CN106824291B - 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 46
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 18
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000013291 MIL-100 Substances 0.000 claims abstract description 71
- 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 29
- 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 21
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 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
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 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
- 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
- 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 14
- 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
- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [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
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 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
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 5
- 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
- 229960004756 ethanol Drugs 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000013144 Fe-MIL-100 Substances 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
- 230000000694 effects Effects 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
- 239000000203 mixture Substances 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
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 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
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000003912 environmental pollution 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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
- B01J31/26—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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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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.The method are as follows: (1) metal organic framework MIL-100 (Fe) is prepared using hydro-thermal reaction method；(2) MIL-100 (Fe) ultrasonic disperse in dehydrated 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), stirs, be placed in solvent thermal reaction kettle, hydro-thermal reaction, be centrifuged, washed, it is dry, obtain bismuth molybdate-metal organic framework composite photo-catalyst.Method of the invention is simple and easy；The advantages that obtained composite photo-catalyst has catalytic activity strong, and stability is strong, reusable, can be used for the fields such as the photocatalytic degradation of organic matter.
Description
Technical field
The invention belongs to catalysis material technical fields, disclose a kind of visible light-responded organic bone of bismuth molybdate-metal
Frame composite photo-catalyst (i.e. Bi2MoO6- MIL-100 (Fe) composite photo-catalyst) and preparation method and application.
Background technique
In recent years, as energy crisis and environmental pollution become increasingly conspicuous, Photocatalitic Technique of Semiconductor is dirty in liberation of hydrogen and degradation
Research in dye object is increasingly valued by people.It develops 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 lower quantum yield and visible absorption in practical applications
The restriction of utilization rate.In order to further increase Bi2MoO6Photocatalysis performance, researchers have done a large amount of exploration work,
Including designing reasonable architectural characteristic, doping and other semiconductors couplings etc..Wherein, it is 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 catalytic activity becomes the emphasis studied in industry.
Metal-organic framework materials MOFS (Metal Organic Frameworks) is by organic linker and metal sun
Ion is combined by coordination, and a kind of heterozygosis supra polymer material with regular network mechanism formed.MOFs shows excess of export
High specific surface area and Kong Rong, open pore structure, uniform pore-size distribution, the coordination of unsaturated metal, adjustable hole
Thousands of kinds of types of structure and surface property and a variety of fit systems composition.
Therefore, how metal organic framework in conjunction with molybdate and to be prepared the photochemical catalysts of better performances a kind of and had become
For one of the direction of people's research.
Summary of the invention
Present invention aim to address Bi2MoO6For the problems such as visible light utilization efficiency is low, photocatalytic activity is low, one kind is provided
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-catalysts
(i.e. Bi2MoO6- MIL-100 (Fe) composite photo-catalyst) answering in catalytic degradation organic pollutant, such as rhodamine B substance
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
Light combination catalyst) preparation method, comprising 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 dehydrated 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；Dropwise by mixed liquor
It being added in the dispersion liquid of step (2), stirring is placed in solvent thermal reaction kettle, hydro-thermal reaction, is centrifuged, and is washed, and it is dry, obtain molybdenum
Sour bismuth-metal organic framework composite photo-catalyst, that is, Bi2MoO6- MIL-100 (Fe) composite photo-catalyst.
Metal organic framework MIL-100 (Fe) described in step (1) is specific the preparation method comprises the following steps: 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, wash, dry, obtain metal organic framework
MIL-100(Fe)。
The iron powder, 1,3,5- benzenetricarboxylic acid, nitric acid, hydrofluoric acid and water molar 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 is washed for several times with dehydrated alcohol and deionized water；The drying refers to 60~75 DEG C of dry 10~12h.
The mass volume ratio of MIL-100 (Fe) described in step (2) and dehydrated alcohol is (0.2~1.1) g:20mL, preferably
For (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 molar ratio of O is 2:1；Bi described in step (3)
(NO3)3·5H2The molal volume of O and ethylene glycol ratio is 2mmol:(15~25) mL, preferably 2mmol:20mL；In step (3)
The volume ratio of dehydrated alcohol is 20mL:(15~25 in the ethylene glycol and dispersion liquid) 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~for 24 hours, 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 dry 10~12h, preferably 60 DEG C dry 12h.
Washing described in step (3) refers to alternately is washed for several times with dehydrated alcohol and deionized water.
