CN106824291A - A kind of bismuth molybdate metal organic framework composite photo-catalyst and its preparation and application - Google Patents
A kind of bismuth molybdate metal organic framework composite photo-catalyst and its preparation and application Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 title claims abstract 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 23
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims abstract description 9
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 77
- 239000013291 MIL-100 Substances 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 8
- 229940043267 rhodamine b Drugs 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 210000000988 bone and bone Anatomy 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000004237 Crocus Nutrition 0.000 description 4
- 241000596148 Crocus Species 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 3
- 239000013144 Fe-MIL-100 Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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 belongs to catalysis material technical field, a kind of bismuth molybdate metal organic framework composite photo-catalyst and its preparation and application are disclosed.Methods described is：(1) metal organic framework MIL 100 (Fe) is prepared using hydro-thermal reaction method；(2) MIL 100 (Fe) ultrasonic disperse in absolute ethyl alcohol, is obtained into dispersion liquid；(3) by Bi (NO3)3·5H2O and Na2MoO4·2H2O is dissolved in ethylene glycol, obtains mixed liquor；Mixed liquor is added dropwise in the dispersion liquid of step (2), is stirred, be placed in solvent thermal reaction kettle, hydro-thermal reaction, be centrifuged, washing is dried, and obtains bismuth molybdate metal organic framework composite photo-catalyst.The method of the present invention is simple and easy to apply；Resulting composite photo-catalyst has catalysis activity strong, and stability is strong, repeats the advantages of utilizing, and can be used for the fields such as the photocatalytic degradation of organic matter.
Description
Technical field
The invention belongs to catalysis material technical field, a kind of visible light-responded organic bone of bismuth molybdate-metal is disclosed
Frame composite photo-catalyst (i.e. Bi2MoO6- MIL-100 (Fe) composite photo-catalyst) and preparation method and application.
Background technology
In recent years, as energy crisis and environmental pollution become increasingly conspicuous, Photocatalitic Technique of Semiconductor is dirty in liberation of hydrogen and degraded
Research in dye thing is increasingly valued by people.Develop and exploitation is efficiently mesh with visible light-responded photochemical catalyst
One important subject of preceding photocatalysis field.Bi2MoO6By [Bi2O2]2+Layer and MoO4 2-Layer be staggered to be formed it is similar
The layer structure of sandwich shape, is a kind of visible light-responded photochemical catalyst.It has been investigated that, Bi2MoO6In degradation of contaminant
Aspect shows preferable photocatalytic activity, but has also suffered from relatively low quantum yield and visible absorption in actual applications
The restriction of utilization rate.In order to further improve Bi2MoO6Photocatalysis performance, researchers have done substantial amounts of exploration work,
Including architectural characteristic reasonable in design, doping and other semiconductors couplings etc..Wherein, prepared with other semiconductors couplings compound
Catalyst is a kind of method that can effectively improve photocatalytic activity, therefore, Bi2MoO6The preparation and raising of composite photo-catalyst
Its catalysis activity turns into the emphasis studied in industry.
Metal-organic framework materials MOFS (Metal Organic Frameworks) is by organic linker and metal sun
Ion is combined by being coordinated, and a kind of heterozygosis supra polymer material with regular network mechanism for being formed.MOFs shows excess of export
Specific surface area high and pore volume, open pore structure, homogeneous pore-size distribution, undersaturated metal-complexing, adjustable hole
Structure and surface property, and the thousands of kinds of species that various fit systems are constituted.
Therefore, how metal organic framework to be combined with molybdate and prepare a kind of photochemical catalyst of better performances into
One of direction for people's research.
The content of the invention
Present invention aim to address Bi2MoO6For visible light utilization efficiency is low, the low problem of photocatalytic activity, there is provided a kind of
Visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst (i.e. Bi2MoO6- MIL-100 (Fe) composite photo-catalyst)
And preparation method thereof.
Another object of the present invention is to provide visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst
(i.e. Bi2MoO6- MIL-100 (Fe) composite photo-catalyst) in catalytic degradation organic pollution, answering such as in rhodamine B material
With.
The object of the invention is achieved through the following technical solutions：
A kind of visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst (Bi2MoO6- MIL-100 (Fe) is multiple
Closing light catalyst) preparation method, comprise the following steps：
(1) metal organic framework MIL-100 (Fe) is prepared using hydro-thermal reaction method；
(2) metal organic framework MIL-100 (Fe) ultrasonic disperse in absolute ethyl alcohol, is obtained into dispersion liquid i.e. EtOH-
MIL-100 (Fe) dispersion liquid；
(3) by Bi (NO3)3·5H2O and Na2MoO4·2H2O is dissolved in ethylene glycol, obtains mixed liquor；By mixed liquor dropwise
Add in the dispersion liquid of step (2), stirring is placed in solvent thermal reaction kettle, hydro-thermal reaction, is centrifuged, washing is dried, and obtains molybdenum
Sour bismuth-metal organic framework composite photo-catalyst is Bi2MoO6- MIL-100 (Fe) composite photo-catalyst.
