CN109317210A - A kind of bimetallic organic framework material and the preparation method and application thereof - Google Patents
A kind of bimetallic organic framework material and the preparation method and application thereof Download PDFInfo
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- CN109317210A CN109317210A CN201811210372.1A CN201811210372A CN109317210A CN 109317210 A CN109317210 A CN 109317210A CN 201811210372 A CN201811210372 A CN 201811210372A CN 109317210 A CN109317210 A CN 109317210A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
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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
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Abstract
The invention discloses a kind of bimetallic organic framework material and preparation method thereof and its in selective catalytic oxidation H2Application in S is with ZrCl4And FeCl3•6H2For O as raw material metal, terephthalic acid (TPA) is organic ligand, using a series of bimetallic organic framework material of difference Fe/Zr ratios of solvent structure.The bimetallic organic framework material is in selective oxidation H2S be sulphur reaction in show high H2The selective and high catalytic stability of S conversion ratio, high the product sulfur, and preparation method is easy, it is at low cost, it is easy to operate, it has a extensive future.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of bimetallic organic framework material and preparation method thereof
With it in selective catalytic oxidation H2Application in S.
Background technique
Hydrogen sulfide is the by-product in many industrial productions.Currently, there are more than 70 kinds of industry that can generate hydrogen sulfide, including adopt
Mine, oil exploitation and refinement, coal gas are produced.H2Major pollutants one of of the S as atmosphere are a kind of high irritation severe toxicity gas
Body, under aerobic and wet heat condition, H2S can not only cause equipment and corrosion of piping, catalyst poisoning, but also can seriously threaten people
Body safety.With the development of economy, the enhancing of people's environmental consciousness, the removing problem of hydrogen sulfide is increasingly by the pass of people
Note, while country has also formulated corresponding law, regulation, to H2S discharge amount has made stringent limitation.
Currently, H2The removing of S mainly uses Crouse (Claus) technique.The technique need to first absorb H2Concentrate after S, then pass through
Elemental sulfur is produced in further catalytic treatment, can reach removing H2The purpose of S gas, and can realize the recycling of wherein element sulphur
It utilizes.But due to the limitation of thermodynamical equilibrium, the still sulfide containing 3%-5% fails to be converted to simple substance in Claus tail gases
Sulphur.As environmental legislation is increasingly strict, needs to find one kind and do not limited by thermodynamical equilibrium, it can efficient removal H2S simultaneously realizes that S is mono-
The processing method that matter recycles.
In recent years, selective catalytic oxidation H2The method of S attracts widespread attention, reaction equation are as follows: H2S+O2→Sn
+H2O。H2S selective catalytic oxidation method is not limited by thermodynamical equilibrium, theoretical H2S conversion ratio can achieve 100 %.And this is anti-
Answer technique advanced, process is simple.Because reaction is exothermic reaction, H2S content can not need heat credit, energy in 0.5 % or more
It consumes low.Therefore, which has a good application prospect.But by the reactive applications in H2The removing of S, the key for needing to solve are asked
Topic is to develop a kind of new catalyst with high-efficiency catalytic activity and selectivity.
It is applied to H at present2The catalyst in S selective catalytic oxidation field mainly has traditional carbon material, molecular sieve and metal
Oxide.From literature survey the results show that existing catalyst is still there are many shortcoming.For example, active carbon, molecular sieve material
Material is enriched because of its large specific surface area, duct accelerates its mass transport process and the product sulfur desorption rate, but the material lacks itself
Active site could enhance catalytic performance after needing load active component or being modified, thus that there are preparation process is numerous
The problems such as trivial and active component is easy to run off in the reaction；Metal oxide itself has active site, and stability compares
Height, but specific surface area is smaller, limits it to H2The absorption of S, and sulphur is easy covering activated centre in the reaction, makes to be catalyzed
Agent performance is greatly reduced.Therefore, other than modified on original carrier, the efficient H of Development of Novel2S selective catalytic oxidation is urged
Agent is of great significance.
