CN110368996A - A kind of catalyst CuBr2@UiO-66-NH2-CF3COOH and the preparation method and application thereof - Google Patents
A kind of catalyst CuBr2@UiO-66-NH2-CF3COOH and the preparation method and application thereof Download PDFInfo
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- CN110368996A CN110368996A CN201910548897.4A CN201910548897A CN110368996A CN 110368996 A CN110368996 A CN 110368996A CN 201910548897 A CN201910548897 A CN 201910548897A CN 110368996 A CN110368996 A CN 110368996A
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- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 229910021590 Copper(II) bromide Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 56
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 26
- 239000012265 solid product Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000031709 bromination Effects 0.000 claims abstract description 6
- 238000005893 bromination reaction Methods 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000007654 immersion Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- -1 p-nitrophenyl diazonium tetrafluoroborate Chemical compound 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 8
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000003459 sulfonic acid esters Chemical class 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010701 ester synthesis reaction Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ORGROGADTAVCJL-UHFFFAOYSA-N [O-][N+](=O)C1=CC=C([S])C=C1 Chemical compound [O-][N+](=O)C1=CC=C([S])C=C1 ORGROGADTAVCJL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000012954 diazonium Substances 0.000 claims 1
- 150000001989 diazonium salts Chemical class 0.000 claims 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims 1
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 108010022394 Threonine synthase Proteins 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 102000005497 Thymidylate Synthase Human genes 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
-
- 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
- B01J2231/49—Esterification or transesterification
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to catalyst technical field more particularly to a kind of catalyst CuBr2@UiO‑66‑NH2‑CF3COOH and the preparation method and application thereof.The described method includes: 1) by UiO-66-NH2It is placed in CF3Immersion treatment is carried out in the aqueous solution of COOH, reaction solution is separated after the completion, obtained solid product is washed, up to UiO-66-NH after drying2‑CF3COOH；2) by the UiO-66-NH of step 1)2‑CF3COOH is placed in bromination copper solution and impregnates, separates after the completion to reaction solution, and obtained solid product is washed, up to CuBr after drying2@UiO‑66‑NH2‑CF3COOH.Catalyst CuBr of the invention2@UiO‑66‑NH2‑CF3COOH utilization rate is high, and reaction condition is mild, environmentally protective, can be effectively reduced catalysis cost.
Description
Technical field
The present invention relates to catalyst technical fields more particularly to a kind of for synthesizing the catalyst CuBr of sulphonic acid ester2@
UiO-66-NH2-CF3COOH and the preparation method and application thereof.
Background technique
It is only intended to increase understanding of the overall background of the invention for information disclosed in background of invention, without
It is existing well known to persons skilled in the art so to be considered as recognizing or imply that information composition has become in any form
Technology.
Metal organic frame (MOFs) is to pass through coordinate bond self assembly by organic ligand and inorganic metal ion or cluster
The hybrid inorganic-organic materials with molecule inner pore formed.MOFs can control the structure and large specific surface area in hole, therefore
There are wider application prospect, such as adsorbing separation, catalysis, magnetic material and optical material than other porous materials.UiO-
66-NH2It is then one of MOFs, it is with Zr4+It is synthesized for metal ion and using 2- amino terephthalic acid (TPA) as ligand
The MOF arrived, it has preferable thermal stability and chemical stability.Therefore, UiO-66-NH2It is being urged as crystalline state porous material
There is very big advantage in the application for changing aspect.
Sulphonic acid ester is segment common in many drugs and other biological activities compound.For example, sulfonic acid esters drug can
To prevent or treat undesirable thrombosis or the bacterium thymidylate synthetase inhibitor new as one kind.Traditional sulphonic acid ester
Synthetic method is the esterification of sulfonic acid chloride in the presence of a base, this needs to prepare harmful sulfonic acid chloride.Scientists are not yet
Study new more " green " synthetic method disconnectedly: copper bromide homogeneous catalysis sulfonic acid esters drug under the auxiliary of trifluoroacetic acid closes
At being made great progress compared to synthetic method more in front.
