CN108607610A - It is a kind of can magnetic recycling Fe-MOF photochemical catalysts preparation method and applications - Google Patents
It is a kind of can magnetic recycling Fe-MOF photochemical catalysts preparation method and applications Download PDFInfo
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/33—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses it is a kind of can magnetic recycling Fe MOF photochemical catalysts preparation method and applications, preparation method includes：(1) 2 MI are dispersed in methanol, obtain 2 MI solution；By Fe (NO3)3It is dispersed in methanol and obtains Fe3+Solution；(2) gained Fe is added dropwise in 2 MI solution of gained3+In solution, suspension is stirred and evenly mixed to obtain；(3) suspension obtains Fe MOF photochemical catalysts after standing, washing and vacuum drying successively.The preparation method of photochemical catalyst of the present invention is simple, low in raw material price, and photohole and electronics are easily isolated, and the catalyst has certain magnetism, can be realized and be separated and recovered by externally-applied magnetic field, have very high economic benefit.
Description
Technical field
The present invention relates to catalysis material technical fields, especially visible light responsible photocatalytic material technical field, specifically
It is related to a kind of preparation method and application of novel Fe-MOF photochemical catalysts.
Background technology
In recent years, due to the polluter excess emissions that generate in various industry, agricultural and mining process, global environment by
To the serious pollution of toxic heavy metal.Chromium (Cr) is pollutant common in surface and underground water, it is widely used in being electroplated, skin
Remove from office tanning, printing, pigment, the industries such as polishing.The aquatic ecosystem and drinking water source of Cr (VI) pollutions can lead to severe diarrhea
And carcinoma of urinary bladder, liver cancer, kidney and cutaneum carcinoma, seriously threaten environmental and human health impacts.Even if under relatively low concentration, by
In the high toxicity of Cr (VI), carcinogenicity and by the bioconcentration of food chain, Cr (VI) can still cause human body very big danger
Evil.
Cr (III) is environmentally friendly, to plant and human life's important role, so Cr (VI) is reduced into Cr
(III) it is considered as the available strategy for removing Cr (VI) in waste water.And carry out light-catalyzed reaction, condition temperature using photochemical catalyst
With non-secondary pollution.Photocatalysis method is to be more than the electricity generated under the light irradiation of catalysis band gap based on the energy in catalysis material
Son-hole is to (e--h+), Cr can be become by Cr (VI) reduction in the solution by moving to these electronics of catalyst surface
(III).Many researchers report TiO2Photo catalytic reduction Cr (VI), but TiO2Application by its broad stopband width (3-
Limitation 3.2eV) can only absorb ultraviolet light.Photochemical catalyst with visible light activity such as CdS, SnS2, Ag2S and WO3It is wide
General report, but these photochemical catalysts are not very high to the activity of reduction Cr (VI), and reduction process usually requires for a long time.It is another
Aspect, sulfide material may be caused secondary since photoetch is usually insufficient to photocatalyst due to its high toxicity
Pollution.Therefore, it is necessary to explore novel visible active photocatalyst.
The hybridization porous material of one kind that metal-organic framework (MOFs) is made of metal-oxygen cluster and organic structure ele,
It is with a wide range of applications, especially MOFs increasingly attracts attention at present in the application prospect of photocatalysis field.With tradition
Photochemical catalyst compare, MOFs has ideal topological structure and high surface area, also, between the band gap and HOMO-LUMO of MOFs
Gap is closely related, and the gaps HOMO-LUMO can flexibly be adjusted by the rational modification of inorganic unit in building-up process or organic linking
It is whole, to realize effective trapping to visible light.In fact, some MOFs such as titanium, zirconium and iron-based MOF have been demonstrated to urge with light
Change activity, is used for dyestuff degradation, splitting water and carbon dioxide reduction etc..Its main catalytic mechanism is related to photoinduced electron from light
The organic linker of excitation is transferred to the metal-oxide cluster in MOFs and the direct excitation by metal-oxide cluster.Although
It makes great progress so far, but the photocatalysis performance of MOFs is fully played not yet.Especially with respect to application
MOFs is also seldom to the research of photo catalytic reduction Cr (VI), and the recycling and separation of many MOFs photochemical catalysts prepared at present
Ability is not paid attention to, and cost problem also inhibits the research of MOFs photochemical catalysts.
Therefore, it on the basis of the MOFs studied, by the adjustment to organic ligand and metal center atom, prepares high
Visible light-responded MOF photochemical catalysts test the efficient degradation to chromate waste water, have very high researching value.
Invention content
The present invention provides it is a kind of can magnetic recycling Fe base MOF photochemical catalysts preparation method and application, photochemical catalyst
Preparation method is simple, low in raw material price, and photohole and electronics are easily isolated, and the catalyst has certain magnetism,
It can be realized and be separated and recovered by externally-applied magnetic field, there is very high economic benefit.