In recent years, a kind of emerging porous functional material metal-organic framework materials (Metal-Organic
Frameworks, MOFs) due to its unique physicochemical characteristics, it is always grinding for materials science field in the past few decades
Study carefully hot spot.MOFs material is that have periodically solid by what coordinate bond and inorganic metal ion were self-assembly of by organic ligand
Network structure crystal.Compared with traditional inorganic material, MOFs material has specific surface area, the orderly cellular structure of super large,
It is all widely used in fields such as absorption, sensing, pharmaceutical carrier and gas storages.MOFs material is also showed that in catalytic field
Huge application prospect: (1) its biggish specific surface area is conducive to the absorption to reaction substrate, promotes the progress of catalysis reaction；
(2) it since MOFs material has the characteristics that form multiplicity, structure tailorability, designability, easy modulation, may be implemented to tie it
The flexible modulation of structure and performance；(3) due to the presence of space steric effect, metal center in MOFs structure can only with partially have
Machine ligand combines.Therefore, to meet coordination demand, metal ion can be with DMF, CH3The molecule of some small sizes such as O is mutually tied
It closes.But this combination is unstable, is activated by heating in vacuum, can expose unsaturated coordination site, these active metals opened
Center directly and substrate-function can make MOFs have good catalytic performance.And it can between each discrete metal-oxygen unit
There can be synergistic effect, be conducive to the stability for keeping catalyst, generate high catalytic activity.Therefore MOFs material is that one kind has
The catalyst of potentiality, but MOFs material is in H2S selective catalytic oxidation has currently been still within step using upper research
Section.
It is current studies have shown that there are synergistic effects between two different metals in bimetallic MOFs material, compared with monometallic
MOFs material it is more advantageous.The present invention uses solvent-thermal method, with ZrCl4And FeCl3•6H2O is as raw material metal, to benzene
Dioctyl phthalate is organic ligand, by adjusting the content of two kinds of elements, synthesizes a series of catalyst of difference Fe/Zr ratios.With it
He compares at document with the similar material of patent report, and catalyst prepared by the present invention has more ligand unsatuated metals
Point, while having the specific surface area of super large, be conducive in H2S selective catalytic oxidation application.
Summary of the invention
The present invention is directed to the deficiency of current material, provides a kind of bimetallic organic framework material and preparation method thereof and answers
With.Gained bimetallic organic framework material has fabulous catalytic performance, is applied to H2The selective catalytic oxidation of S reacts
In, the application field of MOFs material can be not only widened significantly, be also the novel H of exploitation2S catalyst for selective oxidation provides experiment
Basis and mentality of designing.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of bimetallic organic framework material, is with ZrCl4With FeCl3•6H2O is as raw material metal, terephthalic acid (TPA)
The Fe-UIO-66 organic framework structured with bimetallic is made through solvent thermal reaction, vacuum activating in organic ligand.Its preparation side
Method specifically comprises the following steps:
(1) by ZrCl4With terephthalic acid (TPA) (H2BDC it) is added in anhydrous DMF, stirring 15-20 min makes it completely dissolved, and obtains
Clear mixed solution A；
(2) by FeCl3•6H2O is rapidly joined in mixed solution A under agitation, and continues to stir 55-65 min, is formed mixed
Close uniform solution B；
(3) solution B is put into cell crushing instrument, handles 30min at 50 DEG C；
(4) by step (3), treated, and solution B is transferred in reaction kettle, 120 DEG C of reaction 40-50 h；
(5) to after reaction, reaction kettle is cooled to room temperature, product is collected, is first washed 3-4 times with DMF and dehydrated alcohol, so
Centrifugal treating afterwards, and product is crossed 20-40 mesh, then at 120 DEG C of dryings after 100 DEG C of drying by the solid that centrifugation is obtained
12-16 h obtains the bimetallic organic framework material.
Wherein, ZrCl4, terephthalic acid (TPA) and FeCl3•6H2The molar ratio of O is 1:(1-2): (0.5 ~ 2).
The microscopic particles size of gained bimetallic organic framework material of the invention is 100-200nm, with high H2S conversion
The selective and high catalytic stability of rate, high the product sulfur can be used for selective catalytic oxidation hydrogen sulfide and generate sulphur.