Nevertheless, but inventor find current bromination copper catalyst there are still following during synthesizing sulphonic acid ester
Problem: (1) copper bromide causes the pollution of environment as discharging after metal salt catalyst；(2) trifluoroacetic acid is as cocatalyst
It cannot recycle, cause to waste；(3) catalyst system cannot be recycled, and utilization rate reduces.
Summary of the invention
In view of the above problems, the present invention is intended to provide a kind of catalyst CuBr2@UiO-66-NH2-CF3COOH and
Preparation method and application.Experiment proves that catalyst CuBr proposed by the present invention2@UiO-66-NH2-CF3COOH utilization rate
Height, reaction condition is mild, environmentally protective, can be effectively reduced catalysis cost, has good application value.
An object of the present disclosure: a kind of catalyst CuBr is provided2@UiO-66-NH2-CF3COOH。
Second purpose of the invention: a kind of catalyst CuBr is provided2@UiO-66-NH2-CF3The preparation method of COOH.
Third purpose of the present invention: the catalyst CuBr is provided2@UiO-66-NH2-CF3The application of COOH.
For achieving the above object, the invention discloses following technical proposals:
Firstly, the present invention discloses a kind of catalyst CuBr2@UiO-66-NH2-CF3COOH, by CuBr2、 UiO-66-NH2
And CF3COOH composition, wherein the CF3COOH is coordinated in UiO-66-NH2In metal zirconium cluster node on, the CuBr2Load
In UiO-66-NH2On.
As further technical solution, the CuBr2、UiO-66-NH2、CF3The ratio of COOH are as follows: 1-2:1:6.
As further technical solution, the CuBr2@UiO-66-NH2-CF3The partial size of COOH are as follows: 100-500nm.
Catalyst CuBr of the present invention2@UiO-66-NH2-CF3The characteristics of COOH, is: CuBr2、UiO-66-NH2And CF3COOH
It is organically combined together by way of physical absorption and chemical coordination, is urged relative to individually addition copper bromide and its auxiliary
Agent trifluoroacetic acid, it is easy to operate, and the transformation of homogeneous catalysis to heterocatalysis is realized, so that catalyst recycles simply
It is easy.
Secondly, the present invention discloses a kind of catalyst CuBr2@UiO-66-NH2-CF3The preparation method of COOH, including walk as follows
It is rapid:
(1) UiO-66-NH is synthesized2-CF3COOH: by UiO-66-NH2It is placed in CF3It is carried out at immersion in the aqueous solution of COOH
Reason, after the completion separates reaction solution, obtained solid product is washed, up to UiO-66-NH after drying2-
CF3COOH；
(2) CuBr is synthesized2@UiO-66-NH2-CF3COOH: by the UiO-66-NH of step (1)2-CF3COOH is placed in bromination
It impregnates in copper solution, reaction solution is separated after the completion, obtained solid product is washed, up to CuBr after drying2@
UiO-66-NH2-CF3COOH。
The present invention synthesizes CuBr2@UiO-66-NH2-CF3The principle of COOH is as follows:
As further technical solution, in step (1), the UiO-66-NH2Existing product can be directlyed adopt, or
The method of use synthesizes, and the present invention provides a kind of specific synthetic method, comprising: weighs ZrCl4And CH3COOH is dissolved in DMF solution
In, 2- amino terephthalic acid (TPA) is added after solution clarification in ultrasonic disperse, and re-ultrasonic dispersion transfers the solution into enclosed high pressure
It is reacted in kettle, after reaction, centrifuge separation, washing, drying obtain UiO-66-NH2。
As further technical solution, the temperature of the reaction is 110-135 DEG C, reaction time 22-26h, preferably
For for 24 hours.
