CN109529934A - MIL-101 loaded catalyst and the preparation method and application thereof - Google Patents
MIL-101 loaded catalyst and the preparation method and application thereof Download PDFInfo
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- CN109529934A CN109529934A CN201811485075.8A CN201811485075A CN109529934A CN 109529934 A CN109529934 A CN 109529934A CN 201811485075 A CN201811485075 A CN 201811485075A CN 109529934 A CN109529934 A CN 109529934A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
Abstract
The present invention relates to a kind of MIL-101 loaded catalysts and the preparation method and application thereof, catalytic activity transition metal ions is carried on MIL-101 by the preparation method, this method is simple and easy, the catalyst activity of preparation is high, it is applied in phenol hydroxylation catalysis reaction, phenol conversion can reach 61.2%, and catechol selectively can reach 94.6%.
Description
Technical field
The present invention relates to catalyst field, more particularly to a kind of MIL-101 loaded catalyst and preparation method thereof with
Using.
Background technique
Benzenediol (catechol and hydroquinone) is important organic intermediate, and added value is high, widely used.Adjacent benzene two
Phenol is the important organic intermediate of synthetic pesticide, medicine, fragrance etc., it may also be used for production dyestuff, photosensitive material, plated material,
Extraordinary ink, auxiliary agent etc..Hydroquinone is important industrial chemicals, is mainly used for developer, anthraquinone dye, azo dyes, conjunction
Ammonification cosolvent, rubber antioxidant, polymerization inhibitor, coating and essence stabilizer, antioxidant.The production technology of traditional benzenediol
Complexity, by-product is more, has been eliminated mostly, and hydrogen peroxide direct oxidation phenol is now mostly used to generate the technique of benzenediol.The technique
Process is simple, and reaction condition is mild, and hydrogen peroxide is inexpensive, and oxidized byproduct is water, and no pollution to the environment meets Green Chemistry
Requirement.The exploitation of green catalysis phenol hydroxylation focuses on developing and develop the phenol hydroxyl that preparation is simple, catalytic activity is high
Base catalyst.However, that there are catalytic activity is lower, catechol selectivity is not high asks for traditional phenyl hydroxylating catalyst
Topic.
Summary of the invention
Based on this, the present invention provides a kind of MIL-101 loaded catalyst and the preparation method and application thereof, to solve tradition
Phenyl hydroxylating catalyst existing for catalytic activity is lower, catechol selectivity is not high problem.
A kind of preparation method of MIL-101 loaded catalyst, which comprises the following steps:
Take transition metal salt to be dissolved in ethyl alcohol, be added MIL-101, after being stirred, be dried to get；
Wherein, the volume ratio of MIL-101 and ethyl alcohol is 1:(0.8~1.5), the metal ion choosing in the transition metal salt
From at least one of iron ion, ferrous ion, copper ion and nickel ion.
MIL-101 is 6 to surpass the secondary of tetrahedron (ST) by ligand and trivalent metal core Cr3O (CO2) of terephthalic acid (TPA) and tie
Structure unit has three-dimensional open-framework complex by what hydrothermal synthesis method synthesized.Wherein, Cr3+ ion is in octahedron
Environment in, each octahedral crystal by 1 Cr3+ ion and 4 terephthalic acid (TPA)s O atom, 1 shared O and 1
F (or O in H2O) composition in HF.Be joined together to form 4 octahedrons by terephthaldehyde's acid molecule three
Aggressiveness, combination form big tetrahedral structure, and multiple big tetrahedrons are connected further through shared oxygen atom, form big caged knot
The aperture of structure, resulting cage structure hole reaches mesoporous range.The three-dimensional open-framework of MIL-101 is similar to a cage
Son, there are two types of the internal gutter sizes of cage, is respectivelyWithAnd there is the internal diameter to be outside cage respectivelyFive jiaos
Shape window andHexagonal window openings.The framework material of macropore range, specific surface area is huge, and cell volume is super
It crossesAnd its chemical stability and good thermal stability, thermal stable temperature are highly suitable as urging close to 250 DEG C
Agent carrier.Highly active catalytic benzene is prepared by the way that catalytic activity transition metal ions to be carried on MIL-101 in the present invention
The catalyst of phenolic hydroxyl group.
