CN105642349A - Preparation method of manganese-based MOF (metal-organic framework) magnetic material - Google Patents
Preparation method of manganese-based MOF (metal-organic framework) magnetic material Download PDFInfo
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- CN105642349A CN105642349A CN201610088438.9A CN201610088438A CN105642349A CN 105642349 A CN105642349 A CN 105642349A CN 201610088438 A CN201610088438 A CN 201610088438A CN 105642349 A CN105642349 A CN 105642349A
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- magnetic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention provides a preparation method of a manganese-based MOF (metal-organic framework) magnetic material. 8-hydroxyquinoline is dissolved in absolute ethyl alcohol, and a solution with the concentration being 10-20 mol/L is formed; manganese salt is dissolved in water, a solution B with the concentration being 5-10 mol/L is formed, then, the solution A is added to the solution B, and reflux is performed for 2-8 h; centrifugation is performed, and obtained precipitates are washed and then dried; the dried solids are heated to 500-900 DEG C at the speed of 0.5-1.5 DEG C/min in the hydrogen atmosphere and calcined for 3-9 h, and the manganese-based MOF magnetic material is obtained. The prepared composite catalytic material can be easily separated and recovered from a reaction system with a magnetic separation method, the reuse efficiency of a catalyst is improved, secondary pollution to the environment is reduced, and the catalytic performance of the MOF structure is greatly improved.
Description
Technical field
The invention belongs to materialogy field, the preparation method relating to a kind of manganio metallic organic framework magnetic material.
Background technology
Along with development and the social progress of science and technology, environmental problem is day by day serious. Catalytic oxidation technologies plays more and more important effect in environmental improvement, and catalysis engineering plays very important effect, therefore the exploitation of new catalyst and performance study thereof always are a priority research areas.
Metallic organic framework (MOFs) the material representative organic-inorganic supramolecular materials of one class heterozygosis, is the ordered network structure being bonded by organic bridge ligand and inorganic metal ion. MOFs presents specific surface area the highest at present, minimum crystalline density and adjustable hole dimension and functional structure, shows the catalysis activity and selectivity of excellence in catalytic process, and metal-organic framework materials attracts wide attention at catalytic field. But when it is as liquid reactive catalyst, post catalyst reaction is cumbersome with the segregation ratio of product, and this brings difficulty to reusing of catalyst, environment can be caused secondary pollution simultaneously.
Conventional catalyst system has problems in the recovery of catalyst, and the method reclaiming main use mechanical separation of catalyst, such as centrifugal and filtration, length consuming time, efficiency are low, energy consumption is big, separating effect is unsatisfactory. Magnetic Isolation is a kind of novel green separation process, it is possible to fast and effeciently reclaim catalyst, reduces the energy consumption of separation process, reduces the secondary pollution that environment is caused by catalyst. Therefore, preparation the organometallic skeletal catalysis material of magnetic recovery can suffer from profound significance in concrete research and practical application.
Summary of the invention
For above-mentioned technical problem of the prior art, the preparation method that the invention provides a kind of manganio metallic organic framework magnetic material, the preparation method of described this manganio metallic organic framework magnetic material solves in prior art the technical problem that the catalyst efficiency for environmental improvement is low, be not easily recycled.
The preparation method that the invention provides a kind of manganio metallic organic framework magnetic material, comprises the steps:
1) oxine is dissolved in dehydrated alcohol, forms the solution A that concentration is 10��20mol/L;
2) by soluble in water for manganese salt, form the solution B of 5��10mol/L, then control the speed of 0.5��5mL/min, above-mentioned solution A is joined in solution B, after, at 100��200 DEG C of 2��8h that reflux;
3) controlling rotating speed is 5000��10000r/min, centrifugal 5��15min, by gained precipitate successively with dehydrated alcohol and water washing, then carries out vacuum drying at the temperature of 50 ~ 70 DEG C;
4) dried gained solid carries out calcining 3��9h with the ramp of 0.5 ~ 1.5 DEG C/min to 500��900 DEG C in a hydrogen atmosphere, obtains manganio metallic organic framework magnetic material.
Further, described manganese salt is manganese nitrate, manganese chloride, manganese acetate or manganese sulfate.
Further, gained precipitate is successively with dehydrated alcohol and water washing 4��6 times.