As further technical solution, the ZrCl4、CH3The molar ratio of COOH and 2- amino terephthalic acid (TPA) is 1:
(14-17):1。
As further technical solution, in step (1), the CF3The concentration of the aqueous solution of COOH is 5-7mol/L.
As further technical solution, in step (2), the copper bromide solution concentration is 3-6mg/mL.
As further technical solution, in step (2), the bromination copper solution is ethyl alcohol/methanol/second of copper bromide
The solution such as nitrile.
As further technical solution, the UiO-66-NH2-CF3COOH and ethyl alcohol/methanol/acetonitrile quality volume
Than for (8-12) mg:8ml.
As further technical solution, in step (1) and (2), the washing is necessary to be washed with water or ethyl alcohol
When can repeatedly be washed, preferably to remove remaining reaction solution in solid product.
As further technical solution, in step (1) and (2), the condition of the drying process are as follows: treatment temperature is
60-90 DEG C, the processing time is 8-16 hours；Further preferably are as follows: treatment temperature is 80 DEG C, and the processing time is 12 hours.
Finally, the present invention discloses the CuBr2@UiO-66-NH2-CF3COOH answering in catalysis sulfonic acid ester synthesis reaction
With.
As further technical solution, the application method particularly includes: by p-nitrophenyl diazonium tetrafluoroborate,
DABSO, methanol, methylene chloride and CuBr2@UiO-66-NH2-CF3COOH is reacted after mixing to get p-nitrophenyl sulphur
Sour methyl esters.
As further technical solution, the reaction temperature is 25-29 DEG C, that is, uses CuBr of the invention2@UiO-
66-NH2-CF3When catalyst of the COOH as sulfonic acid Lipase absobed, additional cocatalyst, and reaction temperature temperature had not both been needed
With, it does not need heating and consumes the additional energy again, without worry because of a series of danger of pyroreaction bring, and easy control
System.
As further technical solution, the p-nitrophenyl diazonium tetrafluoroborate, DABSO, methanol and CuBr2@
UiO-66-NH2-CF3The molar ratio of COOH is sequentially 1:1:245:0.002.The methylene chloride be as Conventional solvents, can
It is added as needed.
Catalyst CuBr of the present invention2@UiO-66-NH2-CF3The principle that COOH is catalyzed sulfonic acid ester synthesis reaction is as follows:
Compared with prior art, the present invention achieve it is following the utility model has the advantages that
(1) catalyst provided by the invention reduces environmental pollution instead of some transition metal applications.
(2) it is catalyzed using catalyst of the invention, is not needed to make catalyst with transition metal salt, realize out-phase and urge
Change, catalyst is easy to reduce the pollution of catalyst bring, while can repeat benefit by simply filtering or being centrifugated recycling
With more than five times, and catalyst recycling is easy, and is improved the utilization rate of catalyst, is reduced costs.
(3) reaction temperature of the invention is mild, and catalyst amount is few, does not need additional cocatalyst.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.
Fig. 1 is UiO-66-NH prepared by the embodiment of the present invention 12Infrared spectrum.
Fig. 2 is UiO-66-NH prepared by the embodiment of the present invention 22-CF3The infrared spectrum of COOH.
Fig. 3 is UiO-66-NH prepared by the embodiment of the present invention 22-CF3The SEM of COOH schemes.
Fig. 4 is CuBr prepared by the embodiment of the present invention 32@UiO-66-NH2-CF3The infrared spectrum of COOH.
Fig. 5 is CuBr prepared by the embodiment of the present invention 32@UiO-66-NH2-CF3The SEM of COOH schemes.