Specifically preparation method is metal organic framework MIL-100 (Fe) described in step (1):By iron powder, 1,3,5- benzene three
Formic acid, nitric acid, hydrofluoric acid and water are added in hydrothermal reaction kettle, carry out hydro-thermal reaction, are washed, and are dried, and obtain metal organic framework
MIL-100(Fe)。
The iron powder, 1,3,5- benzenetricarboxylic acids, nitric acid, hydrofluoric acid and water mol ratio are 1:0.67:2:0.6:277；It is described
The temperature of hydro-thermal reaction is 140~160 DEG C, preferably 150 DEG C；The time of the hydro-thermal reaction is 10~14h, preferably 12h；
The washing refers to alternately to be washed for several times with absolute ethyl alcohol and deionized water；The drying refers to 60~75 DEG C of 10~12h of drying.
MIL-100 (Fe) described in step (2) is (0.2~1.1) g with the mass volume ratio of absolute ethyl alcohol：20mL, preferably
It is (0.2614~1.0455) g：20mL；
Ultrasonic disperse described in step (2) refers to 25~40min of ultrasonic disperse under conditions of frequency is 20~60kHz,
Preferably 30min.
Bi (NO described in step (3)3)3·5H2O and Na2MoO4·2H2The mol ratio of O is 2:1；Bi described in step (3)
(NO3)3·5H2O is 2mmol with the molal volume ratio of ethylene glycol：(15~25) mL, preferably 2mmol：20mL；In step (3)
The ethylene glycol is 20mL with the volume ratio of absolute ethyl alcohol in dispersion liquid：(15~25) mL, preferably 20mL：20mL；
The temperature of solvent thermal reaction described in step (3) is 150~170 DEG C, preferably 160 DEG C；The solvent thermal reaction
Time be 10~24h, preferably 12h；Mixing time described in step (3) is 20~40min, preferably 30min；It is described dry
Dry condition is 60~75 DEG C of 10~12h of drying, and preferably 60 DEG C dry 12h.
Washing described in step (3) refers to alternately to be washed for several times with absolute ethyl alcohol and deionized water.
Bi described in step (3)2MoO6In-MIL-100 (Fe) catalyst the weight/mass percentage composition of MIL-100 (Fe) be 3~
12%.
A kind of visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst is Bi2MoO6- MIL-100 (Fe) is multiple
Closing light catalyst, is prepared by above method.
Above-mentioned bismuth molybdate-metal organic framework composite photo-catalyst is Bi2MoO6- MIL-100 (Fe) composite photo-catalyst exists
Application in catalytic degradation organic pollution, such as rhodamine B material.
Metal-organic framework materials MOFS (Metal Organic Frameworks) is by organic linker and metal sun
Ion is combined by being coordinated, and a kind of heterozygosis supra polymer material with regular network mechanism for being formed.MOFs shows excess of export
Specific surface area high and pore volume, open pore structure, homogeneous pore-size distribution, undersaturated metal-complexing, adjustable hole
Structure and surface property, and the thousands of kinds of species that various fit systems are constituted.Metal organic framework is combined with photochemical catalyst,
The photochemical catalyst of MOFs@semi-conductor types can be prepared, utilization rate of the catalysis to visible ray is improved, promotes the fast of photo-generate electron-hole pair
Speed is separated, while suppress the compound of light induced electron, so as to improve the performance of photochemical catalyst.
Preparation method of the invention and resulting product have the following advantages that and beneficial effect：
(1) preparation process is simple of the invention, environmental protection, it is easy to relatively produce in enormous quantities；
(2) Bi prepared by the present invention2MoO6- MIL-100 (Fe) composite photo-catalyst, can be by adjusting MIL-100 (Fe)
Load capacity is optimal its catalytic performance；
(3) Bi prepared by the present invention2MoO6- MIL-100 (Fe) composite photo-catalysts have preferably degraded to rhodamine B
Effect, has very big exploitation and application prospect in terms of degraded organic dye pollutant under visible light conditions.