In one of the embodiments, in the transition metal salt metal ion quality be the transition metal salt with
The 0.5%~10% of the quality sum of MIL-101.
The volume ratio of MIL-101 and ethyl alcohol is 1:(1~1.2 in one of the embodiments).
The drying process is vacuum drying 1h~3h at 60 DEG C~90 DEG C in one of the embodiments,.
The drying process is dry under the conditions of postcritical in one of the embodiments,.
Drying includes: under the conditions of postcritical described in one of the embodiments,
Ethyl alcohol is added into reaction kettle, by the mixture being stirred be placed in the reaction kettle liquid level it
On, after being passed through protective gas discharge air, the overcritical value of increasing temperature and pressure to ethyl alcohol, heat-insulation pressure keeping 0.5h~2h；Temperature is maintained,
Pressure release is passed through protective gas purging 0.5h~2h, cools down, discharge to normal pressure.
MIL-101 is to be made by the steps to obtain in one of the embodiments:
It takes terephthalic acid (TPA) to be added in chromium nitrate solution, hydrofluoric acid is added, is stirred to react, the mixed liquor after reaction is carried out
Ultrasonic treatment, is warming up to 200 DEG C~220 DEG C insulation reactions, reaction product is filtered, wash, is dried.
The molar ratio of terephthalic acid (TPA) and chromic nitrate is 1:(0.9~1.1 in one of the embodiments).
The time of the insulation reaction is 7h~9h in one of the embodiments,.
The present invention also provides a kind of MIL-101 supported catalysts that the preparation method by any of the above-described embodiment is prepared
Agent.
The present invention also provides application of the MIL-101 loaded catalyst in catalysis of phenol hydroxylating.
Compared with prior art, the invention has the following advantages:
Catalytic activity transition metal ions is carried on MIL-101 by the preparation method of above-mentioned MIL-101 loaded catalyst
On, this method is simple and easy, and the catalyst activity of preparation is high.
Above-mentioned MIL-101 loaded catalyst is applied in phenol hydroxylation catalysis reaction, phenol conversion can reach
61.2%, catechol selectively can reach 94.6%.
Detailed description of the invention
Fig. 1 is the SEM figure of MIL-101 loaded catalyst prepared by embodiment 1；
Fig. 2 is the XRD test chart of MIL-101 loaded catalyst prepared by embodiment 1.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give presently preferred embodiments of the present invention.But the invention can be realized in many different forms, however it is not limited to this paper institute
The embodiment of description.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more thorough
Comprehensively.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
The preparation method of the MIL-101 loaded catalyst of one embodiment of the invention, comprising the following steps:
Take transition metal salt to be dissolved in ethyl alcohol, be added MIL-101, after being stirred, be dried to get.
Wherein, the volume ratio of MIL-101 and ethyl alcohol is 1:(0.8~1.5).Metal ion in transition metal salt is selected from iron
Ion (Fe3+), ferrous ion (Fe2+), copper ion (Cu2+) and nickel ion (Ni2+At least one of).
At least one of nitrate, sulfate can be selected in transition metal salt.
In a wherein example, the quality of metal ion is transition metal salt and MIL-101 mass in transition metal salt
The sum of 0.5%~10%.Further, in a wherein example, the quality of metal ion is transition gold in transition metal salt
Belong to the 2%~4% of salt and MIL-101 quality sum, can get higher phenol conversion in phenol hydroxylation catalytic process.
In a wherein example, the volume ratio of MIL-101 and ethyl alcohol is 1:(1~1.2).
In a wherein example, the method for drying process is that 1h~3h is dried in vacuo at 60 DEG C~90 DEG C.