Due to the fact that employing metal one organic framework materials (MOFs), having the pore structure of three-dimensional, with metal ion for junction point, organic ligand supports Special composition 3D and extends, it is the important novel porous materials of a class, is conducive to the enhancing of catalytic performance. Utilize the manganio metallic organic framework magnetic material of the present invention as heterogeneous catalysis, catalytic oxidation for the high-level oxidation technology aniline degradation waste water based on potentiometric titrations, under certain conditions, 100% aniline degradation only needs 30min, and is prone to magnetic recovery recycling. And at identical conditions, utilize the material that prior art synthesizes as heterogeneous catalysis, for the catalysis catalytic degradation reaction based on the high-level oxidation technology aniline degradation waste water of potentiometric titrations, 100% aniline degradation needs more than 60min, and is not easily recycled recycling. The material of the present invention has metallo-organic framework, substantially increases its catalytic performance, and catalytic performance can improve more than 1 times relative to prior art.
The present invention compares with prior art, and its technological progress is significant. The method of the present invention solves the conventional catalyst system problem big, inefficient of energy consumption in catalyst recovery. The feature that the manganio metallic organic framework magnetic material of the present invention is maximum is exactly that catalyst is realized recycling by the mode that can adopt magnetic recovery, reduces its secondary pollution that environment is caused, the energy loss reduced in separation process; The MOFs structure of this material is more better catalysis activity than traditional catalyst owing to its bigger specific surface area and adjustable aperture structure demonstrate simultaneously. And the preparation process of the method for the present invention does not need the condition such as low temperature, high pressure, therefore this preparation method technique is simple, and condition is gentleer, and equipment is convenient, and manufacturing cycle is short, it is adaptable to industrialized production.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of manganio metallic organic framework magnetic material.
Fig. 2 is the transmission electron microscope picture of manganio metallic organic framework magnetic material.
Detailed description of the invention
Below by specific embodiment and in conjunction with accompanying drawing, the present invention is further elaborated, but is not limiting as the present invention.
Embodiment 1
The preparation method of a kind of manganio metallic organic framework magnetic material, specifically includes following steps:
(1), oxine is dissolved in dehydrated alcohol, forms the solution A that concentration is 10mol/L;
(2), by soluble in water for manganese salt, forming the solution B of 5mol/L, above-mentioned solution A is added drop-wise in solution B by the speed then controlling 0.5mL/min, after dropwising, and 200 DEG C of backflow 2h;
Described manganese salt is manganese chloride;
(3), control rotating speed be 5000r/min, centrifugal 15min, dry after gained precipitate is washed.Gained precipitate with dehydrated alcohol and water washing 4 times, then controls temperature 60 C and carries out vacuum drying 12h successively;
(4), dried gained solid in a hydrogen atmosphere with the ramp of 1 DEG C/min to 500 DEG C carry out calcining 9h, obtain manganio metallic organic framework magnetic material.
Adopt X-ray diffractometer (model that Japan RIGAKU produces is D/Max 2550PC) that the manganio metallic organic framework magnetic material of above-mentioned gained is measured, the X-ray diffractogram of the manganio metallic organic framework magnetic material of gained is as shown in Figure 1, as can be seen from Figure 1 it is positioned at 34.9 degree, 40.5 degree, 58.7 degree, 70.0 degree and 74.8 degree (111), (200), (220), (400) and (511) crystal face peaks representing manganese oxide respectively, has been indicated above in the manganio metallic organic framework magnetic material prepared and there is manganese oxide crystal.
Adopt transmission electron microscope (model that HIT produces is H-7650) that the manganio metallic organic framework magnetic material of above-mentioned gained is scanned, the transmission electron microscope picture of the manganio metallic organic framework magnetic material of gained is as shown in Figure 2, as can be seen from Figure 2 in the manganio metallic organic framework magnetic material prepared, cobalt oxide forms circulus, and has obvious organic framework.
Application Example 1
Utilizing the manganio metallic organic framework magnetic material of embodiment 1 gained as heterogeneous catalysis, for the catalytic oxidation of the high-level oxidation technology aniline degradation waste water based on potentiometric titrations, its detailed process is as follows:
Take aniline waste water that 100mL concentration is 30ppm in the conical flask of 250mL, add the Oxone of 300mg, be subsequently added into 5mg(0.05g/L) catalyst (product of embodiment 1). With the NaHCO of 0.5M3Solution regulates pH value to neutral. Conical flask is placed on 25 DEG C of water bath with thermostatic control shaking tables and carries out stirring reaction, to add oxidant for time zero, take sample at set intervals, add isopyknic methanol cancellation reaction immediately, with the ultraviolet absorptivity measuring solution after the membrane filtration of 0.22 ��m. And then the degradation efficiency of the relation calculating aniline degradation according to concentration of aniline in solution and absorbance: 100% aniline degradation only needs 30min, simultaneously because material has very strong magnetic, it is easy to be utilized after being reclaimed by magnetic again.