Brief description of the drawings
Fig. 1 is the visible light-responded Bi of the gained of embodiment 32MoO6The Electronic Speculum of the composite photo-catalysts of-MIL-100 (Fe) -9 is swept
Tracing；Figure a, b are respectively 50K times and 30K times；
Fig. 2 is the visible light-responded Bi of the gained of embodiment 1~42MoO6- MIL-100 (Fe) composite photo-catalysts and
Bi2MoO6Under visible light to the degradation curve figure of rhodamine B；Bi2MoO6- MIL-100 (Fe) -3~Bi2MoO6-MIL-100
(Fe) -12 embodiment 1~4 is corresponded to respectively.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
(1) hydro-thermal reaction method prepares metal organic framework MIL-100 (Fe)：By iron powder, 1,3,5- benzenetricarboxylic acids, nitric acid,
Hydrofluoric acid and water are according to 1:0.67:2:0.6:It is the hydrothermal reaction kettle of polytetrafluoroethylene (PTFE) that 277 molar ratio adds 50ML liners
In, be put into 150 DEG C of baking ovens and react 12h, product absolute ethyl alcohol and deionized water alternately washing for several times, vacuum is done at 60 DEG C
Dry 12h, obtains crocus solid MIL-100 (Fe)；
(2) step (1) gained 0.2614g MIL-100 (Fe) is taken in 20mL absolute ethyl alcohols, ultrasonic (frequency is 40KHz)
Dispersion 35min forms uniform EtOH-MIL-100 (Fe) dispersion liquid；
(3) Bi is prepared2MoO6- MIL-100 (Fe) composite photo-catalyst：By 2mmol Bi (NO3)3·5H2O and 1mmol
Na2MoO4·2H2O is dissolved in the ethylene glycol of 20mL, and solution is added dropwise over into EtOH-MIL-100 (Fe) dispersion liquid, in room temperature
Lower stirring 30min (speed of agitator is 400rpm), is then transferred to the hydro-thermal that 50ML liners are polytetrafluoroethylene (PTFE) anti-by mixed solution
In answering kettle, it is put into 160 DEG C of baking ovens and reacts 12h, with the centrifugation 3min of 4000r/min, uses ethanol and deionized water respectively
Washing, in vacuum drying chamber 60 DEG C dry 12h, that is, obtain composite photo-catalyst Bi2MoO6- MIL-100 (Fe) -3 is (in reality
Course of reaction in can cause certain loss, therefore MIL-100 (Fe) in composite photo-catalyst Bi2MoO6-MIL-100(Fe)
Middle content is w=3%).
Embodiment 2
(1) hydro-thermal reaction method prepares metal organic framework MIL-100 (Fe)：By iron powder, 1,3,5- benzenetricarboxylic acids, nitric acid,
Hydrofluoric acid and water are according to 1:0.67:2:0.6:It is the hydrothermal reaction kettle of polytetrafluoroethylene (PTFE) that 277 molar ratio adds 50ML liners
In, be put into 150 DEG C of baking ovens and react 12h, product absolute ethyl alcohol and deionized water alternately washing for several times, vacuum is done at 60 DEG C
Dry 12h, obtains crocus solid MIL-100 (Fe)；
(2) step (1) gained 0.5228g MIL-100 (Fe) is taken in 20mL absolute ethyl alcohols, ultrasonic (frequency is 30KHz)
Dispersion 30min forms uniform EtOH-MIL-100 (Fe) dispersion liquid；
(3) Bi is prepared2MoO6- MIL-100 (Fe) composite photo-catalyst：By 2mmol Bi (NO3)3·5H2O and 1mmol
Na2MoO4·2H2O is dissolved in the ethylene glycol of 20mL, and solution is added dropwise over into EtOH-MIL-100 (Fe) dispersion liquid, in room temperature
Lower stirring 30min (rotating speed is 400rpm), is then transferred to the hydrothermal reaction kettle that 50ML liners are polytetrafluoroethylene (PTFE) by mixed solution
In, it is put into 160 DEG C of baking ovens and reacts 12h, washed with the centrifugation 3min of 4000r/min, respectively with ethanol and deionized water,
60 DEG C dry 12h in vacuum drying chamber, that is, obtain composite photo-catalyst Bi2MoO6- MIL-100 (Fe) -6 is (in actual reaction
During can cause certain loss, therefore MIL-100 (Fe) in composite photo-catalyst Bi2MoO6Content in-MIL-100 (Fe)
It is w=6%), it is placed in standby in sample sack.