In another example, the method for drying process is supercritical drying.Further, supercritical drying can by with
Lower step carries out: ethyl alcohol being added into reaction kettle, the mixture being stirred is placed in reaction kettle on liquid level, leads to
After entering protective gas discharge air, the overcritical value (such as 250 DEG C, 7.1MPa) of increasing temperature and pressure to ethyl alcohol, heat-insulation pressure keeping 0.5h~
2h；Temperature is maintained, pressure release to normal pressure is passed through protective gas purging 0.5h~2h, cools down, discharging.
The cellular structure that can keep MIL-101 well by above-mentioned supercritical drying drying method, is conducive to catalyst
Active raising.
In a wherein example, MIL-101 is prepared by method comprising the following steps:
Take terephthalic acid (TPA) (H2BDC it) is added in chromium nitrate solution, hydrofluoric acid is added, is stirred to react, to mixed after reaction
It closes liquid to be ultrasonically treated, is warming up to 200 DEG C~220 DEG C insulation reactions, reaction product is filtered, wash, is dried.
In a more specific example, Cr (NO is taken3)3·9H2O is placed in a beaker, and a certain amount of deionized water is added and stirs
Mix dissolution, Cr (NO3)3·9H2O and the mass ratio of deionized water are 1:(10~15).It will be by H2It is molten that BDC is slowly added to chromic nitrate
In liquid, stirring is allowed to uniformly mix；The molar ratio of terephthalic acid (TPA) and chromic nitrate is 1:(0.9~1.1).It is slow added into certain
The hydrofluoric acid of amount, stirring are allowed to uniformly mix, and continue to stir 15min.The mass ratio of deionized water and hydrofluoric acid is 1:(0.001
~0.02).
In this example, the time of ultrasonic treatment is 10~20min, and the time of insulation reaction is 7h~9h.The side of washing
Method is that the product of suction filtration is first washed with deionized water to unreacted chromic salts and is dissolved in the by-product of water, then washes away product with DMF
In H2BDC, then dehydrated alcohol wash away extra DMF, and remaining dehydrated alcohol passes through dry removal.
Further, the present invention also provides a kind of MIL-101 support types obtained by any of the above-described exemplary preparation method
Catalyst.
Further, the application the present invention also provides above-mentioned MIL-101 loaded catalyst in catalysis of phenol hydroxylating.
Specifically, the application method the following steps are included:
Above-mentioned MIL-101 loaded catalyst, phenol, hydrogen peroxide and deionized water mixing are taken, at 70 DEG C~90 DEG C
1~3h is reacted, filtering is extracted filtrate using extractant, phenol and benzenediol content in analytical extraction object.
Wherein, the mass ratio of MIL-101 loaded catalyst and phenol is 1:(7~9).Concentration of hydrogen peroxide be 25%~
35%, the volume ratio of phenol and hydrogen peroxide is 1:(14~16).The volume ratio of phenol and deionized water is 1:(28~32).Extraction
Agent is taken to be selected from least one of ethyl acetate, chloroform and carbon tetrachloride.
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
(1) preparation of MIL-101:
Weigh 3.2022g (8mmol) Cr (NO3)3·9H2O is placed in beaker, and the stirring of 50mL deionized water is added and is allowed to molten
Solution.Weigh 1.3304g (8mmol) H2BDC (terephthalic acid (TPA)), is slowly added to Cr (NO3)3In solution, stirring is allowed to uniformly mixed
It closes.After 0.25mL hydrofluoric acid is added, continue to stir 15min.Beaker is transferred to ultrasonic disperse 15min in ultrasonic cleaner,
It is transferred in autoclave polytetrafluoroethyllining lining.Autoclave is placed in high temperature furnace, is warming up to by room temperature 80min
220 DEG C, room temperature is down to after keeping the temperature 8h.Polytetrafluoroethyllining lining generation has blackish green MIL-101 and unreacted H2BDC white is brilliant
Body etc..
(2) purifying of MIL-101:
Polytetrafluoroethyllining lining is taken out from autoclave, is filtered product, is obtained with the blackish green of white needle-like crystals
Color crystal.Product is rinsed three times with deionized water, with the by-product for removing unreacted chromic salts He being dissolved in water.Successively use DMF, nothing
Water-ethanol cleans product, removes H in product respectively2BDC and extra DMF.The MIL-101 cleaned up in 150 DEG C of dryings
It is dried overnight in case, removes ethyl alcohol, sealing is stand-by.