Application comparative examples 1
Utilizing common oxidation manganese material that prior art synthesizes as heterogeneous catalysis, for the catalysis catalytic oxidation based on the high-level oxidation technology aniline degradation of potentiometric titrations, its detailed process is as follows:
Take aniline waste water that 100mL concentration is 30ppm in the conical flask of 250mL, add the Oxone of 300mg, be subsequently added into 5mg(0.05g/L) catalyst. With the NaHCO of 0.5M3Solution regulates pH value to neutral. Conical flask is placed on 25 DEG C of water bath with thermostatic control shaking tables and carries out stirring reaction, to add oxidant for time zero, take sample at set intervals, add isopyknic methanol cancellation reaction immediately, with the ultraviolet absorptivity measuring solution after the membrane filtration of 0.22 ��m. And then the degradation efficiency of the relation calculating aniline degradation according to concentration of aniline in solution and absorbance: 100% aniline degradation needs more than 60min, and is not easily recycled recycling.
Contrasted by above-mentioned Application Example 1 and application comparative examples 1, the common oxidation manganese material that the manganio metallic organic framework magnetic material prepared by the method is prepared than art methods is at identical conditions, catalytic degradation efficiency improves 1 times, it is easier to recycling.The preparation method being indicated above the present invention, the manganio metallic organic framework magnetic material formed by ligand complex can well improve the catalytic performance of material, and have stronger magnetic and be easily recycled.
Embodiment 2
The preparation method of a kind of manganio metallic organic framework magnetic material, specifically includes following steps:
(1), oxine is dissolved in dehydrated alcohol, forms the solution A that concentration is 20mol/L;
(2), by soluble in water for manganese salt, forming the solution B of 5mol/L, above-mentioned solution A is added drop-wise in solution B by the speed then controlling 5mL/min, after dropwising, and 100 DEG C of backflow 8h;
Described manganese salt is manganese acetate;
(3), control rotating speed be 10000r/min, centrifugal 5min, dry after gained precipitate is washed. Gained precipitate with dehydrated alcohol and water washing 4 times, then controls temperature 60 C and carries out vacuum drying 12h successively;
(4), dried gained solid in a hydrogen atmosphere with the ramp of 1 DEG C/min to 900 DEG C carry out calcining 3h, obtain manganio metallic organic framework magnetic material.
Embodiment 3
The preparation method of a kind of manganio metallic organic framework magnetic material, specifically includes following steps:
(1), oxine is dissolved in dehydrated alcohol, forms the solution A that concentration is 10mol/L;
(2), by soluble in water for manganese salt, forming the solution B of 8mol/L, above-mentioned solution A is added drop-wise in solution B by the speed then controlling 3mL/min, after dropwising, and 180 DEG C of backflow 5h;
Described manganese salt is manganese sulfate;
(3), control rotating speed be 8000r/min, centrifugal 10min, dry after gained precipitate is washed. Gained precipitate with dehydrated alcohol and water washing 5 times, then controls temperature 60 C and carries out vacuum drying 12h successively;
(4), dried gained solid carry out calcining 3��9h with the ramp of 1 DEG C/min to 500��900 DEG C in a hydrogen atmosphere, obtain manganio metallic organic framework magnetic material.
Embodiment 4
The preparation method of a kind of manganio metallic organic framework magnetic material, specifically includes following steps:
(1), oxine is dissolved in dehydrated alcohol, forms the solution A that concentration is 10mol/L;
(2), by soluble in water for manganese salt, forming the solution B of 5mol/L, above-mentioned solution A is added drop-wise in solution B by the speed then controlling 4mL/min, after dropwising, and 150 DEG C of backflow 5h;
Described manganese salt is manganese nitrate;
(3), control rotating speed be 5000r/min, centrifugal 15min, dry after gained precipitate is washed. Gained precipitate with dehydrated alcohol and water washing 6 times, then controls temperature 60 C and carries out vacuum drying 12h successively;
(4), dried gained solid in a hydrogen atmosphere with the ramp of 1 DEG C/min to 700 DEG C carry out calcining 7h, obtain manganio metallic organic framework magnetic material.