It is a kind of can magnetic recycling Fe-MOF photochemical catalysts, which is characterized in that there is the atomic ratio that is indicated with formula (I) to form：
[Fe(2-mim)3·nH2O] (Ⅰ)
It is a kind of can magnetic recycling Fe-MOF photochemical catalysts preparation method, include the following steps：
(1) 2-MI is dispersed in methanol, obtains 2-MI solution；By Fe (NO3)3It is dispersed in methanol and obtains Fe3+
Solution；
(2) gained Fe is added dropwise in gained 2-MI solution3+In solution, suspension is stirred and evenly mixed to obtain；
(3) suspension obtains Fe-MOF photochemical catalysts after standing, washing and vacuum drying successively.
One-step method is used to prepare at room temperature, by 2-MI and Fe3+It is dissolved in methanol respectively, after mixing by two kinds of solution
Mixing, makes Fe3+Complexation reaction occurs at room temperature with 2-MI and generates sample, the sample is passed through into washing, drying after standing,
Finally obtained Fe-MOF photochemical catalysts.
The present invention realizes [Fe (2-mim) at room temperature by one-step method3·nH2O] preparation, preparation method is simple, easily
In realization, and with excellent visible light catalysis activity and magnetic recuperability energy.
Preferably, in step (1) 2-MI solution a concentration of 0.1~2mmol/mL, Fe3+The concentration 0.05 of solution~
0.2mmol/mL.It is further preferred that in step (1) 2-MI solution a concentration of 0.8~1.2mmol/mL；Fe3+Solution it is dense
Spend 0.08~0.12mmol/mL；Most preferably, in step (1) 2-MI solution a concentration of 1mmol/mL；Fe3+The concentration of solution
0.1mmol/mL。
Further, the volume fraction for preparing the solvent methanol of 2-MI solution is 99.5%, and mixing time is 30~60 points
Clock；Prepare Fe3+The volume fraction of the solvent methanol of solution is 99.5%, and mixing time is 60~120 minutes.
Preferably, Fe in step (2)3+The mixed proportion of solution and 2-MI solution is with Fe3+It is 1 with 2-MI molar ratios:20~
1:1 meter.It is 60~120 minutes that the time, which is mixed,.
It is further preferred that Fe3+The mixed proportion of solution and 2-MI solution is with Fe3+It is 1 with 2-MI molar ratios:15~1:5
Meter.Most preferably, Fe3+The mixed proportion of solution and 2-MI solution is with Fe3+It is 1 with 2-MI molar ratios:10 meters.
Preferably, time of repose in step (3)>20h, vacuum drying temperature be 60~80 DEG C, drying time be 10~
12h.Washing is washed respectively using ethyl alcohol and water.
A kind of most preferred preparation method, includes the following steps：
(1) 2-MI is dispersed in methanol, obtains 2-MI solution；By Fe (NO3)3It is dispersed in methanol and obtains Fe3+
Solution；A concentration of 1mmol/mL, Fe of 2-MI solution in step (1)3+The concentration 0.1mmol/mL of solution；Fe3+Solution and 2-MI
The mixed proportion of solution is with Fe3+It is 1 with 2-MI molar ratios:10 meters；
(2) gained Fe is added dropwise in gained 2-MI solution3+In solution, stirring 60min mixings obtain suspension；
(3) suspension successively through stand for 24 hours, washing, 10h is dried under the conditions of 80 DEG C of permanent vacuum after Fe-MOF light
Catalyst.
The present invention also provides a kind of Fe-MOF photochemical catalysts being prepared such as the preparation method.
The present invention also provides a kind of methods of degradation Cr containing chromium (VI) waste water, include the following steps：
(1) Fe-MOF photochemical catalysts as claimed in claim 5 are added in pending Cr containing chromium (VI) waste water, in dark place
Stirring opens visible light source, photocatalytic degradation to adsorption equilibrium；
(2) after reaction, add magnetic field to recycle Fe-MOF photochemical catalysts, recycled after washing and drying.
Preferably, the addition of Fe-MOF photochemical catalysts is 0.1~0.5g/L.
Preferably, the pH that waste water is adjusted in step (1) is 2~5, and most preferably, it is 2 to adjust pH.
The object of the present invention is to provide it is a kind of can magnetic recycling Fe bases MOF preparation method and as visible light catalyst at
Manage chromate waste water.Metallic atom centered on Fe is combined by the present invention with 2-MI as organic ligand for the first time, be made have it is visible
The MOFs photochemical catalysts of photoresponse, and relative to common at present Fe bases MOF or the metal centered on other metallic elements
The MOFs photochemical catalysts of atom can advantageously promote electron-hole separation, improve light induced electron quantity, have preferably visible
Photocatalytic activity, and with the magnetism not available for other MOFs photochemical catalysts, preferably can recycle and recycle.
