CN110526381A - Co-MOFs base macroscopic view composite material generates the method that active oxygen species remove emerging pollutant - Google Patents
Co-MOFs base macroscopic view composite material generates the method that active oxygen species remove emerging pollutant Download PDFInfo
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The present invention provides a kind of method that Co-MOFs base macroscopic view composite material generates the emerging pollutant (ECs) of active oxygen species (ROS) removal.The method for generating ROS removal ECs using Co-MOFs base macroscopic view composite material, which includes the following steps: that 1) macroscopical carrier is placed in the precursor liquid of MOFs containing cobalt, impregnates, and takes out carrier, washing, drying, calcining can obtain the composite material；2) under room temperature, above-mentioned composite material is added in the aqueous solution containing peroxide, that is, can produce a large amount of ROS(OH, SO4, O2 etc.)；3) ECs such as water removal Chinese medicine object, antibiotic and resistance bacterium/gene are removed using the ROS that the above process generates；4) the Co-MOFs base macroscopic view composite material after peroxide aqueous solution processing aging is to restore its activity.Method provided by the invention can generate ROS and efficiently remove ECs in water removal, solve the problems, such as that MOFs class material is difficult to separation and recovery in sewage/wastewater application field and regeneration cost is high；The composite material of offer has environment friendly and wide market development potential.
Description
Technical field
The invention belongs to metal organic frame composite materials and emerging pollutant catabolic gene field, and in particular to a kind of Co-
MOFs base macroscopic view composite material generates the method that active oxygen species remove emerging pollutant.
Background technique
Metal organic frame (Metal organic frameworks, MOFs) and its derived material are as novel nano
Functional material is used for the environment remediation extensive concern by domestic and international researcher and Environmental Engineer.The porous material of MOFs class
Expect that most representative feature is exactly that can realize its structure and performance by changing metallic atom in skeleton structure and organic ligand
Regulation.Currently, the MOFs class material category synthesized is greater than 10,000 kinds, these materials are widely used in chemical liquid or gas
The fields such as body separation, industry urge, photoelectricity or semiconductor；It screens and designs the MOFs base functional material safety with specific function
And efficiently remove the hot spot and difficulty that remove water, toxic pollutant is environment remediation and field of functional materials research in soil and atmosphere
Point.
The Fenton-like process degradation toxic pollutant that MOFs based composites mediate is that one, environmental catalysis field is important
Emerging research direction.If Liu et al. (2019 358:408 of Chem. Eng. J.) is by imidazoles MOFs material ZIF-67 high temperature
Calcining forms porous carbon materials containing N and carries Co, for activating persulfate to remove parachloroanilinum in water removal；But the research and utilization
ZIF-67 derived material does not have magnetism, it has not been convenient to recycle, activator when increasing practical water process/catalyst recycling at
This.Based on this, the sight of research is focused on building novel magnetic MOFs based composites by water environment engineering scholar, passes through introducing
Fe can not only form magnetic bimetallic MOFs derived material but also can increase its stability, such as Yang (Chem. Eng. J. 2019
353:329) synthesize that the magnetic MOFs derived material CoFe2O4 of tool is nanocrystalline, which shows preferable Magneto separate
Energy；But CoFe2O4 after the recovery is nanocrystalline to need high-temperature calcination that could restore its activity function, therefore explores a kind of economical, high
Effect and the strong MOFs based composites of reusable property have apparent technical need for aquatic ecological restoration.
Theoretically, by macroscopical carrier surface functional group abundant and Microstructure Information, MOFs presoma can pass through original position
The method formation Co-MOFs base macroscopic view composite material of epitaxial growth can be realized simple and quick while meeting its catalytic applications
It is at high cost really to solve the problems, such as that MOFs class material reuses for separation；However, literature search early period confirms: utilizing Co-MOFs
Base macroscopic view composite material generates the method that active oxygen species remove emerging pollutant and is rarely reported.
Summary of the invention
It is emerging that primary and foremost purpose of the present invention is to provide a kind of Co-MOFs base macroscopic view composite material generation active oxygen species removal
The method of pollutant.