The catalyst is suitable for H2The reaction of S selective catalytic oxidation generation sulphur.
Remarkable advantage of the invention is:
(1) in order to overcome existing H2Deficiency existing for S selective oxidation catalyst, the present invention are prepared for a kind of catalytic performance
Superior H2S selective oxidation catalyst Fe-UIO-66.Compared with the UIO-66 of existing report, Fe- produced by the present invention
UIO-66 has better crystal form, and there is the catalyst itself bimetallic unsaturation coordination site abundant can be used as active sites
Point can show height in the application that selective catalytic oxidation hydrogen sulfide generates sulphur without other supporting catalytic active component
Conversion ratio and selectivity.
(2) synthetic method of the present invention is simple and easy in preparation process of the present invention, is conducive to promote on a large scale.Wherein use
Cell crushing instrument processing, enables to Elemental redistribution in sample more uniform, and promote ferro element with organic ligand with phase interworking
The mode of position enters in skeleton.
Detailed description of the invention
Fig. 1 is the XRD diagram of sample obtained by embodiment 1-3；
Fig. 2 is that the SEM of embodiment 2 schemes；
Fig. 3 is the low temperature nitrogen adsorption desorption isothermal curve of sample and UIO-66 obtained by embodiment 1-3；
Fig. 4 is the pore size distribution curve of sample and UIO-66 obtained by embodiment 1-3；
Fig. 5 is embodiment 1-3 and comparative example 1-2 gained sample is in H2H in S catalysis oxidation catalytic performance test2S conversion ratio with
The curve graph of temperature change；
Fig. 6 is embodiment 1-3 and comparative example 1-2 gained sample is in H2S selectivity in S catalysis oxidation catalytic performance test is with temperature
Spend the curve graph of variation；
Fig. 7 is embodiment 1-3 and comparative example 1-2 gained sample is in H2Sulphur yield in S catalysis oxidation catalytic performance test is with temperature
Spend the curve graph of variation；
Fig. 8 is 2 gained sample of embodiment in H2S catalysis oxidation catalytic stability can evaluate in H2S conversion ratio is with the reaction time
The curve graph of variation；
Fig. 9 is the element spectrum curve and each element content of 2 gained sample of embodiment.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1:
By 4mmol ZrCl4With 4mmol H2BDC is dissolved in 240 mL anhydrous DMFs, is stirred 15 minutes, is obtained until completely dissolved
To mixed solution A；Weigh 2mmol FeCl3•6H2O is rapidly added in mixed solution A under agitation, and continues stirring 60
Minute, obtain clear mixed solution B；Mixed solution B is put into the broken pure instrument of cell, 30min is handled at 50 DEG C, then will be mixed
It closes solution B to be transferred in reaction kettle, reaction kettle is put into 120 DEG C of constant temperature oven and is reacted 40 hours；To after reaction, incite somebody to action
Reaction kettle is cooled to room temperature, collects product, is centrifuged after being washed 3-4 times with DMF and dehydrated alcohol, the solid that centrifugation is obtained
After being dried in 100 DEG C of baking ovens, product is sieved, the particle of 20-40 mesh is collected, then proceedes to the vacuum oven at 120 DEG C
Middle 12 h of drying collects sample and is denoted as S1.
Embodiment 2(most preferred embodiment):
By 2mmol ZrCl4With 2mmol H2BDC is dissolved in 120 mL anhydrous DMFs, is stirred 15 minutes, is obtained until completely dissolved
To mixed solution A；Weigh 2mmol FeCl3•6H2O is rapidly added in mixed solution A under agitation, and continues stirring 65
Minute, obtain clear mixed solution B；Mixed solution B is put into the broken pure instrument of cell, 30min is handled at 50 DEG C, then will be mixed
It closes solution B to be transferred in reaction kettle, reaction kettle is put into 120 DEG C of constant temperature oven and is reacted 48 hours；To after reaction, incite somebody to action
Reaction kettle is cooled to room temperature, collects product, is centrifuged after being washed 3-4 times with DMF and dehydrated alcohol, the solid that centrifugation is obtained
After being dried in 100 DEG C of baking ovens, product is sieved, the particle of 20-40 mesh is collected, then proceedes to the vacuum oven at 120 DEG C
Middle 14 h of drying collects sample and is denoted as S2.