Beneficial effects of the present invention have：
(1) Fe base MOF photochemical catalyst preparation methods of the invention are simple, of low cost；
(2) Fe base MOF photochemical catalysts of the invention have very high visible light activity.
(3) Fe base MOF photochemical catalysts of the invention are easily recycled with magnetism.
Description of the drawings
Fig. 1 is photochemical catalyst [Fe (2-mim) in the present invention3·nH2O] figure that is shot under scanning electron microscope (SEM).
Fig. 2 is the metallic atom centered on Fe in the embodiment of the present invention 2, the MOFs reduction of different organic ligand synthesis
Cr (VI) effect contrast figure.
Fig. 3 is in the embodiment of the present invention 3, and using 2-MI as organic ligand, the MOFs of different central metal atom synthesis is also
Former Cr (VI) effect contrast figure.
Fig. 4 is different Fe in the embodiment of the present invention 43+Cr (VI) effect pair is restored with the Fe bases MOF synthesized under 2-MI ratios
Than figure.
Fig. 5 is in the embodiment of the present invention 5, and Fe bases MOF restores Cr (VI) effect contrast figure under different pH.
Fig. 6 is the cycle performance measurement chart of Fe bases MOF reduction Cr (VI) effects in the embodiment of the present invention 6.
Specific implementation mode
In conjunction with Figure of description and specific embodiment, the present invention is further described.
Raw material used below is commercial goods.
Embodiment 1
MOF photochemical catalysts [Fe (2-mim)3·nH2O] preparation method, steps are as follows：
(1) 40mmol organic ligands 2-MI is dissolved in 50ml methanol solutions, by being mixed 30 minutes or so, is obtained
The methanol solution of uniform 2-MI；
(2) by 4mmol Fe (NO3)3·9H2O is dissolved in 50ml methanol solutions, by being mixed, obtains uniform Fe3+
Fe is added dropwise in the methanol solution of the uniform 2-MI obtained in step (1) by solution3+In solution, it is stirred to react 60 minutes left sides
The right side obtains suspension；
(3) it after standing reaction product made from step (2) more than 20h at room temperature, is carried out respectively by ethyl alcohol and water
Then 10h is dried under the conditions of 80 DEG C of permanent vacuum, finally obtained [Fe (2- in reaction product after washing by washing
mim)3·nH2O] photochemical catalyst.
Fig. 1 is [Fe (2-mim)3·nH2O] figure that is shot under scanning electron microscope (SEM).As can be seen from the figure
[Fe(2-mim)3·nH2O] it is sheet, not of uniform size, structure is than more loose.
Embodiment 2
Different organic ligands and Fe3+The MOFs of the different atoms centered on Fe can be formed.Using it has been reported that
H is respectively adopted by changing organic ligand in method2BDC、NH2-H2BDC and fumaric acid are as organic ligand, with ferric nitrate
(nine hydrations) prepares MOFs.
Catalyst activity is tested by taking Cr containing chromium (VI) waste water of degrading as an example, it is 100mL, concentration that volume is added into reactor
For Fe base MOF visible light catalysts prepared by 10mg different proportions in Cr containing chromium (VI) waste water of 80 μm of ol/L, are added, do not adjust
PH, it is lasting to stir, 30min is stirred to adsorption equilibrium in dark place, opens visible light source, interval 15min samplings.
Such as Fig. 2, prepared by the present invention, which using 2-MI is the Fe bases MOF of organic ligand, has best Visible Light Induced Photocatalytic Cr
(VI) effect, and uniquely there is magnetism.
Embodiment 3
Different central metal atoms can form the MOFs of different central metal atoms from organic ligand 2-MI.With M
(NO3)X(wherein M=Ce, Co, Bi, Fe, Zn) provide central metal atom, using methanol as solvent, using with preparation Fe-MOF
Similar method, one-step method prepare a series of MOFs of different central metal atoms.And the chromium restoring operation of embodiment 2 is pressed, into
Row comparison.
Such as Fig. 3, the Fe bases MOF of metallic atom centered on Fe prepared by the present invention has best Visible Light Induced Photocatalytic Cr
(VI) effect, and uniquely there is magnetism.
