CN109718859A - A kind of Ag/TiO2/ MIL-125 (Ti) composite material and preparation method and Morphological control - Google Patents
A kind of Ag/TiO2/ MIL-125 (Ti) composite material and preparation method and Morphological control Download PDFInfo
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Abstract
Present invention firstly provides a kind of silver-titanium dioxide-metallo-organic framework composite material and preparation method and Morphological controls, belong to field of compound material.The composite material is expressed as Ag/TiO2/MIL-125(Ti).This method is the MIL-125 (Ti) for first synthesizing different-shape, determines MIL-125 (Ti) pattern with optimum activity by reduction nitrate.Then in isopropanol solvent be added butyl titanate, silver nitrate, preferably after MIL-125 (Ti) and deionized water be mixed, formation sol-gel, obtain Ag/TiO in conjunction with solvent thermal technology2/ MIL-125 (Ti) composite material.Using the composite material prepared as photocatalyst applications in reduction nitrate, the results showed that the material has good silver nitrate conversion ratio and high nitrogen selective, and it is excellent that performance is recycled.
Description
Technical field
The invention belongs to field of compound material, and in particular to a kind of silver-titanium dioxide-metallo-organic framework composite wood
Expect (Ag/TiO2/ MIL-125 (Ti)) preparation method and Morphological control.
Background technique
With the fast development of China's industry, quantity of wastewater effluent improves increasingly, and azotate pollution is increasingly severe in water body.
Traditional nitrate removal method can generate the nitrites by-product with carcinogenicity during nitrate removal, and deposit
Cost is excessively high, the reaction time is long, transformation efficiency is low, easily causes the disadvantages of secondary pollution, thus it is badly in need of new and effective turn of exploitation
Change the processing technique of the high nitrogen selective of nitrate.Photocatalysis technology has relative to traditional nitrate removal method without secondary dirt
Dye, reaction condition are mild, the advantages of capable of converting nitrogen for the highly selective high conversion of nitrate in water, are expected to become and administer water
Middle azotate pollution provides the scheme of sustainable development.But the quantum efficiency of catalysis material is not high, it is therefore desirable to develop nitre
The highly selective high conversion of hydrochlorate is converted into the catalysis material of nitrogen.
TiO2It is a kind of semiconductor catalysis material cheap and easy to get, nontoxic, chemical property is more stable, due to its forbidden band
Width is larger, hole and electronics be easy it is compound, so its photocatalysis efficiency is lower.In order to further increase TiO2Photocatalysis effect
Rate, many researchers are modified research to it.MIL-125 (Ti) has big specific surface area, regulatable pattern, rule
Cellular structure then, the advantages that modifiability is strong, all have potential application prospect in many fields.On the one hand, specific surface area
Big MIL-125 (Ti) can adsorb Ag and TiO2On its surface, it can provide more reaction active sites using Ag nanoparticle
Point can produce the reaction that more light induced electrons participate in reduction nitrate under ultraviolet excitation；And Ag nanoparticle has
Surface plasmon resonance effect can widen TiO2Spectral absorption range, extend the service life of light induced electron.On the other hand,
MIL-125 (Ti) has not only acted as the effect of carrier, and its skeleton provides way as good conductor for electronics transfer
Diameter promotes TiO2The separation of electrons and holes.The electrons generated in photocatalytic process accelerate reduction reaction, and hole can accelerate
Oxidation reaction, to further generate the stronger COO of reducing power-, improve the efficiency of reduction nitrate.
Currently, using having the MIL-125 (Ti) of regular morphology to prepare Ag/ by sol-gal process combination solvent thermal technology
TiO2/ MIL-125 (Ti) composite material and be applied to photo catalytic reduction nitrate be nitrogen research have not been reported.Design
In terms of the advantage of such catalysis material mainly has following four: the morphology controllable of first, MIL-125 (Ti)；Second, synthesis side
Method is simple, can be by Ag, TiO using sol-gal process2With MIL-125 (Ti) one-step synthesis；Third, the catalysis material can be by nitre
The highly selective high conversion of hydrochlorate is converted into nitrogen；4th, the material circulation service performance is relatively stable.Design such photocatalysis
Material is primarily intended in terms of solving the problems, such as following two: first, improve the efficiency that nitrate transformation is nitrogen；Second, subtract
The nitrites by-product with carcinogenicity is generated during few nitrate removal.