(3) load of catalytic active site:
Take Fe (NO3)3·9H2O is added to absolute ethanol, and at room temperature after stirring and dissolving, 5g MIL-101 is added to solution
In.Wherein, the volume of dehydrated alcohol is identical as the volume of 5g MIL-101, and the quality of iron ion is Fe (NO3)3·9H2O and
The 3% of MIL-101 quality sum.After being thoroughly mixed, at 70 DEG C vacuum drying treatment 2h to get arrive Fe (III)/MIL-101
Catalyst.
Fig. 1 is above-mentioned Fe (III)/MIL-101 catalyst electron microscope, it can be seen that the pattern of catalyst is in irregular
Sheet has more gap.
Fig. 2 is above-mentioned Fe (III)/MIL-101 catalyst XRD test chart, it can be seen that the feature in gained map
Peak and the characteristic peak of MIL-101 are almost the same, and since load capacity is very little, the characteristic peak of iron ion is unobvious.
Embodiment 2
(1) preparation of MIL-101:
Weigh 2.8820g (7.2mmol) Cr (NO3)3·9H2O is placed in beaker, and the stirring of 43mL deionized water is added and is allowed to
Dissolution.Weigh 1.3304g (8mmol) H2BDC (terephthalic acid (TPA)), is slowly added to Cr (NO3)3In solution, stirring is allowed to uniformly mixed
It closes.After 0.04mL hydrofluoric acid is added, continue to stir 15min.Beaker is transferred to ultrasonic disperse 10min in ultrasonic cleaner,
It is transferred in autoclave polytetrafluoroethyllining lining.Autoclave is placed in high temperature furnace, is warming up to by room temperature 80min
200 DEG C, room temperature is down to after keeping the temperature 7h.Polytetrafluoroethyllining lining generation has blackish green MIL-101 and unreacted H2BDC white is brilliant
Body etc..
(2) purifying of MIL-101:
Polytetrafluoroethyllining lining is taken out from autoclave, is filtered product, is obtained with the blackish green of white needle-like crystals
Color crystal.Product is rinsed three times with deionized water, with the by-product for removing unreacted chromic salts He being dissolved in water.Successively use DMF, nothing
Water-ethanol cleans product, removes H in product respectively2BDC and extra DMF.The MIL-101 cleaned up in 150 DEG C of dryings
It is dried overnight in case, removes ethyl alcohol, sealing is stand-by.
(3) load of catalytic active site:
Take Cu (NO3)2·3H2O is added to absolute ethanol, and at room temperature after stirring and dissolving, 5g MIL-101 is added to solution
In.Wherein, the volume ratio of dehydrated alcohol and 5g MIL-101 are 0.8:1, and the quality of copper ion is Cu (NO3)2·3H2O and MIL-
The 0.5% of 101 quality sums.After being thoroughly mixed, vacuum drying treatment 3h urges at 60 DEG C to get to Cu (II)/MIL-101
Agent.
Embodiment 3
(1) preparation of MIL-101:
Weigh 3.5224g (8.8mmol) Cr (NO3)3·9H2O is placed in beaker, and the stirring of 35mL deionized water is added and is allowed to
Dissolution.Weigh 1.3304g (8mmol) H2BDC (terephthalic acid (TPA)), is slowly added to Cr (NO3)3In solution, stirring is allowed to uniformly mixed
It closes.After 1mL hydrofluoric acid is added, continue to stir 15min.Beaker is transferred to ultrasonic disperse 20min in ultrasonic cleaner, is shifted
Into autoclave polytetrafluoroethyllining lining.Autoclave is placed in high temperature furnace, is warming up to 200 DEG C by room temperature 80min,
Room temperature is down to after heat preservation 7h.Polytetrafluoroethyllining lining generation has blackish green MIL-101 and unreacted H2BDC white crystal etc..