Embodiment 3:
By 2mmol ZrCl4With 4mmol H2BDC is dissolved in 120 mL anhydrous DMFs, is stirred 15 minutes, is obtained until completely dissolved
To mixed solution A；Weigh 4mmol FeCl3•6H2O is rapidly added in mixed solution A under agitation, and continues stirring 55
Minute, obtain clear mixed solution B；Mixed solution B is put into the broken pure instrument of cell, 30min is handled at 50 DEG C, then will be mixed
It closes solution B to be transferred in reaction kettle, reaction kettle is put into 120 DEG C of constant temperature oven and is reacted 50 hours；To after reaction, incite somebody to action
Reaction kettle is cooled to room temperature, collects product, is centrifuged after being washed 3-4 times with DMF and dehydrated alcohol, the solid that centrifugation is obtained
After being dried in 100 DEG C of baking ovens, product is sieved, the particle of 20-40 mesh is collected, then proceedes to the vacuum oven at 120 DEG C
Middle 14 h of drying collects sample and is denoted as S3.
Comparative example 1:
By 2mmol ZrCl4With 2mmol H2BDC is dissolved in 120 mL anhydrous DMFs, is stirred 15 minutes, is obtained until completely dissolved
To mixed solution A；Mixed solution A is transferred in reaction kettle, it is small that reaction kettle is put into reaction 48 in 120 DEG C of constant temperature oven
When；To after reaction, reaction kettle is cooled to room temperature, collects product, carried out after being washed 3-4 times with DMF and dehydrated alcohol from
Product is sieved by the heart after drying the solid that centrifugation obtains in 100 DEG C of baking ovens, collects the particle of 20-40 mesh, then proceedes to
Dry 14 h in 120 DEG C of vacuum oven, collect sample and are denoted as D1(i.e. UIO-66).
Comparative example 2:
Commercial iron is denoted as D2.
Evaluate example
Table 1 is 1 gained UIO-66's of bimetallic organic framework catalyst sample and comparative example prepared by 1-3 of the embodiment of the present invention
BET characterization parameter and ICP characterize data.
Table 1 characterizes the texture parameter of sample S1-S3 obtained by embodiment
From table 1 it is recognised that with Fe element ratio in S1-S3 catalyst increase, the specific surface area and Kong Rongxian of sample increase
Reduce after big, ICP's the result shows that there is the presence of ferro element in prepared sample.
Fig. 1 is the XRD diagram of sample obtained by 1-3 of the embodiment of the present invention.It can be seen that its map and Zr reported in the literature
The XRD spectral peak of base MOF matches each other, and is not found the characteristic peak of iron in spectrogram, this illustrates that ferro element may be to match
The mode of position enters, and the addition of ferro element and the crystal structure for having not been changed Zr base MOF.
Fig. 2 is the electron microscopic picture of sample S2 prepared by embodiment 2.It can be seen from the figure that the microcosmic grain of synthesized sample
Diameter is about 0.1 μm or so, and particle size distribution is uniform, in special microballoon pattern.
Fig. 3 and Fig. 4 is respectively the low temperature N of sample and UIO-66 obtained by 1-3 of the embodiment of the present invention2Physics adsorption desorption isothermal is bent
Line and pore size distribution curve.As seen from the figure, the low-pressure area of the Adsorption and desorption isotherms of four samples has intensive point, this four kinds of explanation
There is microcellular structure in sample；It also can intuitively find out that its micropore size is 0.5-0.8 nm from the result of pore-size distribution,
In addition, in sample S3, there is also mesoporous；From the rule of pore-size distribution it can be found that with Fe constituent content increase, sample well
Diameter has the tendency that from micropore to mesoporous transition.
Correlated performance judgement schematics are as follows:
；
；
；
In formula:H 2 S Conversion For hydrogen sulfide conversion ratio；H 2 S Selectivity The selectivity of sulphur is catalytically oxidized to for hydrogen sulfide；S yield For sulphur yield；(H 2 S) in For unstripped gas air inlet H2S concentration；(H 2 S) out H is exported for reaction2S gas concentration；(SO 2 ) out
To react exit SO2Gas concentration.