Summary of the invention
The object of the present invention is to provide a kind of Ag/TiO2/ MIL-125 (Ti) composite material and preparation method and pattern tune
Control, the preparation method is simple, and the ratio by changing reactant terephthalic acid (TPA) and butyl titanate prepares the MIL- of different-shape
125 (Ti) prepare a kind of Ag/TiO by sol-gal process combination solvent thermal technology based on the substance2/ MIL-125 (Ti) is compound
Material, can be used as efficient selective photochemical catalyst reduction nitrate is nitrogen.
Present invention firstly provides silver-titanium dioxide-metallo-organic framework composite material of morphology controllable, the composite woods
Material is expressed as Ag/TiO2/MIL-125(Ti)。
Preferably, in the composite material, Ag, TiO2Mass ratio with MIL-125 (Ti) is 10:(4-9): (1-
6)。
The present invention provides a kind of Ag/TiO of morphology controllable2The preparation method of/MIL-125 (Ti) composite material is specific to wrap
It includes:
Step 1: stirring terephthalic acid (TPA) and butyl titanate in n,N-Dimethylformamide and methanol mixed solution,
Mixed solution is formed, the MIL-125 (Ti) of different-shape is obtained；
Step 2: isopropanol is added in MIL-125 (Ti), butyl titanate, silver nitrate and the deionized water that step 1 is obtained
It is mixed in solvent, forms gel, obtain the Ag/TiO of morphology controllable2/ MIL-125 (Ti) composite material.
Preferably, the amount (mole) of the step 1 terephthaldehyde acid substance: the amount (mole) of butyl titanate substance: N,
Dinethylformamide volume (milliliter): methanol volume (milliliter) is (1-9): 1:(20-25): (2-5).
Preferably, the step 2 MIL-125 (Ti) is nitrate transformation in MIL-125 (Ti) material of different-shape
The optimal MIL-125 of efficiency (Ti).
Preferably, the step diisopropanol volume (milliliter): the quality (gram) of MIL-125 (Ti): the matter of silver nitrate
Measure (gram): deionized water volume (milliliter) is (20-25): (0.045-0.45): (0.008-0.078): (0.5-1.0).
Preferably, the stirring rate of the step 2 is 100-200 revs/min.
Preferably, the mixing time of the step 2 is 6-10 hours.
The present invention further has rated the MIL-125 (Ti) and Ag/TiO of above-mentioned different-shape2/ MIL-125 (Ti) is compound
Material selectivity restores the performance that nitrate is nitrogen.
Beneficial effects of the present invention
The present invention provides a kind of Ag/TiO of morphology controllable2The preparation method of/MIL-125 (Ti) composite material.This method
It is that during the preparation process, butyl titanate is dispersed in aqueous isopropanol, silver nitrate is added, after Morphological control then is added
Preferred MIL-125 (Ti) powder is stirred.Wherein, different-shape MIL-125 (Ti) is adjusted during the preparation process to benzene
The molar ratio of dioctyl phthalate and butyl titanate is made.MIL-125 (Ti) big specific surface area is conducive to adsorb butyl titanate, and addition is gone
Ionized water, stirring at low speed gelled state can guarantee that Ag nanoparticle, butyl titanate and the dispersion of MIL-125 (Ti) powder are more equal
It is even, in conjunction with more secured, make composite material that there is the ability of photo catalytic reduction nitrate nitrogen of efficient stable.Meanwhile this
The catalyst raw material of invention is easy to get, and synthesis is simple, save the cost and time.
MIL-125 (Ti) the selective reduction nitrate that the present invention has rated above-mentioned different-shape first is the property of nitrogen
Energy.The results showed that being followed successively by disc-shaped > random particle > square to the conversion ratio sequence of nitrate after illumination 30 minutes
Shape > decahedron.Wherein disc-shaped MIL-125 (Ti) nitrate transformation rate is up to 41.65%, nitrogen selective 98.58%.