(2) purifying of MIL-101:
Polytetrafluoroethyllining lining is taken out from autoclave, is filtered product, is obtained with the blackish green of white needle-like crystals
Color crystal.Product is rinsed three times with deionized water, with the by-product for removing unreacted chromic salts He being dissolved in water.Successively use DMF, nothing
Water-ethanol cleans product, removes H in product respectively2BDC and extra DMF.The MIL-101 cleaned up in 150 DEG C of dryings
It is dried overnight in case, removes ethyl alcohol, sealing is stand-by.
(3) load of catalytic active site:
Take Cu (NO3)2·3H2O is added to absolute ethanol, and at room temperature after stirring and dissolving, 5g MIL-101 is added to solution
In.Wherein, the volume ratio of dehydrated alcohol and 5g MIL-101 are 1.5:1, and the quality of copper ion is Cu (NO3)2·3H2O and MIL-
The 10% of 101 quality sums.After being thoroughly mixed, vacuum drying treatment 1h urges at 90 DEG C to get to Cu (II)/MIL-101
Agent.
Embodiment 4
The present embodiment step is substantially the same manner as Example 1, and difference is, the quality of iron ion is Fe (NO3)3·9H2O and
The 2% of MIL-101 quality sum.
Embodiment 5
The present embodiment step is substantially the same manner as Example 1, and difference is, the quality of iron ion is Fe (NO3)3·9H2O and
The 4% of MIL-101 quality sum.
Embodiment 6
The present embodiment step is substantially the same manner as Example 1, and difference is, the quality of iron ion is Fe (NO3)3·9H2O and
The 5% of MIL-101 quality sum.
Embodiment 7
In the present embodiment the step of compared with Example 1, step is essentially identical, and difference is, the load of catalytic active site
Dry mode is as follows:
Dehydrated alcohol is added in autoclave, reaches the 1/2 of autoclave volume, place the product in be fixed on reaction in small beaker
On kettle liquid face, walls of beaker is made to be higher than ethyl alcohol liquid level about 4cm or more in kettle, guarantees that ethyl alcohol will not enter beaker in kettle.It again will be high
Pressure kettle is sealed and purges 5 minutes discharge air of autoclave with nitrogen, starts to warm up；After temperature and pressure reaches critical value,
Under (about 250 DEG C, 7.1MPa) state, 1 hour is kept the temperature；It maintains critical-temperature pressure release to normal pressure, purges 1h, cooling with nitrogen；Temperature
Degree is cooled to room temperature, and opens kettle discharging to get Fe (III)/MIL-101 catalyst is arrived.
Embodiment 8
In the present embodiment the step of compared with Example 1, step is essentially identical, and difference is, the load of catalytic active site
Dry mode is as follows:
Dehydrated alcohol is added in autoclave, reaches the 1/2 of autoclave volume, place the product in be fixed on reaction in small beaker
On kettle liquid face, walls of beaker is made to be higher than ethyl alcohol liquid level about 4cm or more in kettle, guarantees that ethyl alcohol will not enter beaker in kettle.It again will be high
Pressure kettle is sealed and purges 5 minutes discharge air of autoclave with nitrogen, starts to warm up；After temperature and pressure reaches critical value,
Under (about 250 DEG C, 7.1MPa) state, 0.5 hour is kept the temperature；It maintains critical-temperature pressure release to normal pressure, purges 2h, cooling with nitrogen；
Temperature is cooled to room temperature, and opens kettle discharging to get Fe (III)/MIL-101 catalyst is arrived.
Embodiment 9
In the present embodiment the step of compared with Example 1, step is essentially identical, and difference is, the load of catalytic active site
Dry mode is as follows:
Dehydrated alcohol is added in autoclave, reaches the 1/2 of autoclave volume, place the product in be fixed on reaction in small beaker
On kettle liquid face, walls of beaker is made to be higher than ethyl alcohol liquid level about 4cm or more in kettle, guarantees that ethyl alcohol will not enter beaker in kettle.It again will be high
Pressure kettle is sealed and purges 5 minutes discharge air of autoclave with nitrogen, starts to warm up；After temperature and pressure reaches critical value,
Under (about 250 DEG C, 7.1MPa) state, 2 hours are kept the temperature；It maintains critical-temperature pressure release to normal pressure, purges 0.5h, cooling with nitrogen；
Temperature is cooled to room temperature, and opens kettle discharging to get Fe (III)/MIL-101 catalyst is arrived.