The purpose of the present invention is realized by following technology path: Co-MOFs base macroscopic view composite material generates active oxygen object
The method that kind (ROS) removes emerging pollutant (ECs), which comprises the steps of: 1) configure the forerunner of MOFs containing cobalt
Macroscopical carrier is placed in precursor liquid and impregnates by liquid, and washing, drying and calcining can obtain the composite material after taking out carrier；2) room temperature
Under the conditions of, above-mentioned composite material is added in the aqueous solution containing peroxide, that is, can produce a large amount of ROS(OH, SO4, O2
Deng)；3) ROS is generated using the above process remove the ECs such as water removal Chinese medicine object, antibiotic and resistance bacterium/gene；4) peroxide is utilized
Co-MOFs base macroscopic view composite material after aqueous solution processing aging is to restore its activity.
The macroscopic view carrier is at least one of the spherical activated alumina of diameter >=1 mm or zeolite molecular sieve.
The Co-MOFs material is zeolite imidazole class skeleton (ZIFs).
The peroxide is at least one of ozone or peroxy-monosulfate.
The Co-MOFs base macroscopic view composite material is that Co-MOFs is supported on load using the method for epitaxial growth in situ
On body.
The method of the Co-MOFs base macroscopic view composite material, which comprises the following steps: (1) configure MOFs
Ligand solution is denoted as the first maceration extract by precursor liquid, and cobalt salt solution is denoted as the second maceration extract, mole of the ligand and metal salt
Than for 8:1；(2) macroscopical carrier is impregnated with first maceration extract, room temperature is pulled out after standing 30 min, and clear with solvent
It washes 3 ~ 5 times；(3) step (2) products obtained therefrom being impregnated with second maceration extract, room temperature is pulled out after standing 30 min, and
It is cleaned 3 ~ 5 times with solvent；(4) with the mixed solution of first maceration extract and the second maceration extract to step (3) products obtained therefrom into
Row impregnates, and room temperature is pulled out after standing at least 24 h, and is cleaned 3 ~ 5 times with solvent, is subsequently placed in 105 DEG C of drying；(5) by step
(4) products obtained therefrom carries out calcination processing, obtains the Co-MOFs base macroscopic view composite material.
The solvent includes at least one of water, methanol, ethyl alcohol or n,N-Dimethylformamide.
The calcination processing process: under aerobic conditions, with the heating rate of 5 DEG C/min by step (5) products obtained therefrom liter
To 350~650 DEG C and 3 h of constant temperature, product takes out temperature after being cooled to room temperature.
Detailed description of the invention
Fig. 1 is the curve synoptic diagram that Co-MOFs base macroscopic view composite material activates that PMS removes metronidazole (MNZ) in water removal.
Fig. 2 is the curve signal that Co-MOFs base macroscopic view composite material activates that PMS removes sulfamethoxazole (SMX) in water removal
Figure.
Fig. 3 is that different quenchers remove MNZ effect tendency figure in water removal to Co-MOFs base macroscopic view composite material activation PMS.
Fig. 4 is that Co-MOFs base macroscopic view composite material activation PMS goes MNZ cycle performance and its regenerability in water removal to show
It is intended to.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below with reference to the embodiment of the present invention
Attached drawing carries out clear, complete description to the technical solution of the embodiment of the present invention.Obviously, described embodiment is the present invention
A part of the embodiment, rather than whole embodiments.Based on the described embodiment of the present invention, those of ordinary skill in the art exist
Every other embodiment obtained, belongs to the scope of protection of the invention under the premise of without creative work.
Embodiment 1.
It is a kind of to generate the emerging pollutant (ECs) of active oxygen species (ROS) removal using Co-MOFs base macroscopic view composite material
Method, include the following steps.
(1) preparation of Co-MOFs base macroscopic view composite material: a) the 2-methylimidazole methanol solution of 480 mM is respectively configured
The cobalt nitrate methanol solution (the second maceration extract) of (the first maceration extract) and 60 mM；B) by the spherical activated alumina (3 ~ 5 of 60 g
Mm it) is placed in the first maceration extract after being standing and soaking 30 min and pulls out, cleaned 3 times with methanol；C) step b) products obtained therefrom is placed in
It pulls out after being standing and soaking 30 min in second maceration extract, is cleaned 3 times with methanol；D) step c) products obtained therefrom is placed in the first dipping
It pulls out after being standing and soaking at least 24 h in the mixed solution of liquid and the second maceration extract, is respectively cleaned 5 times with methanol and deionized water, after
Place it in 105 DEG C of drying；E) under aerobic conditions, step d) products obtained therefrom is calcined with the heating rate of 5 DEG C/min
Handle (350 DEG C, 450 DEG C or 650 DEG C 3 h of constant temperature), product takes out after being cooled to room temperature, be denoted as respectively ZA350, ZA450 or
ZA650。
(2) investigate Co-MOFs base macroscopic view composite material activation PMS and go MNZ efficiency in water removal: measuring 80 mL concentration is
The MNZ aqueous solution of 20 mg/L is separately added into ZA350(20 g/L in clean reaction flask) and PMS(1 mM), it is placed in room temperature (25
± 2 DEG C) 100 min of (300 rpm) reaction are stirred, separated in time sampling is analyzed；Change ZA350 into business nanometer
Cobalt oxide (Aladdin, Co3O4, CAS:1308-06-1,100 nm) (0.4 g/L), other conditions are constant, carry out business nanometer
Cobalt oxide catalysis PMS comparative experiments (cobalt oxide is catalyst optimal to PMS activation efficiency in all metal oxides).