So having synthesized Ag/TiO on this basis2/ MIL-125 (Ti) composite material.The present invention also further has rated Ag/TiO2/
MIL-125 (Ti) composite material selective reduction nitrate is the performance of nitrogen.The results showed that after illumination 15 minutes, nitre
Hydrochlorate conversion ratio is 100%, nitrogen selective 99.08%, and only produces less nitrite and ammonia.In addition, Ag/
TiO2After being recycled 3 times, catalytic effect remains unchanged/MIL-125 (Ti), illustrates that it has high stable in use
Property.
Detailed description of the invention
Fig. 1 is different-shape MIL- prepared by the embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5
The transmission electron microscope picture of 125 (Ti) materials.
Fig. 2 is different-shape MIL- prepared by the embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5
125 (Ti) materials nitrate under photocatalysis experimental system changes with time.
Fig. 3 is Ag/TiO prepared by the embodiment of the present invention 62/ MIL-125 (Ti) material nitric acid under photocatalysis experimental system
Salt changes with time.
Fig. 4 is Ag/TiO prepared by the embodiment of the present invention 62/ MIL-125 (Ti) material is continuous under photocatalysis experimental system
The 3 circulating effect figures carried out.
Specific embodiment
The present invention provides a kind of silver-titanium dioxide-metallo-organic framework composite material of morphology controllable, the composite wood
Material is expressed as Ag/TiO2/ MIL-125 (Ti), in the composite material, Ag, TiO2Mass ratio with MIL-125 (Ti) is 10:
(4-9): (1-6).
The present invention provides a kind of Ag/TiO of morphology controllable2The preparation method of/MIL-125 (Ti) composite material is specific to wrap
It includes:
Step 1: stirring terephthalic acid (TPA) and butyl titanate in n,N-Dimethylformamide and methanol mixed solution,
Form mixed solution；
Step 2: the mixed liquor that step 1 is obtained is transferred in reaction kettle, is risen to 2 DEG C/min of rate from room temperature
130-170 DEG C, and kept for 20-28 hours, obtain mixture；
Step 3: the mixture that step 2 is obtained is centrifuged, is washed, is filtered, is dried, and obtains the MIL- of different-shape
125 (Ti), it is spare after grinding；
Step 4: butyl titanate, silver nitrate, MIL-125 (Ti) and deionized water being mixed in isopropanol solvent,
Form gel；
Step 5: the gel that step 4 is obtained is transferred in reaction kettle, is risen to 2 DEG C/min of rate from room temperature
130-150 DEG C, and kept for 8-12 hours, obtain mixture；
Step 6: the mixture that step 5 is obtained is centrifuged, is washed, is filtered, is dried, and obtains the silver-of morphology controllable
Titanium dioxide-metallo-organic framework composite material.
According to the present invention, terephthalic acid (TPA) and butyl titanate are stirred in n,N-Dimethylformamide and methanol mixed solution
It mixes；The raw material addition sequence is preferred are as follows: terephthalic acid (TPA) is first added, adds n,N-Dimethylformamide solution and stirs
It mixes, methanol solution is then added, be eventually adding butyl titanate, obtain yellow transparent shape solution；Terephthaldehyde's acid substance
Amount (mole): the amount (mole) of butyl titanate substance: N,N-dimethylformamide volume (milliliter): methanol volume (milliliter) is
(1-9): 1:(20-25): (2-5).
According to the present invention, solution obtained above is put into reaction kettle, the reaction kettle is preferably polytetrafluoroethylene (PTFE)
Then the reaction kettle of liner rises to 130-170 DEG C, preferably 150 DEG C from room temperature with 2 DEG C/min of speed, and keeps 20-28
Hour, preferably 24 hours, obtain mixture.
According to the present invention, the powder obtained after mixture obtained above is centrifuged preferably uses N, N- dimethyl methyl
Amide and methanol wash 3 times respectively, and by obtained solid, drying 8 is small at drying 6-10 hours, preferably 50 DEG C at 40-60 DEG C
When, obtain the metallo-organic framework material of different-shape.