Fig. 5 is H of the sample in performance evaluation obtained by embodiment 1-3 and comparative example 1-22S conversion ratio varies with temperature
Curve graph.It can be seen from the figure that the H of catalyst prepared by the present invention2S conversion ratio is higher than comparative sample, wherein implementing
Close to 100 %, and as the temperature rises, conversion ratio does not occur hydrogen sulfide conversion ratio of the example S2 catalyst at 100 DEG C
Apparent decline.
Fig. 6 is embodiment 1-3 and sulphur simple substance of the comparative example 1-2 gained sample in performance evaluation selectively varies with temperature
Curve graph.It can be seen from the figure that catalyst prepared by the present invention is intended to the selectivity of sulphur simple substance to be substantially better than comparison
The selectivity of sample, three samples prepared by embodiment is held in 90 % or more.
The curve that Fig. 7 is embodiment 1-3 and sulphur yield with temperature of the comparative example 1-2 gained sample in performance evaluation changes
Figure.It can be seen from the figure that the sulphur yield of prepared catalyst of the present invention is better than comparative sample.
Fig. 8 is sample S2 H in catalyst performance evaluation2The conversion ratio time history plot of S, can be with from figure
Find out, with excellent catalytic stability, do not occur apparent deactivation phenomenom after reaction carries out 50 hours, this is also embodied
Bimetallic organic framework material prepared by the present invention has superior H2S selective catalytic oxidation performance.
Fig. 9 is the spectrum curve and each element content of sample S2, thus in conjunction with the data of ICP and XRD it is recognised that iron is first
Element successfully introduces in Zr base MOF, and the addition of ferro element and the crystal structure for having not been changed Zr base MOF, i.e., successfully makes
For ferrozirconium bimetallic organic framework material.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (5)
1. a kind of bimetallic organic framework material, it is characterised in that: with ZrCl4With FeCl3•6H2O is as raw material metal, to benzene
Dioctyl phthalate is organic ligand, and through solvent thermal reaction, vacuum activating, the Fe-UIO-66 organic framework structured with bimetallic is made.
2. bimetallic organic framework material according to claim 1, it is characterised in that: its microscopic particles size is 100-
200nm。
3. a kind of preparation method of bimetallic organic framework material as described in claim 1, it is characterised in that: including walking as follows
It is rapid:
(1) by ZrCl4It is added in anhydrous DMF with terephthalic acid (TPA), stirring 15-20 min makes it completely dissolved, and obtains clear mixed
Close solution A；
(2) by FeCl3•6H2O is rapidly joined in mixed solution A under agitation, and continues to stir 55-65 min, is formed mixed
Close uniform solution B；
(3) solution B is put into cell crushing instrument, handles 30min at 50 DEG C；
(4) by step (3), treated, and solution B is transferred in reaction kettle, 120 DEG C of reaction 40-50 h；
(5) to after reaction, reaction kettle is cooled to room temperature, product is collected, is first washed 3-4 times with DMF and dehydrated alcohol, so
Centrifugal treating afterwards, and product is crossed 20-40 mesh, then at 120 DEG C of dryings after 100 DEG C of drying by the solid that centrifugation is obtained
12-16 h obtains the bimetallic organic framework material.
4. the preparation method of bimetallic organic framework material according to claim 3, it is characterised in that: ZrCl used4, to benzene
Dioctyl phthalate and FeCl3•6H2The molar ratio of O is 1:(1-2): (0.5 ~ 2).