Bi described in step (3)2MoO6In-MIL-100 (Fe) catalyst the mass percentage of MIL-100 (Fe) be 3~
12%.
A kind of visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst, that is, Bi2MoO6- MIL-100 (Fe) is multiple
Light combination catalyst, is prepared by above method.
Above-mentioned bismuth molybdate-metal organic framework composite photo-catalyst, that is, Bi2MoO6- MIL-100 (Fe) composite photo-catalyst exists
Application in catalytic degradation organic pollutant, such as rhodamine B substance.
Metal-organic framework materials MOFS (Metal Organic Frameworks) is by organic linker and metal sun
Ion is combined by coordination, and a kind of heterozygosis supra polymer material with regular network mechanism formed.MOFs shows excess of export
High specific surface area and Kong Rong, open pore structure, uniform pore-size distribution, the coordination of unsaturated metal, adjustable hole
Thousands of kinds of types of structure and surface property and a variety of fit systems composition.Metal organic framework is compound with photochemical catalyst,
The photochemical catalyst of MOFs@semi-conductor type can be prepared, catalysis is improved to the utilization rate of visible light, promotes the fast of photo-generate electron-hole pairs
Speed separation, while inhibiting the compound of light induced electron, to improve the performance of photochemical catalyst.
Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
(1) preparation process of the invention is simple and environmentally-friendly, 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-catalyst has preferable degradation to rhodamine B
Effect has very big exploitation and application prospect in terms of degradation organic dye pollutant under visible light conditions.
Detailed description of the invention
Fig. 1 is the visible light-responded Bi of 3 gained of embodiment2MoO6The Electronic Speculum of -9 composite photo-catalyst of-MIL-100 (Fe) is swept
Tracing；Scheming a, b is respectively 50K times and 30K times；
Fig. 2 is Bi visible light-responded obtained by Examples 1 to 42MoO6- MIL-100 (Fe) composite photo-catalyst and
Bi2MoO6Under visible light to the degradation curve figure of rhodamine B；Bi2MoO6- MIL-100 (Fe) -3~Bi2MoO6-MIL-100
(Fe) -12 Examples 1 to 4 is respectively corresponded.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) hydro-thermal reaction method prepares metal organic framework MIL-100 (Fe): by iron powder, 1,3,5- benzenetricarboxylic acid, nitric acid,
The hydrothermal reaction kettle that 50ML liner is polytetrafluoroethylene (PTFE) is added according to the molar ratio of 1:0.67:2:0.6:277 for hydrofluoric acid and water
In, it is put into 150 DEG C of baking ovens and reacts 12h, alternately for several times, vacuum is dry at 60 DEG C for washing for product dehydrated alcohol and deionized water
Dry 12h obtains crocus solid MIL-100 (Fe)；
(2) take 0.2614g MIL-100 (Fe) obtained by step (1) in 20mL dehydrated alcohol, ultrasonic (frequency 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 EtOH-MIL-100 (Fe) dispersion liquid is added dropwise in solution, in room temperature
Then it is anti-to be transferred to the hydro-thermal that 50ML liner is polytetrafluoroethylene (PTFE) by lower stirring 30min (speed of agitator 400rpm) for mixed solution
It answers in kettle, is put into 160 DEG C of baking ovens and reacts 12h, with the speed centrifugation 3min of 4000r/min, use ethyl alcohol and deionized water respectively
Washing, in a vacuum drying oven 60 DEG C of dry 12h, i.e. acquisition composite photo-catalyst Bi2MoO6- MIL-100 (Fe) -3 is (in reality
Reaction process in will cause certain loss, therefore MIL-100 (Fe) is 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 acid, nitric acid,
The hydrothermal reaction kettle that 50ML liner is polytetrafluoroethylene (PTFE) is added according to the molar ratio of 1:0.67:2:0.6:277 for hydrofluoric acid and water
In, it is put into 150 DEG C of baking ovens and reacts 12h, alternately for several times, vacuum is dry at 60 DEG C for washing for product dehydrated alcohol and deionized water
Dry 12h obtains crocus solid MIL-100 (Fe)；
(2) take 0.5228g MIL-100 (Fe) obtained by step (1) in 20mL dehydrated alcohol, ultrasonic (frequency 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 EtOH-MIL-100 (Fe) dispersion liquid is added dropwise in solution, in room temperature
Then mixed solution is transferred to the hydrothermal reaction kettle that 50ML liner is polytetrafluoroethylene (PTFE) by lower stirring 30min (revolving speed 400rpm)
In, it is put into 160 DEG C of baking ovens and reacts 12h, washed with the speed centrifugation 3min of 4000r/min, respectively with ethyl alcohol and deionized water,
60 DEG C of dry 12h in a vacuum drying oven, i.e. acquisition composite photo-catalyst Bi2MoO6- MIL-100 (Fe) -6 is (in actual reaction
It will cause certain loss in the process, therefore MIL-100 (Fe) is in composite photo-catalyst Bi2MoO6Content in-MIL-100 (Fe)
For w=6%), it is placed in spare in sample sack.