According to the present invention, butyl titanate and silver nitrate are added in isopropanol solvent and are stirred, is added MIL-125 (Ti)
And deionized water, stir at low speed gelled state；The raw material addition sequence is preferred are as follows: first plus isopropanol solvent, adds
Butyl titanate simultaneously stirs, and silver nitrate, MIL-125 (Ti) is then added, is eventually adding deionized water, and mixing time 6-10 hours,
100-200 revs/min of mixing speed, more preferable 150 revs/min, obtain brown gel；The isopropanol volume (mL):
The quality (gram) of MIL-125 (Ti): the quality (gram) of silver nitrate: deionized water volume (milliliter) is (20-25): (0.045-
0.45): (0.008-0.078): (0.5-1.0).
According to the present invention, mixed liquor obtained above is put into reaction kettle, the reaction kettle is preferably polytetrafluoroethyl-ne
Then the reaction kettle of alkene liner rises to 130-150 DEG C, preferably 140 DEG C from room temperature with 2 DEG C/min of speed, and keeps 8-12
Hour, preferably 10 hours, obtain mixture.
According to the present invention, the powder obtained after mixture obtained above is centrifuged is preferably washed with deionized 2
Secondary obtained powder obtains the silver-two of morphology controllable in dry 8 hours at 5-10 hours, preferably 50 DEG C dry at 40-60 DEG C
Titanium oxide-metallo-organic framework composite material.
According to the present invention, MIL-125 (Ti) material and Ag/TiO of the different-shape2/ MIL-125 (Ti) composite wood
Expect that as photochemical catalyst reduction nitrate be nitrogen method particularly includes:
By 0.20 gram of catalysis material put into 200 milliliters of 100 milligrams of nitrogen/liter nitrate solution in, in dark place stir
To reach adsorption equilibrium, 0.1 mol/L formic acid is added into solution system within 45 minutes, as hole trapping agents, then connects and follow
Ring water-cooling apparatus, then light source is opened, reaction system is irradiated after light stability, in taking out a small amount of sample for a period of time, is passed through
It takes supernatant to be detected after centrifugation, thymol spectrophotometry method, hydrochloride naphthodiamide spectrophotometry and indigo is respectively adopted
The concentration of phenol indigo plant spectrophotometry nitrate, nitrite and ammonia, is measured using ultraviolet-visible spectrophotometer
To analyze nitrate transformation rate and nitrogen selective.
The Ag/TiO of morphology controllable of the invention2The reaction effect of/MIL-125 (Ti) photo catalytic reduction nitrate is excellent
Reason are as follows:
The spectral absorptive capacity of the MIL-125 (Ti) of different-shape is different, the electrons and holes number generated after being excited by light
Amount is different, different so as to cause MIL-125 (Ti) the photo catalytic reduction nitrate effect of different-shape.In synthesis Ag/TiO2/
During MIL-125 (Ti), the MIL-125 (Ti) of large specific surface area can adsorb Ag and TiO2On its surface, Ag nanometers are utilized
Particle can provide more reactivity sites, can produce more light induced electrons under ultraviolet excitation and participates in reduction nitrate
Reaction；And Ag nanoparticle has surface plasmon resonance effect, can widen TiO2Spectral absorption range, extend light
The service life of raw electronics.In addition, MIL-125 (Ti) has not only acted as the effect of carrier, and its skeleton is as good conductor
Electronics transfer provides approach, promotes TiO2The separation of electrons and holes.The electrons generated in photocatalytic process are accelerated also
Original reaction, hole can accelerate oxidation reaction, to further generate the stronger COO of reducing power-, improve reduction nitrate
Efficiency.
Further detailed description is done to the present invention combined with specific embodiments below, raw material involved in embodiment is quotient
Purchase obtains.