Fig. 6 is CuBr prepared by the embodiment of the present invention 32@UiO-66-NH2-CF3COOH is after being catalyzed sulfonic acid ester synthesis reaction
Correspondence PXRD spectrogram.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the present invention.Unless another
It indicates, all technical and scientific terms used herein has usual with general technical staff of the technical field of the invention
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to exemplary embodiments of the present invention.Such as, used herein, unless the context clearly indicates otherwise, otherwise singular shape
Formula is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As previously mentioned, current bromination copper catalyst still deposits copper bromide as metal during synthesizing sulphonic acid ester
It is discharged after salt catalysis, causes the pollution of environment；Trifluoroacetic acid can not be recycled as cocatalyst, cause to waste；Catalyst
A series of problems, such as system cannot be recycled, and utilization rate reduces.Therefore, the present invention proposes to plant the catalysis for synthesizing sulphonic acid ester
Agent CuBr2@UiO-66-NH2-CF3COOH and preparation method thereof；It is further to the present invention now in conjunction with the drawings and specific embodiments
It is illustrated.
Embodiment 1
UiO-66-NH2Preparation, include the following steps:
(1) by ZrCl4(139mg, 0.6mmol) and CH3COOH (538 μ L, 9.4mmol) is dissolved in 15mL DMF solution,
Ultrasonic disperse 30min is added 2- amino terephthalic acid (TPA) (108mg, 0.6mmol), re-ultrasonic dispersion after solution clarification
10min；
(2) solution obtained after ultrasonic disperse in step (1) is transferred in autoclave, is heated 24 hours at 120 DEG C, it is complete
Reaction solution is separated at rear, three times with ethanol washing by obtained solid product, then in 80 DEG C of dry 12h, is obtained
UiO-66-NH295.0mg, yield 89.7%.
Embodiment 2
UiO-66-NH2-CF3The synthesis of COOH includes the following steps: UiO-66-NH prepared by Example 12
20.0mg is placed in the CF that 10mL concentration is 6mol/L3After being stirred 12 hours in COOH aqueous solution, reaction solution is divided after the completion
From three times with ethanol washing by obtained solid product, then in 80 DEG C of dry 12h, obtaining UiO-66-NH2-CF3COOH。
Embodiment 3
Catalyst CuBr2@UiO-66-NH2-CF3The preparation of COOH includes the following steps: to take the preparation of 10mg embodiment 2
UiO-66-NH2-CF3The 8mL ethanol solution (concentration 5mg/mL) containing copper bromide is added in COOH, stirs into uniform turbid
Liquid impregnates 12 hours, is centrifugated up to CuBr2@UiO-66-NH2-CF3COOH。
Embodiment 4
A kind of catalyst CuBr2@UiO-66-NH2-CF3The preparation method of COOH, includes the following steps:
1、UiO-66-NH2Preparation, include the following steps:
(1) by ZrCl4(1mmol) and CH3COOH (14mmol) is dissolved in 15mL DMF solution, ultrasonic disperse 30min, to
After solution clarification, it is added 2- amino terephthalic acid (TPA) (1mmol), re-ultrasonic dispersion 10min；
(2) solution obtained after ultrasonic disperse in step (1) is transferred in autoclave, is heated 26 hours at 110 DEG C, it is complete
Reaction solution is separated at rear, three times with ethanol washing by obtained solid product, then in 80 DEG C of dry 12h, is obtained
UiO-66-NH2。
2、UiO-66-NH2-CF3The synthesis of COOH includes the following steps: UiO-66-NH prepared by Example 12
20.0mg is placed in the CF that 10mL concentration is 5mol/L3After being stirred 12 hours in COOH aqueous solution, reaction solution is divided after the completion
From three times with ethanol washing by obtained solid product, then in 60 DEG C of dry 16h, obtaining UiO-66-NH2-CF3COOH。