5. a kind of bimetallic organic framework material as claimed in claim 4 generates in sulphur in selective catalytic oxidation hydrogen sulfide
Application.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591108A (en) * | 2019-09-24 | 2019-12-20 | 福州大学 | Preparation and application of bimetallic MOFs material |
| CN111393664A (en) * | 2020-04-14 | 2020-07-10 | 天津大学 | Bimetallic MOF material, preparation method thereof and application thereof in hydrogenation reaction |
| CN111848972A (en) * | 2020-08-12 | 2020-10-30 | 南昌航空大学 | Preparation method and application of bimetallic MOF based on MOF-808 |
| CN113307982A (en) * | 2021-06-24 | 2021-08-27 | 河南中医药大学 | Preparation method and application of Cd/Zr-UIO-66 bimetallic organic framework material |
| CN114685801A (en) * | 2022-03-08 | 2022-07-01 | 清华大学 | Precious metal recovery organic polymer and preparation method and application thereof |
| CN115403491A (en) * | 2021-05-26 | 2022-11-29 | 中国石油化工股份有限公司 | Metal organic framework material with benzenesulfonyl structure, preparation method and application thereof, and carboxylic acid esterification method |
| WO2023240891A1 (en) * | 2022-06-14 | 2023-12-21 | 浙江大学 | Cyano group-modified zr-fe mof, preparation method therefor, and zinc-based flow battery zinc negative electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160208047A1 (en) * | 2015-01-20 | 2016-07-21 | Chung Yuan Christian University | Metal-organic framework polymer for solid-phase microextraction |
| CN105977040A (en) * | 2016-07-18 | 2016-09-28 | 南昌航空大学 | Metal organic skeleton electrode material of supercapacitor and preparation method of the electrode material |
| CN106732782A (en) * | 2016-11-23 | 2017-05-31 | 福州大学 | A kind of H2The preparation method and applications of S catalyst for selective oxidation |
-
2018
- 2018-10-17 CN CN201811210372.1A patent/CN109317210B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160208047A1 (en) * | 2015-01-20 | 2016-07-21 | Chung Yuan Christian University | Metal-organic framework polymer for solid-phase microextraction |
| CN105977040A (en) * | 2016-07-18 | 2016-09-28 | 南昌航空大学 | Metal organic skeleton electrode material of supercapacitor and preparation method of the electrode material |
| CN106732782A (en) * | 2016-11-23 | 2017-05-31 | 福州大学 | A kind of H2The preparation method and applications of S catalyst for selective oxidation |
Non-Patent Citations (2)
| Title |
|---|
| XUEQING XU,ET AL.: "PANI/FeUiO-66 nanohybrids with enhanced visible-light promotedphotocatalytic activity for the selectively aerobic oxidation ofaromatic alcohols", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 王君: "金属有机骨架材料装载阿霉素载药系统的构建及大鼠体内药动学研究", 《中国优秀硕士学位论文全文数据库 医药卫生科技辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591108A (en) * | 2019-09-24 | 2019-12-20 | 福州大学 | Preparation and application of bimetallic MOFs material |
| CN111393664A (en) * | 2020-04-14 | 2020-07-10 | 天津大学 | Bimetallic MOF material, preparation method thereof and application thereof in hydrogenation reaction |
| CN111393664B (en) * | 2020-04-14 | 2021-11-02 | 天津大学 | Bimetallic MOF material, preparation method thereof and application thereof in hydrogenation reaction |
| CN111848972A (en) * | 2020-08-12 | 2020-10-30 | 南昌航空大学 | Preparation method and application of bimetallic MOF based on MOF-808 |
| CN111848972B (en) * | 2020-08-12 | 2021-11-02 | 南昌航空大学 | Preparation method and application of bimetallic MOF based on MOF-808 |
| CN115403491A (en) * | 2021-05-26 | 2022-11-29 | 中国石油化工股份有限公司 | Metal organic framework material with benzenesulfonyl structure, preparation method and application thereof, and carboxylic acid esterification method |
| CN113307982A (en) * | 2021-06-24 | 2021-08-27 | 河南中医药大学 | Preparation method and application of Cd/Zr-UIO-66 bimetallic organic framework material |
| CN114685801A (en) * | 2022-03-08 | 2022-07-01 | 清华大学 | Precious metal recovery organic polymer and preparation method and application thereof |
| WO2023240891A1 (en) * | 2022-06-14 | 2023-12-21 | 浙江大学 | Cyano group-modified zr-fe mof, preparation method therefor, and zinc-based flow battery zinc negative electrode material |
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