Embodiment 4
The molar ratio of adjusting central metal atom and organic ligand can influence the production quantity and generation state of complex, center
Metallic atom Fe3+Deficiency complex formation speed may be caused slow, production quantity is few, causes reduction efficiency not high；Central metal
Atom Fe3+The excessive Fe that can cause to have free again3+, inhibit the generation of Fe bases MOF, so as to cause the efficiency of reduction Cr (VI)
Decline, so we can change in embodiment 1 [Fe (2-mim)3·nH2O] different ligands ratio is adjusted in preparation method, it prepares
Catalyst series, and by the chromium restoring operation of embodiment 2, compared.
Such as Fig. 4, Fe3+Molar ratio with 2-MI is 1:When 10, the reduction effect of Cr (VI) is best, so the Fe prepared3+With
The molar ratio of 2-MI is 1:[Fe (2-mim) 3nH when 102O] photocatalytic activity is best.
Embodiment 5
Different pH can generate large effect to the absorption of MOF photochemical catalysts and photocatalysis effect, at different pH,
State existing for chromium ion is also different.When not adjusting pH, the pH of solution is about 4.64.Prepared by gained to the present invention in order to probe into pH
The influence of catalyst changes the pH of chromium reducing solution in embodiment 2, and it is 2 to adjust pH with 1M sulfuric acid solutions, molten with 1M sodium hydroxides
It is 8 and 10 that liquid, which adjusts pH, and by the chromium restoring operation of embodiment 2, is compared.
Such as Fig. 5, when pH=2, the reduction effect of Cr (VI) is best, and with the raising of pH, MOF light prepared by the present invention
The reduction effect of catalyst continuously decreases.
Embodiment 6
In actual application, the recycling of catalyst and cycle performance are a vital factors.Existing light
Catalyst major part all without good circulating effect and is difficult to recycle.In order to probe into MOF photochemical catalysts prepared by the present invention
It can be recycled outside plus under magnetic field with magnetism, and test the cycle performance restored to chromium, chromium restores in example 2
On the basis of operation, washing and drying repeats the chromium restoring operation in embodiment 2 again after catalyst is recycled, and compares four cycles
Variations of the Fe bases MOF prepared afterwards to chromium reducing property.
Such as Fig. 6, after five times recycle, the reduction effect of Cr (VI) is not decreased obviously, it is believed that Fe bases MOF prepared by the present invention
Photochemical catalyst has good cycle performance, and lasting photocatalytic degradation can be carried out to chromate waste water.
By above example as it can be seen that the Fe base MOF photochemical catalysts that the present invention is prepared have excellent visible light catalytic
Activity.
The foregoing is merely the specific implementation cases of patent of the present invention, but the technical characteristic of patent of the present invention is not limited to
This, any those skilled in the relevant art in the field of the invention, made by changes or modifications all cover the present invention it is special
Among sharp range.
Claims (8)
1. it is a kind of can magnetic recycling Fe-MOF photochemical catalysts, which is characterized in that there is the atomic ratio that is indicated with formula (I) to form：
[Fe(2-mim)3·nH2O] (Ⅰ)。
2. it is a kind of can magnetic recycling Fe-MOF photochemical catalysts preparation method, which is characterized in that include the following steps：
(1) 2-methylimidazole is dispersed in methanol, obtains 2-methylimidazole solution；By Fe (NO3)3It is dispersed in methanol
In Fe3+Solution；
(2) gained Fe is added dropwise in gained 2-methylimidazole solution3+In solution, suspension is stirred and evenly mixed to obtain；
(3) suspension obtains Fe-MOF photochemical catalysts after standing, washing and vacuum drying successively.
3. preparation method according to claim 1, which is characterized in that a concentration of the 0.1 of 2-methylimidazole solution in step (1)
~2mmol/mL, Fe3+0.05~0.2mmol/mL of concentration of solution.
4. preparation method according to claim 1, which is characterized in that Fe in step (2)3+Solution and 2-methylimidazole solution
Mixed proportion is with Fe3+It is 1 with 2-methylimidazole molar ratio:20~1:1 meter.
5. preparation method according to claim 1, which is characterized in that time of repose in step (3)>20h, vacuum drying temperature
It it is 60~80 DEG C, drying time is 10~12h.
6. a kind of Fe-MOF photochemical catalysts that the preparation method as described in any one of Claims 1 to 5 claim is prepared.
The processing method of one kind 7. Cr containing chromium (VI) waste water, which is characterized in that include the following steps：
(1) Fe-MOF photochemical catalysts as claimed in claim 1 or 6 are added in pending Cr containing chromium (VI) waste water, in dark place
Stirring opens visible light source, photocatalytic degradation to adsorption equilibrium；
(2) after reaction, add magnetic field to recycle Fe-MOF photochemical catalysts, recycled after washing and drying.
8. processing method according to claim 7, which is characterized in that the addition of Fe-MOF photochemical catalysts is 0.1~0.5g/
L。
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