Embodiment 3
(1) hydro-thermal reaction method prepares metal organic framework MIL-100 (Fe)：By iron powder, 1,3,5- benzenetricarboxylic acids, nitric acid,
Hydrofluoric acid and water are according to 1:0.67:2:0.6:It is the hydrothermal reaction kettle of polytetrafluoroethylene (PTFE) that 277 molar ratio adds 50mL liners
In, be put into 150 DEG C of baking ovens and react 12h, product absolute ethyl alcohol and deionized water alternately washing for several times, vacuum is done at 60 DEG C
Dry 12h, obtains crocus solid MIL-100 (Fe)；
(2) step (1) gained 0.7842g MIL-100 (Fe) is taken in 20mL absolute ethyl alcohols, ultrasonic (frequency is 50KHz)
Dispersion 30min forms uniform EtOH-MIL-100 (Fe) dispersion liquid；
(3) Bi is prepared2MoO6- MIL-100 (Fe) composite photo-catalyst：By 2mmol Bi (NO3)3·5H2O and 1mmol
Na2MoO4·2H2O is dissolved in the ethylene glycol of 20mL, and solution is added dropwise over into EtOH-MIL-100 (Fe) dispersion liquid, in room temperature
Lower stirring 30min (rotating speed is 400rpm), is then transferred to the hydrothermal reaction kettle that 50ML liners are polytetrafluoroethylene (PTFE) by mixed solution
In, it is put into 160 DEG C of baking ovens and reacts 12h, washed with the centrifugation 3min of 4000r/min, respectively with ethanol and deionized water,
60 DEG C dry 12h in vacuum drying chamber, that is, obtain composite photo-catalyst Bi2MoO6- MIL-100 (Fe) -9 is (in actual reaction
During can cause certain loss, therefore MIL-100 (Fe) in composite photo-catalyst Bi2MoO6Content in-MIL-100 (Fe)
It is w=9%).The scanning electron microscope (SEM) photograph of catalyst manufactured in the present embodiment is as shown in Figure 1.
Embodiment 4
(1) hydro-thermal reaction method prepares metal organic framework MIL-100 (Fe)：By iron powder, 1,3,5- benzenetricarboxylic acids, nitric acid,
Hydrofluoric acid and water are according to 1:0.67:2:0.6:It is the hydrothermal reaction kettle of polytetrafluoroethylene (PTFE) that 277 molar ratio adds 50ML liners
In, be put into 150 DEG C of baking ovens and react 12h, product absolute ethyl alcohol and deionized water alternately washing for several times, vacuum is done at 60 DEG C
Dry 12h, obtains crocus solid MIL-100 (Fe)；
(2) step (1) gained 1.0455g MIL-100 (Fe) is taken in 20mL absolute ethyl alcohols, ultrasonic (frequency is 60KHz)
Dispersion 40min, forms uniform EtOH-MIL-100 (Fe) dispersion liquid；
(3) Bi is prepared2MoO6- MIL-100 (Fe) composite photo-catalyst：By 2mmol Bi (NO3)3·5H2O and 1mmol
Na2MoO4·2H2O is dissolved in the ethylene glycol of 20mL, and solution is added dropwise over into EtOH-MIL-100 (Fe) dispersion liquid, in room temperature
Lower stirring 30min (rotating speed is 400rpm), is then transferred to the hydrothermal reaction kettle that 50ML liners are polytetrafluoroethylene (PTFE) by mixed solution
In, it is put into 160 DEG C of baking ovens and reacts 12h, washed with the centrifugation 3min of 4000r/min, respectively with ethanol and deionized water,
60 DEG C dry 12h in vacuum drying chamber, that is, obtain composite photo-catalyst Bi2MoO6- MIL-100 (Fe) -12 is (in the anti-of reality
Certain loss, therefore MIL-100 (Fe) can be caused in composite photo-catalyst Bi during answering2MoO6Contain in-MIL-100 (Fe)
It is w=12% to measure).