(3) the data obtained is depicted as curve graph, ZA350/PMS system can be aoxidized in 100 min and be gone as shown in Figure 1:
Except 98% or more MNZ；In addition, as seen from the figure, ZA350 is individual to MNZ to the absorption of MNZ and PMS within entire reaction time
The main reason for oxidation is not its removal, the removal of MNZ mainly generate active oxygen species by ZA350 activation PMS to realize；
Comparative experiments shows that ZA350 has higher catalysis PMS efficiency than business nanometer cobalt oxide.
Embodiment 2.
(1) investigate Co-MOFs base macroscopic view composite material activation PMS and go SMX efficiency in water removal: measuring 80 mL concentration is
ZA650(20 g/L is added in clean reaction flask in the SMX aqueous solution of 10 mg/L) and PMS(0.25 mM), it is placed in room temperature (25 ± 2
DEG C) 60 min of (300 rpm) reaction are stirred, separated in time sampling is analyzed.
(3) the data obtained is depicted as curve graph, as shown in Figure 3: ZA650/PMS system can oxidation removal in 60 min
95% or more SMX；In addition, as seen from the figure, ZA650 is to the absorption of SMX or PMS to the individual oxygen of SMX within entire reaction time
The main reason for change is not its removal, the removal of SMX mainly generate active oxygen species by ZA650 activation PMS to realize.
Embodiment 3.
(1) it investigates Co-MOFs base macroscopic view composite material activation PMS and goes resistance bacterium efficiency in water removal: measuring 80 mL concentration
Tetracycline resistance gene is carried for the E. coli(of 107 cfu/mL) in clean reaction flask, ZA450(20 g/L is added in aqueous solution)
With PMS(1 mM), it is placed in (25 ± 2 DEG C) of room temperature stirrings (300 rpm) and reacts 45 min, separated in time sampling is divided
Analysis；The result shows that: in 45 min, ZA650/PMS system can not after can completely removing the E. coli(of tetracycline resistance and inactivating
Culture), and 2.5log is less than to the removal of target resistance bacterium when ZA450 and PMS individualism in entire reaction time, target is anti-
Property bacterium removal mainly since ZA450 activation PMS is generated caused by its eucaryotic cell structure of ROS fast-crushing and resistant gene.
Embodiment 4.
(1) the ROS type analysis generated when Co-MOFs base macroscopic view composite material activation PMS: by taking ZA450 as an example, pass through
Quenching experiments study it and activate the ROS type formed when PMS, and measuring 80 mL concentration is the MNZ aqueous solution of 20 mg/L in cleaning
ZA450(20 g/L is added in reaction flask, and the preparation method is the same as that of Example 1, the difference is that calcination temperature is 450 DEG C) and PMS(1
MM)；Control sample is not added quencher, and experiment sample is separately added into 100 mM ethyl alcohol, the 100 mM tert-butyl alcohols, 1 mM histidine or 1 mM pairs
Benzoquinones is placed on (25 ± 2 DEG C) of room temperature stirrings (300 rpm) and reacts 100 min, and separated in time sampling is analyzed.
(2) the data obtained is depicted as curve graph, as shown in Figure 3: 100 mM ethyl alcohol and the 100 mM tert-butyl alcohols for
ZA450/PMS system removal MNZ shows inhibiting effect, and the inhibition of 100 mM ethyl alcohol is eager to excel than the 100 mM tert-butyl alcohols,
Illustrating ZA450/PMS system, there are SO4 and OH, and SO4 is greater than OH to the contribution that metronidazole aoxidizes；In addition, 1 mM group
Propylhomoserin and 1 mM 1,4-benzoquinone also show stronger inhibiting effect, illustrate that ZA450/PMS system exists simultaneously O2 and 1O2 and promotes
The oxidative degradation of MNZ.