Embodiment 3
(1) hydro-thermal reaction method prepares metal organic framework MIL-100 (Fe): by iron powder, 1,3,5- benzenetricarboxylic acid, nitric acid,
The hydrothermal reaction kettle that 50mL liner is polytetrafluoroethylene (PTFE) is added according to the molar ratio of 1:0.67:2:0.6:277 for hydrofluoric acid and water
In, it is put into 150 DEG C of baking ovens and reacts 12h, alternately for several times, vacuum is dry at 60 DEG C for washing for product dehydrated alcohol and deionized water
Dry 12h obtains crocus solid MIL-100 (Fe)；
(2) take 0.7842g MIL-100 (Fe) obtained by step (1) in 20mL dehydrated alcohol, ultrasonic (frequency 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 EtOH-MIL-100 (Fe) dispersion liquid is added dropwise in solution, in room temperature
Then mixed solution is transferred to the hydrothermal reaction kettle that 50ML liner is polytetrafluoroethylene (PTFE) by lower stirring 30min (revolving speed 400rpm)
In, it is put into 160 DEG C of baking ovens and reacts 12h, washed with the speed centrifugation 3min of 4000r/min, respectively with ethyl alcohol and deionized water,
60 DEG C of dry 12h in a vacuum drying oven, i.e. acquisition composite photo-catalyst Bi2MoO6- MIL-100 (Fe) -9 is (in actual reaction
It will cause certain loss in the process, therefore MIL-100 (Fe) is in composite photo-catalyst Bi2MoO6Content in-MIL-100 (Fe)
For 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 acid, nitric acid,
The hydrothermal reaction kettle that 50ML liner is polytetrafluoroethylene (PTFE) is added according to the molar ratio of 1:0.67:2:0.6:277 for hydrofluoric acid and water
In, it is put into 150 DEG C of baking ovens and reacts 12h, alternately for several times, vacuum is dry at 60 DEG C for washing for product dehydrated alcohol and deionized water
Dry 12h obtains crocus solid MIL-100 (Fe)；
(2) take 1.0455g MIL-100 (Fe) obtained by step (1) in 20mL dehydrated alcohol, ultrasonic (frequency 60KHz)
Disperse 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 EtOH-MIL-100 (Fe) dispersion liquid is added dropwise in solution, in room temperature
Then mixed solution is transferred to the hydrothermal reaction kettle that 50ML liner is polytetrafluoroethylene (PTFE) by lower stirring 30min (revolving speed 400rpm)
In, it is put into 160 DEG C of baking ovens and reacts 12h, washed with the speed centrifugation 3min of 4000r/min, respectively with ethyl alcohol and deionized water,
60 DEG C of dry 12h in a vacuum drying oven, i.e. acquisition composite photo-catalyst Bi2MoO6- MIL-100 (Fe) -12 is (actual anti-
Certain loss should be will cause in the process, therefore MIL-100 (Fe) is in composite photo-catalyst Bi2MoO6Contain in-MIL-100 (Fe)
Amount is w=12%).