The test of catalysis of phenol hydroxylating
The catalyst and phenol (mass ratio of catalyst and phenol is in 1:8) that Example 1~9 is prepared respectively, one
Quantitative 30% hydrogen peroxide (volume ratio of phenol and hydrogen peroxide is in 1:15) and 300mL deionized water (phenol and deionization
The volume ratio of water is in 1:30) in round-bottomed flask, 2h is reacted under conditions of magnetic agitation at a temperature of 80 DEG C, waits mistake after reaction
Filter, filtrate is extracted with ethyl acetate three times, then with phenol and benzenediol content in gas chromatograph-mass spectrometer analytical extraction object.
Catalysis of phenol hydroxylating experimental test result is as shown in table 1.
Table 1
Catalytic activity transition metal ions is carried on MIL-101 by the preparation method of above-mentioned MIL-101 loaded catalyst
On, this method is simple and easy, and the catalyst activity of preparation is high, is applied in phenol hydroxylation catalysis reaction, phenol
Conversion ratio can reach 61.2%, and catechol selectively can reach 94.6%.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of MIL-101 loaded catalyst, which comprises the following steps:
Take transition metal salt to be dissolved in ethyl alcohol, be added MIL-101, after being stirred, be dried to get；
Wherein, the volume ratio of MIL-101 and ethyl alcohol is 1:(0.8~1.5), the metal ion in the transition metal salt is selected from iron
At least one of ion, ferrous ion, copper ion and nickel ion.
2. preparation method as described in claim 1, which is characterized in that the quality of metal ion is institute in the transition metal salt
State the 0.5%~10% of transition metal salt and the quality sum of MIL-101.
3. preparation method as described in claim 1, which is characterized in that the volume ratio of MIL-101 and ethyl alcohol is 1:(1~1.2).
4. preparation method as described in claim 1, which is characterized in that the drying process is that vacuum is dry at 60 DEG C~90 DEG C
Dry 1h~3h.
5. preparation method as described in claim 1, which is characterized in that the drying process is done under the conditions of postcritical
It is dry.
6. preparation method as claimed in claim 5, which is characterized in that drying under the conditions of postcritical includes:
Ethyl alcohol is added into reaction kettle, the mixture being stirred is placed in the reaction kettle on liquid level,
After being passed through protective gas discharge air, the overcritical value of increasing temperature and pressure to ethyl alcohol, heat-insulation pressure keeping 0.5h~2h；Temperature is maintained, is let out
It is depressed into normal pressure, protective gas purging 0.5h~2h is passed through, cools down, discharging.
7. preparation method as described in any one of claims 1 to 6, which is characterized in that MIL-101 is to be made by the steps
It obtains:
It takes terephthalic acid (TPA) to be added in chromium nitrate solution, hydrofluoric acid is added, is stirred to react, ultrasound is carried out to the mixed liquor after reaction
Processing, is warming up to 200 DEG C~220 DEG C insulation reactions, reaction product is filtered, wash, is dried.
8. preparation method as claimed in claim 7, which is characterized in that the molar ratio of terephthalic acid (TPA) and chromic nitrate is 1:(0.9
~1.1)；And/or
The time of the insulation reaction is 7h~9h.
9. a kind of MIL-101 loaded catalyst being prepared by preparation method as described in any one of claims 1 to 8.
10. application of the MIL-101 loaded catalyst as claimed in claim 9 in catalysis of phenol hydroxylating.
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Cited By (1)
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| CN112981456A (en) * | 2021-03-17 | 2021-06-18 | 扬州大学 | Preparation method of Cu @ MIL-101-Cr electrocatalyst for efficiently preparing acetone |
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