Embodiment 5.
(1) investigating Co-MOFs base macroscopic view composite material (by taking ZA450 as an example) activation PMS goes MNZ in water removal to be recycled
Performance and its regenerability: first circulation, measuring 80 mL concentration is the MNZ aqueous solution of 20 mg/L in clean reaction flask, respectively
ZA450(20 g/L is added) and PMS(1 mM), it is placed in (25 ± 2 DEG C) of room temperature stirrings (300 rpm) and reacts 100 min, interval
Certain time sampling is analyzed；After reaction, ZA450 is pulled out from solution, is cleaned 5 times, is placed in deionized water
105 DEG C of drying；ZA450 is pulled out after reaction, is cleaned and dry by second circulation, the reaction step for repeating first circulation；
Third circulation, repeats the reaction step of first circulation or second circulation, and reaction terminates, ZA450 is pulled out, after cleaning, drying by it
It is placed in PMS aqueous solution (1 mM) and handles 30 min, then ZA450 is pulled out, cleans, dry；4th circulation, repeats the first or second
The reaction step of circulation.
(3) the data obtained is depicted as curve graph, as shown in Figure 3: ZA450/PMS system energy in the reaction of first circulation
Reaching 97% or more removal rate, second circulation is declined slightly (92%), and third circulation removal rate is decreased obviously, and only 79%, this can
It can be the intermediate product in loss or the first, second circular response due to ZA450 surface-active site after the degradation of MNZ parent
Composite material surface is accumulated in, the mass transport process between MNZ molecule and ZA450 is hindered；Composite material is handled through PMS aqueous solution
Afterwards, the degradation capability to MNZ has been restored, as shown, the ZA450 after regeneration is to the removal rate of MNZ 60 in the 4th circulation
Just reach 100% in min, sufficiently illustrate its catalytic performance after Co-MOFs base macroscopic view composite material aging provided by the present invention
The method of the advantages of being easy to activating and regenerating, Oxidation at room temperature agent activating and regenerating is suitable for actual industrial wastewater treatment.
It should be understood that although carrying out particularly shown and description to the present invention with reference to its illustrative embodiment,
It should be understood by those skilled in the art that without departing substantially from by spirit and model of the invention as defined in the claims
Under conditions of enclosing, any combination of various embodiments can be carried out in the variation for wherein carrying out various forms and details.
Claims (7)
1. a kind of generate the emerging pollutant (ECs) of active oxygen species (ROS) removal using Co-MOFs base macroscopic view composite material
Method, which comprises the steps of: 1) prepare MOFs precursor liquid, macroscopical carrier is placed in precursor liquid and is impregnated, take out
Carrier, washing, drying and calcining can obtain the composite material；2) under room temperature, above-mentioned composite material is added and contains peroxide
Aqueous solution in, that is, can produce a large amount of ROS(OH, SO4, O2 etc.)；3) it is gone in water removal using the ROS that the above process generates
The ECs such as drug, antibiotic and resistance bacterium/gene；4) the Co-MOFs base macroscopic body after peroxide aqueous solution processing aging is utilized
Composite material is to restore its activity.
2. the method that Co-MOFs base macroscopic view composite material generates ROS removal ECs, feature exist according to claim 1
In the macroscopic view carrier is at least one of the spherical activated alumina of diameter >=1 mm or zeolite molecular sieve.
3. the method that Co-MOFs base macroscopic view composite material generates ROS removal ECs, feature exist according to claim 1
In the Co-MOFs material is zeolite imidazole class skeleton (ZIFs).
4. the method that Co-MOFs base macroscopic view composite material generates ROS removal ECs, feature exist according to claim 1
In the peroxide is at least one of ozone or peroxy-monosulfate.
5. the method that Co-MOFs base macroscopic view composite material generates ROS removal ECs, feature exist according to claim 1
In the Co-MOFs base macroscopic view composite material is that Co-MOFs is immobilized on carrier using the method for epitaxial growth in situ
's.