Embodiment 1
0.688 gram of terephthalic acid (TPA) is dissolved in 22.5 milliliters of N,N-dimethylformamides and the mixing of 2.5 ml methanols is molten
It in liquid and stirs, stirring rate is 600 revs/min, and 1.5 milliliters of butyl titanate is added in stirring after ten minutes, persistently stirs 30
It is transferred the solution into the reaction kettle containing polytetrafluoroethyllining lining after minute, temperature programming case is put into, with 2 DEG C/min of speed
150 DEG C are risen to from room temperature, and is kept for 24 hours, mixture after cooling is taken out, by solid N, the N- dimethyl after centrifugation
Formamide and methanol wash 3 times respectively, and obtained powder is dried in vacuo 8 hours at 50 DEG C, obtain terephthalic acid (TPA) and metatitanic acid
Butyl ester molar ratio is the random graininess MIL-125 (Ti) (1:1) of 1:1.
MIL-125 (Ti) (1:1) Surface Physical Chemistry property that embodiment 1 obtains are as follows: average pore size: 3.19 nanometers, BET
Specific surface area: 568.19 meters squared per grams, total pore volume: 0.44 cubic centimetre/gram.Hole type: mesoporous.
Embodiment 2
1.375 grams of terephthalic acid (TPA)s are dissolved in 22.5 milliliters of N,N-dimethylformamides and the mixing of 2.5 ml methanols is molten
It in liquid and stirs, stirring rate is 600 revs/min, and 1.5 milliliters of butyl titanate is added in stirring after ten minutes, persistently stirs 30
It is transferred the solution into the reaction kettle containing polytetrafluoroethyllining lining after minute, temperature programming case is put into, with 2 DEG C/min of speed
150 DEG C are risen to from room temperature, and is kept for 24 hours, mixture after cooling is taken out, by solid N, the N- dimethyl after centrifugation
Formamide and methanol wash 3 times respectively, and obtained powder is dried in vacuo 8 hours at 50 DEG C, obtain terephthalic acid (TPA) and metatitanic acid
Butyl ester molar ratio is the disc-shaped MIL-125 (Ti) (2:1) of 2:1.
MIL-125 (Ti) (2:1) Surface Physical Chemistry property that embodiment 2 obtains are as follows: average pore size: 2.92 nanometers, BET
Specific surface area: 885.29 meters squared per grams, total pore volume: 0.48 cubic centimetre/gram.Hole type: mesoporous.
Embodiment 3
2.75 grams of terephthalic acid (TPA)s are dissolved in 22.5 milliliters of N,N-dimethylformamides and 2.5 ml methanol mixed solutions
In and stir, stirring rate is 600 revs/min, and 1.5 milliliters of butyl titanate is added in stirring after ten minutes, persistently stirs 30 points
Transferred the solution into the reaction kettle containing polytetrafluoroethyllining lining after clock, be put into temperature programming case, with 2 DEG C/min of speed from
Room temperature rises to 150 DEG C, and is kept for 24 hours, mixture after cooling is taken out, by solid N, the N- dimethyl methyl after centrifugation
Amide and methanol wash 3 times respectively, and obtained powder is dried in vacuo 8 hours at 50 DEG C, obtain terephthalic acid (TPA) and metatitanic acid fourth
Ester molar ratio is the MIL-125 (Ti) (4:1) of 4:1.
MIL-125 (Ti) (4:1) Surface Physical Chemistry property that embodiment 3 obtains are as follows: average pore size: 3.35 nanometers, BET
Specific surface area: 1146.40 meters squared per grams, total pore volume: 0.64 cubic centimetre/gram.Hole type: mesoporous.
Embodiment 4
4.125 grams of terephthalic acid (TPA)s are dissolved in 22.5 milliliters of N,N-dimethylformamides and the mixing of 2.5 ml methanols is molten
It in liquid and stirs, stirring rate is 600 revs/min, and 1.5 milliliters of butyl titanate is added in stirring after ten minutes, persistently stirs 30
It is transferred the solution into the reaction kettle containing polytetrafluoroethyllining lining after minute, temperature programming case is put into, with 2 DEG C/min of speed
150 DEG C are risen to from room temperature, and is kept for 24 hours, mixture after cooling is taken out, by solid N, the N- dimethyl after centrifugation
Formamide and methanol wash 3 times respectively, and obtained powder is dried in vacuo 8 hours at 50 DEG C, obtain terephthalic acid (TPA) and metatitanic acid
Butyl ester molar ratio is the square block MIL-125 (Ti) (6:1) of 6:1.