The Bi that embodiment 1-4 is obtained2MoO6- MIL-100 (Fe) composite photo-catalyst is used for visible light photocatalytic degradation rhodamine
B tests specific method and condition is as follows:
Photocatalytic activity test carries out in 100mL quartz reactor.500W atmosphere lamp is used (to be equipped with and filter for radiating light source
Piece λ >=420nm), reaction solution is 100mL 10mg/L rhodamine B aqueous solution, and 0.1g catalyst is added.Under continuous stirring, first
30min is reacted under dark condition, adsorption equilibrium is reached, then reacts 90min under light illumination.4mL is extracted every 15min
Reaction solution centrifugation, takes supernatant to measure its absorbance 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 1~4 gained of example2MoO6- MIL-100 (Fe) composite photo-catalyst 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 best.Therefore, simple Bi is compared2MoO6, Bi prepared by the present invention2MoO6- MIL-100 (Fe) composite photo-catalyst
Catalytic activity significantly increase, will under visible light conditions degrade organic dye pollutant in terms of have very big exploitation and application
Prospect.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst preparation method, it is characterised in that: packet
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 dehydrated 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；Step is added dropwise in mixed liquor
Suddenly in the dispersion liquid of (2), stirring is placed in solvent thermal reaction kettle, hydro-thermal reaction, is centrifuged, and is washed, dry, obtains bismuth molybdate-gold
Belong to organic backbone composite photo-catalyst, that is, Bi2MoO6- MIL-100 (Fe) composite photo-catalyst；
The mass volume ratio of MIL-100 (Fe) described in step (2) and dehydrated alcohol is (0.2 ~ 1.1) g:20 mL；
Bi (NO described in step (3)3)3∙5H2O and Na2MoO4∙2H2The molar ratio of O is 2:1；Bi (NO described in step (3)3)3∙
5H2The molal volume of O and ethylene glycol ratio is 2mmol:(15 ~ 25) mL；Anhydrous second in ethylene glycol described in step (3) and dispersion liquid
The volume ratio of alcohol is 20mL:(15 ~ 25) mL；
The temperature of solvent thermal reaction described in step (3) is 150 ~ 170 DEG C；The time of the solvent thermal reaction be 10 ~ for 24 hours.
2. visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst preparation method according to claim 1,
It is characterized by: metal organic framework MIL-100 (Fe) described in step (1) is specific the preparation method comprises the following steps: by iron powder, 1,3,5-
Benzenetricarboxylic acid, nitric acid, hydrofluoric acid and water are added in hydrothermal reaction kettle, carry out hydro-thermal reaction, wash, dry, and it is organic to obtain metal
Skeleton MIL-100 (Fe).
3. visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst preparation method according to claim 2,
It is characterized by: the iron powder, 1,3,5- benzenetricarboxylic acid, nitric acid, hydrofluoric acid and water molar 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 is washed for several times with dehydrated alcohol and deionized water；The drying refer to 60 ~ 75 DEG C of dryings 10 ~
12h。
4. visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst preparation method according to claim 1,
It is characterized by: ultrasonic disperse described in step (2) refers to 25 ~ 40min of ultrasonic disperse under conditions of frequency is 20 ~ 60kHz；
Mixing time described in step (3) is 20 ~ 40min；The condition of the drying is 60 ~ 75 DEG C of dry 10 ~ 12h；
Washing described in step (3) refers to alternately is washed for several times with dehydrated alcohol and deionized water.
5. visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst preparation method according to claim 1,
It is characterized by: Bi described in step (3)2MoO6The mass percentage of MIL-100 (Fe) point in-MIL-100 (Fe) catalyst
It Wei 3 ~ 12%.
6. a kind of visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst is by any one of claim 1 ~ 5
What the method was prepared.
7. visible light-responded bismuth molybdate-metal organic framework composite photo-catalyst is in catalytic degradation according to claim 6
Application in organic pollutant.
8. application according to claim 7, it is characterised in that: the organic pollutant is rhodamine B.
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| CN109420527A (en) * | 2017-08-22 | 2019-03-05 | 南京理工大学 | Bismuth molybdate/metal organic frame composite photo-catalyst and its preparation method and application |
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| CN113234230B (en) * | 2021-05-08 | 2022-02-11 | 江南大学 | Biocompatible MOF crystal material, composite material, preparation and application |
| CN113289685B (en) * | 2021-05-18 | 2022-12-09 | 深圳大学 | Bismuth molybdate/modified MIL-88A-Fe composite photocatalyst and preparation method thereof |
| CN113546688B (en) * | 2021-07-23 | 2022-07-05 | 江南大学 | Bi-MOF-M/Bi for efficiently degrading organic wastewater2MoO6Visible light catalyst and preparation method thereof |
| CN114029090B (en) * | 2021-12-17 | 2023-11-03 | 中国矿业大学 | Preparation method of photocatalyst for removing heavy metals in sewage |
| CN114210371B (en) * | 2021-12-30 | 2024-05-07 | 合肥学院 | Preparation method and application of bismuth molybdate-metal organic framework composite catalyst |
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