6. a kind of method for preparing the described in any item Co-MOFs base macroscopic view composite materials of claim 1 ~ 5, feature exist
In, comprising: (1) MOFs precursor liquid is configured, ligand solution is denoted as the first maceration extract, cobalt salt solution is denoted as the second maceration extract, institute
The molar ratio for stating ligand and metal salt is 8:1；(2) macroscopical carrier is impregnated with first maceration extract, room temperature stands 30
It pulls out after min, and is cleaned 3~5 times with solvent；(3) step (2) products obtained therefrom is impregnated with second maceration extract, often
Temperature is pulled out after standing 30 min, and is cleaned 3~5 times with solvent；(4) mixing with first maceration extract and the second maceration extract is molten
Liquid impregnates step (3) products obtained therefrom, and room temperature is pulled out after standing at least 24 h, and is cleaned 3~5 times with solvent, then sets
It is dried in 105 DEG C；(5) under aerobic conditions, step (4) products obtained therefrom is placed in 350~650 DEG C of 3 h(5 DEG C/min of calcining),
The Co-MOFs base macroscopic view composite material can be obtained.
7. according to the method described in claim 6, it is characterized in that, the solvent includes water, methanol, ethyl alcohol or N, N- dimethyl
At least one of formamide.
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Cited By (7)
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| CN110961159A (en) * | 2019-12-31 | 2020-04-07 | 五邑大学 | Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof |
| CN111205477A (en) * | 2020-02-28 | 2020-05-29 | 三峡大学 | Preparation of ZIF-67 catalyst and application of catalyst in degradation of antibiotics such as tetracycline |
| CN111362449A (en) * | 2020-02-19 | 2020-07-03 | 大连理工大学 | Method for removing antibiotic resistance genes by activating persulfate through silver ammonia solution |
| CN112121798A (en) * | 2020-09-16 | 2020-12-25 | 中国科学院城市环境研究所 | Method for degrading chloramphenicol in water under catalysis of MIL-101(Fe/Co) derived magnetic cobalt ferrite and application |
| CN112892593A (en) * | 2021-01-18 | 2021-06-04 | 广东工业大学 | MOFs/water hyacinth derived material, preparation method thereof and degradation method of organic pollutants |
| CN113042105A (en) * | 2021-04-12 | 2021-06-29 | 西北师范大学 | Preparation method of hydroxyapatite nanowire combined cobalt MOFs beaded catalyst |
| CN115445589A (en) * | 2022-09-28 | 2022-12-09 | 中交上海航道勘察设计研究院有限公司 | Preparation method and application of molecular sieve/Fe-MIL-53 material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110961159A (en) * | 2019-12-31 | 2020-04-07 | 五邑大学 | Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof |
| CN110961159B (en) * | 2019-12-31 | 2022-11-15 | 五邑大学 | Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof |
| CN111362449A (en) * | 2020-02-19 | 2020-07-03 | 大连理工大学 | Method for removing antibiotic resistance genes by activating persulfate through silver ammonia solution |
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| CN111205477B (en) * | 2020-02-28 | 2022-04-22 | 三峡大学 | Preparation of ZIF-67 catalyst and application of catalyst in degradation of antibiotics such as tetracycline |
| CN112121798A (en) * | 2020-09-16 | 2020-12-25 | 中国科学院城市环境研究所 | Method for degrading chloramphenicol in water under catalysis of MIL-101(Fe/Co) derived magnetic cobalt ferrite and application |
| CN112121798B (en) * | 2020-09-16 | 2023-10-20 | 中国科学院城市环境研究所 | Method for degrading chloramphenicol in water under catalysis of MIL-101 (Fe/Co) derived magnetic cobalt ferrite and application thereof |
| CN112892593A (en) * | 2021-01-18 | 2021-06-04 | 广东工业大学 | MOFs/water hyacinth derived material, preparation method thereof and degradation method of organic pollutants |
| CN112892593B (en) * | 2021-01-18 | 2022-11-08 | 广东工业大学 | MOFs/water hyacinth derived material, preparation method thereof and degradation method of organic pollutants |
| CN113042105A (en) * | 2021-04-12 | 2021-06-29 | 西北师范大学 | Preparation method of hydroxyapatite nanowire combined cobalt MOFs beaded catalyst |
| CN115445589A (en) * | 2022-09-28 | 2022-12-09 | 中交上海航道勘察设计研究院有限公司 | Preparation method and application of molecular sieve/Fe-MIL-53 material |
| CN115445589B (en) * | 2022-09-28 | 2024-03-15 | 中交上海航道勘察设计研究院有限公司 | Preparation method and application of molecular sieve/Fe-MIL-53 material |
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