MIL-125 (Ti) (6:1) Surface Physical Chemistry property that embodiment 4 obtains are as follows: average pore size: 3.51 nanometers, BET
Specific surface area: 1344.00 meters squared per grams, total pore volume: 0.76 cubic centimetre/gram.Hole type: mesoporous.
Embodiment 5
5.5 grams of terephthalic acid (TPA)s are dissolved in 22.5 milliliters of N,N-dimethylformamides and 2.5 ml methanol mixed solutions
In and stir, stirring rate is 600 revs/min, and 1.5 milliliters of butyl titanate is added in stirring after ten minutes, persistently stirs 30 points
Transferred the solution into the reaction kettle containing polytetrafluoroethyllining lining after clock, be put into temperature programming case, with 2 DEG C/min of speed from
Room temperature rises to 150 DEG C, and is kept for 24 hours, mixture after cooling is taken out, by solid N, the N- dimethyl methyl after centrifugation
Amide and methanol wash 3 times respectively, and obtained powder is dried in vacuo 8 hours at 50 DEG C, obtain terephthalic acid (TPA) and metatitanic acid fourth
Ester molar ratio is the decahedron MIL-125 (Ti) (8:1) of 8:1.
MIL-125 (Ti) (8:1) Surface Physical Chemistry property that embodiment 5 obtains are as follows: average pore size: 3.46 nanometers, BET
Specific surface area: 1168.63 meters squared per grams, total pore volume: 0.56 cubic centimetre/gram.Hole type: mesoporous.
Embodiment 6
1.759,1.563,1.173,0.782 milliliters of butyl titanate is added, in 24 milliliters of isopropanols with stirring rate
It is stirred for 150 revs/min, 0.078 gram of silver nitrate is added, added 0.045,0.090,0.180,0.270 gram of embodiment 2 and make
Standby MIL-125 (Ti), is eventually adding 0.6 ml deionized water, persistently stirs 8 hours into gel.Gel is transferred to later
In reaction kettle containing polytetrafluoroethyllining lining, it is put into temperature programming case, rises to 140 DEG C from room temperature with 2 DEG C/min of speed, and
It is kept for 10 hours, mixture after cooling is taken out, the solid after centrifugation is washed with deionized 2 times, obtained powder exists
It is dried in vacuo 8 hours at 50 DEG C, respectively obtains different TiO2With MIL-125 (Ti) mass ratio be 9:1,4:1,3:2,2:3's
Ag/TiO2/ MIL-125 (Ti) composite material.
The Ag/TiO that embodiment 6 obtains2/ MIL-125 (Ti) (4:1) Surface Physical Chemistry property are as follows: average pore size: 6.62
Nanometer, BET specific surface area: 144.64 meters squared per grams, total pore volume: 0.30 cubic centimetre/gram.Hole type: mesoporous.
By 0.20 gram of embodiment 1-6 prepare photochemical catalyst put into 200 milliliters of 100 milligrams of nitrogen/liter nitrate solution in,
45 minutes are stirred to reach adsorption equilibrium in dark place, and 0.1 mol/L formic acid is added into solution system, as hole trapping agents,
Then circulating water cooling device is connected, then opens light source, reaction system is irradiated after light stability, is taken out at regular intervals few
Sample is measured, takes supernatant to be detected after centrifugation, thymol spectrophotometry method, hydrochloride naphthodiamide light splitting is respectively adopted
The concentration of photometry and indigo spectrophotometry detection nitrate, nitrite and ammonia, uses spectrophotometry
Meter is measured to analyze nitrate transformation rate and nitrogen selective.
Fig. 1 is different-shape MIL- prepared by the embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5
The transmission electron microscope picture of 125 (Ti) materials.Fig. 1 explanation: the molar ratio of terephthalic acid (TPA) and butyl titanate is to MIL-125 (Ti) pattern
Be it is influential, with the increase of terephthalic acid (TPA), the pattern change procedure of MIL-125 (Ti) is " random particle-disk
Shape-square block-decahedron ".