Embodiment 5
The preparation method of a kind of manganio metallic organic framework magnetic material, specifically includes following steps:
(1), oxine is dissolved in dehydrated alcohol, forms the solution A that concentration is 15mol/L;
(2), by soluble in water for manganese salt, forming the solution B of 8mol/L, above-mentioned solution A is added drop-wise in solution B by the speed then controlling 0.5mL/min, after dropwising, and 100 DEG C of backflow 8h;
Described manganese salt is manganese acetate;
(3), control rotating speed be 10000r/min, centrifugal 6min, dry after gained precipitate is washed. Gained precipitate with dehydrated alcohol and water washing 4 times, then controls temperature 60 C and carries out vacuum drying 12h successively;
(4), dried gained solid in a hydrogen atmosphere with the ramp of 1 DEG C/min to 700 DEG C carry out calcining 9h, obtain manganio metallic organic framework magnetic material.
In sum, the manganio metallic organic framework magnetic material formed by ligand complex can well improve the catalytic performance of material, there is stronger magnetic, and be easily recycled, it is for the high-level oxidation technology aniline degradation waste water based on potentiometric titrations, aniline in degradable water only needs 25��35min, is about 2 times of catalytic efficiency of the catalysis material that traditional method is prepared, and is easily recycled.
The above is only the citing of embodiments of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the technology of the present invention principle; can also making some improvement and modification, these improve and modification also should be regarded as protection scope of the present invention.
Claims (3)
1. the preparation method of a manganio metallic organic framework magnetic material, it is characterised in that comprise the steps:
1) oxine is dissolved in dehydrated alcohol, forms the solution A that concentration is 10��20mol/L;
2) by soluble in water for manganese salt, form the solution B of 5��10mol/L, then control the speed of 0.5��5mL/min, above-mentioned solution A is joined in solution B, after, at 100��200 DEG C of 2��8h that reflux;
3) controlling rotating speed is 5000��10000r/min, centrifugal 5��15min, by gained precipitate successively with dehydrated alcohol and water washing, then carries out vacuum drying at the temperature of 50 ~ 70 DEG C;
4) dried gained solid carries out calcining 3��9h with the ramp of 0.5 ~ 1.5 DEG C/min to 500��900 DEG C in a hydrogen atmosphere, obtains manganio metallic organic framework magnetic material.
2. the preparation method of a kind of manganio metallic organic framework magnetic material according to claim 1, it is characterised in that: described manganese salt is manganese nitrate, manganese chloride, manganese acetate or manganese sulfate.
3. the preparation method of according to claim a kind of manganio metallic organic framework magnetic material, it is characterised in that: gained precipitate is successively with dehydrated alcohol and water washing 4��6 times.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108905976A (en) * | 2018-07-24 | 2018-11-30 | 湖南大学 | Manganese ion doping metal-organic framework materials and its preparation method and application |
| CN110201719A (en) * | 2019-06-06 | 2019-09-06 | 南京科技职业学院 | A kind of pharmacy sewage administering method |
| CN110876804A (en) * | 2019-11-04 | 2020-03-13 | 华中科技大学 | Preparation and application of porous mangano-manganic oxide nano probe |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108905976A (en) * | 2018-07-24 | 2018-11-30 | 湖南大学 | Manganese ion doping metal-organic framework materials and its preparation method and application |
| CN108905976B (en) * | 2018-07-24 | 2020-04-03 | 湖南大学 | Manganese ion doped metal organic framework material and preparation method and application thereof |
| CN110201719A (en) * | 2019-06-06 | 2019-09-06 | 南京科技职业学院 | A kind of pharmacy sewage administering method |
| CN110201719B (en) * | 2019-06-06 | 2020-04-21 | 南京科技职业学院 | Pharmaceutical sewage treatment method |
| CN110876804A (en) * | 2019-11-04 | 2020-03-13 | 华中科技大学 | Preparation and application of porous mangano-manganic oxide nano probe |
| CN110876804B (en) * | 2019-11-04 | 2021-05-18 | 华中科技大学 | Preparation and application of porous mangano-manganic oxide nano probe |
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