, filter are carried out after 4h is adsorbed at 30 DEG C
Pb ion concentrations are used in liquid is measured with inductively coupled plasma atomic emission spectrometry (ICP), filtered Pb ion concentrations
For 115.25mg/L, filter liquor concentration is measured as 469.25mg/L before adsorbing, and Pb removal rates reach 75.44%, and adsorbance reaches
354mg/g。
Claims (10)
1. a kind of ZIF-8/ mycelia composite material, which is characterized in that have ZIF-8 in hyphal surface load, preferably in filamentous fungi
Hyphal surface load has ZIF-8.
2. the preparation method of ZIF-8/ mycelia composite material described in claim 1, which is characterized in that preparing the anti-of ZIF-8
Addition filamentous fungi mycelia is answered in system, product cleaning after reaction is dried to get to ZIF-8/ mycelia composite materials.
3. the preparation method of ZIF-8/ mycelia composite material according to claim 2, which is characterized in that prepare ZIF-8's
The raw material of reaction system addition is zinc salt and 2-methylimidazole, is mixed after being dissolved in solvent respectively, adds mycelia；The mycelia of addition
Dry weight：Zinc salt：Zinc salt solvent：2-methylimidazole：The mass volume ratio of the solvent of 2-methylimidazole is (20mg~100mg):
(0.8000g~1.000g):(25mL~35mL)：(0.9000g~1.100g)：(8mL~12mL)；It is preferred that 50mg:
0.8925g:30mL：0.9852g：10mL.
4. the preparation method of ZIF-8/ mycelia composite material according to claim 3, which is characterized in that the zinc salt packet
It includes：Zinc nitrate, zinc chloride or zinc acetate, preferably zinc nitrate；The filamentous fungi mycelia includes：Mucor, aspergillus niger, root
One or more of mould, mould, preferably Mucor.
5. the preparation method of ZIF-8/ mycelia composite material according to claim 3, which is characterized in that the zinc salt is molten
The solvent of agent and 2-methylimidazole includes methanol.
6. the preparation method of the ZIF-8/ mycelia composite materials according to Claims 2 or 3 or 4 or 5, which is characterized in that anti-
Ultrasonic reaction is should be, the power of ultrasonic reaction is 100~1000w, preferably 800w；The temperature of ultrasonic reaction is excellent no more than 40 DEG C
Select 20 DEG C；1~2h of ultrasonic reaction time, preferably 2h.
7. the preparation method of the ZIF-8/ mycelia composite materials according to Claims 2 or 3 or 4 or 5, which is characterized in that anti-
Mycelia directly takes out after answering, and reuses clear water cleaning and dries 2~6h at 50~80 DEG C, preferably 60 DEG C drying 6h.
8. the preparation method of the ZIF-8/ mycelia composite materials according to Claims 2 or 3 or 4 or 5, which is characterized in that training
Mycelia after supporting filters, drying obtains mycelia film for reacting；It is preferred that mycelia drying temperature be 50~80 DEG C, the time be 1min~
3min。
9. ZIF-8/ mycelia composite material described in claim 1 is removed for water pollutant.
10. ZIF-8/ mycelia composite material described in claim 1 is applied to water body removing heavy metals, lead is preferably removed.
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| CN113044911A (en) * | 2019-12-26 | 2021-06-29 | 西南科技大学 | Method for preparing ZIFs/loofah sponge composite material by using wastewater |
| CN113713776A (en) * | 2021-09-10 | 2021-11-30 | 天津工业大学 | Preparation method of ZIF-67-loaded wool fabric and application of wool fabric in printing and dyeing wastewater |
| CN114657098A (en) * | 2022-03-28 | 2022-06-24 | 深圳大学 | Modified microorganism, modification method and application thereof, and antitumor drug |
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Application publication date: 20181019 |