Fig. 2 is different-shape MIL- prepared by the embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5
125 (Ti) materials nitrate under photocatalysis experimental system changes with time.Fig. 2 explanation: the MIL-125 (Ti) of different-shape
Nitrate transformation rate is different, wherein the nitrate transformation rate highest of MIL-125 (Ti) (2:1), and after illumination 30 minutes, nitrate turns
Rate is 41.65%, nitrogen selective 98.58%.
Fig. 3 is the Ag/TiO that the embodiment of the present invention 6 prepares morphology controllable2/ MIL-125 (Ti) material tests body in photocatalysis
It is that lower nitrate changes with time.Fig. 3 explanation: with the increase of light application time, the concentration of nitrate is on a declining curve, wherein
Ag/TiO2The nitrate transformation rate highest of/MIL-125 (Ti) (4:1), after illumination 15 minutes, nitrate transformation rate is 100%,
Nitrogen selective is 99.08%, illustrates that nitrate transformation can be efficiently nitrogen by the material.
Fig. 4 is the Ag/TiO that the embodiment of the present invention 6 prepares morphology controllable2/ MIL-125 (Ti) material tests body in photocatalysis
3 circulating effect figures being carried out continuously under system.Fig. 4 explanation: 3 times continuous circulating effect is relatively stable, the conversion ratio point of nitrate
Not Wei 100%, 100%, 97.61%, nitrogen selective reaches 95% or more.Illustrate that the material circulation service performance is more steady
It is fixed, there is certain practical value.
Claims (7)
1. a kind of silver-titanium dioxide-metallo-organic framework composite material of morphology controllable, the material are expressed as Ag/TiO2/
MIL-125(Ti)。
2. Ag/TiO according to claim 12/ MIL-125 (Ti) composite material, which is characterized in that the composite material
In, Ag, TiO2Mass ratio with MIL-125 (Ti) is 10:(4-9): (1-6).
3. Ag/TiO described in -2 any one according to claim 12The preparation method and pattern of/MIL-125 (Ti) composite material
Regulation characterized by comprising
Step 1: stirring terephthalic acid (TPA) and butyl titanate in n,N-Dimethylformamide and methanol mixed solution, is formed
Mixed solution obtains the MIL-125 (Ti) of different-shape；
Step 2: isopropanol solvent is added in MIL-125 (Ti), butyl titanate, silver nitrate and the deionized water that step 1 is obtained
Middle mixing forms gel, obtains the Ag/TiO of morphology controllable2/ MIL-125 (Ti) composite material.
4. the MIL-125 (Ti) of different-shape according to claim 3, which is characterized in that step a pair of benzene two
The amount (mole) of formic acid substance: the amount (mole) of butyl titanate substance: N,N-dimethylformamide volume (milliliter): methanol volume
(milliliter) is (1-9): 1:(20-25): (2-5).
5. a kind of Ag/TiO of morphology controllable according to claim 32The preparation method of/MIL-125 (Ti) composite material,
It is characterized in that, the step diisopropanol volume (milliliter): the quality (gram) of MIL-125 (Ti): the quality of silver nitrate
(gram): deionized water volume (milliliter) is (20-25): (0.045-0.45): (0.008-0.078): (0.5-1.0).
6. a kind of Ag/TiO of morphology controllable according to claim 32The preparation method of/MIL-125 (Ti) composite material,
It is characterized in that, step two stirring rate is 100-200 revs/min.
7. a kind of Ag/TiO of morphology controllable according to claim 32The preparation method of/MIL-125 (Ti) composite material,
It is characterized in that, step two mixing time is 6-10 hours.
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| CN111686768A (en) * | 2020-06-30 | 2020-09-22 | 大连民族大学 | Photocatalytic reduction of Cr6+MIL-125/Ag/BiOBr composite catalyst, preparation method and application |
| CN112357954A (en) * | 2020-11-13 | 2021-02-12 | 中国科学院合肥物质科学研究院 | Shuttle structure H2Ti5O11·H2Solvothermal synthesis method of O nano material and application of lithium battery electrode material |
| CN114163650A (en) * | 2020-09-11 | 2022-03-11 | 中国科学院大连化学物理研究所 | Metal organic framework material MIL-125 and preparation method and application thereof |
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