The Bi that embodiment 1-4 is obtained2MoO6- MIL-100 (Fe) composite photo-catalyst is used for visible light photocatalytic degradation rhodamine
B, test specific method and condition are as follows：
Photocatalytic activity test is carried out in 100mL quartz reactors.500W atmosphere lamp is used (to be provided with optical filtering for radiating light source
Piece λ >=420nm), reaction solution is the 100mL 10mg/L rhodamine B aqueous solution, adds 0.1g catalyst.Under continuous stirring, first
30min is reacted under dark condition, adsorption equilibrium is reached, 90min is then reacted under light illumination.4mL is extracted every 15min
Reaction solution is centrifuged, and takes supernatant and its absorbance is determined at 554nm.Curve is recorded and draws, as a result as shown in Figure 2.Fig. 2 is real
Apply the visible light-responded Bi of the gained of example 1~42MoO6- MIL-100 (Fe) composite photo-catalysts and Bi2MoO6Under visible light to sieve
The degradation curve figure of red bright B.As shown in Figure 2, as the mass fraction w=9% of MIL-100 (Fe), catalyst is to rhodamine B
Degradation effect is optimal.Therefore, compared to simple Bi2MoO6, Bi prepared by the present invention2MoO6- MIL-100 (Fe) composite photo-catalyst
Catalysis activity significantly increase, there is very big exploitation with application in terms of the organic dye pollutant that will degrade under the visible light conditions
Prospect.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst, it is characterised in that：Bag
Include following steps：
(1) metal organic framework MIL-100 (Fe) is prepared using hydro-thermal reaction method；
(2) metal organic framework MIL-100 (Fe) ultrasonic disperse in absolute ethyl alcohol, is obtained into dispersion liquid i.e. EtOH-MIL-100
(Fe) dispersion liquid；
(3) by Bi (NO3)3·5H2O and Na2MoO4·2H2O is dissolved in ethylene glycol, obtains mixed liquor；Mixed liquor is added dropwise over
In the dispersion liquid of step (2), stirring, be placed in solvent thermal reaction kettle, hydro-thermal reaction, be centrifuged, washing, dry, obtain bismuth molybdate-
Metal organic framework composite photo-catalyst is Bi2MoO6- MIL-100 (Fe) composite photo-catalyst.
2. the preparation method of bismuth molybdate visible light-responded according to claim 1-metal organic framework composite photo-catalyst,
It is characterized in that：MIL-100 (Fe) described in step (2) is (0.2~1.1) g with the mass volume ratio of absolute ethyl alcohol：20mL；
Bi (NO described in step (3)3)3·5H2O and Na2MoO4·2H2The mol ratio of O is 2:1；Bi described in step (3)
(NO3)3·5H2O is 2mmol with the molal volume ratio of ethylene glycol：(15~25) mL；Ethylene glycol and dispersion liquid described in step (3)
The volume ratio of middle absolute ethyl alcohol is 20mL：(15~25) mL.
3. the preparation method of bismuth molybdate visible light-responded according to claim 1-metal organic framework composite photo-catalyst,
It is characterized in that：The temperature of solvent thermal reaction described in step (3) is 150~170 DEG C；The time of the solvent thermal reaction is 10
~24h.
4. the preparation method of bismuth molybdate visible light-responded according to claim 1-metal organic framework composite photo-catalyst,
It is characterized in that：Specifically preparation method is metal organic framework MIL-100 (Fe) described in step (1):By iron powder, 1,3,5- benzene
Tricarboxylic acid, nitric acid, hydrofluoric acid and water are added in hydrothermal reaction kettle, carry out hydro-thermal reaction, are washed, and are dried, and obtain the organic bone of metal
Frame MIL-100 (Fe).
5. the preparation method of bismuth molybdate visible light-responded according to claim 4-metal organic framework composite photo-catalyst,
It is characterized in that：The iron powder, 1,3,5- benzenetricarboxylic acids, nitric acid, hydrofluoric acid and water mol ratio are 1:0.67:2:0.6:277；
The temperature of the hydro-thermal reaction is 140~160 DEG C；The time of the hydro-thermal reaction is 10~14h；
The washing refers to alternately to be washed for several times with absolute ethyl alcohol and deionized water；The drying refer to 60~75 DEG C of dryings 10~
12h。
6. the preparation method of bismuth molybdate visible light-responded according to claim 1-metal organic framework composite photo-catalyst,
It is characterized in that：Ultrasonic disperse described in step (2) refer to frequency be 20~60kHz under conditions of ultrasonic disperse 25~
40min；
Mixing time described in step (3) is 20~40min；The dry condition is 60~75 DEG C of 10~12h of drying；
Washing described in step (3) refers to alternately to be washed for several times with absolute ethyl alcohol and deionized water.
7. the preparation method of bismuth molybdate visible light-responded according to claim 1-metal organic framework composite photo-catalyst,
It is characterized in that：Bi described in step (3)2MoO6The weight/mass percentage composition of MIL-100 (Fe) point in-MIL-100 (Fe) catalyst
Wei 3~12%.
8. a kind of visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst is by any one of claim 1~7
What methods described was prepared.
9. bismuth molybdate visible light-responded according to claim 8-metal organic framework composite photo-catalyst is in catalytic degradation
Application in organic pollution.
10. application according to claim 9, it is characterised in that：The organic pollution is rhodamine B.
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