3, catalyst CuBr2@UiO-66-NH2-CF3The preparation of COOH includes the following steps: to take the preparation of 8mg embodiment 2
UiO-66-NH2-CF3The 8mL ethanol solution (concentration 6mg/mL) containing copper bromide is added in COOH, stirs into uniform turbid,
It impregnates 12 hours, is centrifugated up to CuBr2@UiO-66-NH2-CF3COOH。
Embodiment 5
A kind of catalyst CuBr2@UiO-66-NH2-CF3The preparation method of COOH, includes the following steps:
1、UiO-66-NH2Preparation, include the following steps:
(1) by ZrCl4(1mmol) and CH3COOH (17mmol) is dissolved in 15mL DMF solution, ultrasonic disperse 30min, to
After solution clarification, it is added 2- amino terephthalic acid (TPA) (1mmol), re-ultrasonic dispersion 10min；
(2) solution obtained after ultrasonic disperse in step (1) is transferred in autoclave, is heated 22 hours at 135 DEG C, it is complete
Reaction solution is separated at rear, three times with ethanol washing by obtained solid product, then in 80 DEG C of dry 12h, is obtained
UiO-66-NH2。
2、UiO-66-NH2-CF3The synthesis of COOH includes the following steps: UiO-66-NH prepared by Example 12
20.0mg is placed in the CF that 10mL concentration is 7mol/L3After being stirred 12 hours in COOH aqueous solution, reaction solution is divided after the completion
From three times with ethanol washing by obtained solid product, then in 90 DEG C of dry 8h, obtaining UiO-66-NH2-CF3COOH。
3, catalyst CuBr2@UiO-66-NH2-CF3The preparation of COOH includes the following steps: that 12mg embodiment 2 is taken to prepare
UiO-66-NH2-CF3The 8mL ethanol solution (concentration 3mg/mL) containing copper bromide is added in COOH, stirs into uniform turbid
Liquid impregnates 12 hours, is centrifugated up to CuBr2@UiO-66-NH2-CF3COOH。
Performance characterization and test:
(1) UiO-66-NH prepared by embodiment 12It is characterized, IR is as shown in Figure 1.As can be seen from the figure: UiO-
66-NH2The peak position value 1550cm of upper metal zirconium cluster coordination carboxylic acid-1And 3450cm-1Near.
(2) UiO-66-NH by IR and SEM prepared by embodiment 22-CF3COOH is characterized, as a result see respectively Fig. 2,
3.As can be seen from the figure: UiO-66-NH2-CF3The upper metal zirconium cluster of COOH is coordinated the peak position value 1600cm of three carboxylic acid fluorides-1With
3500cm-1Near；UiO-66-NH2-CF3COOH particle is irregular spherical, partial size 100-500nm.
(3) CuBr prepared by embodiment 3 is characterized by IR, SEM2@UiO-66-NH2-CF3COOH, as a result see respectively Fig. 4,
5.As can be seen from the figure: CuBr2@UiO-66-NH2-CF3COOH infrared signature peak changes less, CuBr2@UiO-66-NH2-
CF3COOH particle changes, and becomes irregular bulk, partial size 100-500nm.
Embodiment 6
The synthetic reaction of sulphonic acid ester includes the following steps: under room temperature condition (between 25-29 DEG C), in 10mL round-bottomed flask
Middle addition p-nitrophenyl diazonium tetrafluoroborate (0.0236g, 0.1mmol), DABSO (0.0240g, 0.1mmol) and embodiment
The catalyst CuBr of 3 preparations2@UiO-66-NH2-CF3COOH (0.040g), and methanol (10mL) and methylene chloride (2mL) is taken to add
Entering into flask, at room temperature hybrid reaction 48 hours, obtains yellow turbid solution, filtered, the filtrate left is rotated,
It vacuumizes solvent and obtains catalysate later.It recycles catalyst (rate of recovery 98% by mass), direct plunges into subsequent cycle
Reaction, according to above-mentioned condition, catalyst is using 5 circulations, and by gc measuring and calculation yield, catalytic effect is as shown in table 1.Recycling
Catalyst pass through PXRD characterize, CuBr2@UiO-66-NH2-CF3COOH still keeps original frame (as shown in Figure 6).
1 CuBr of table2@UiO-66-NH2-CF3COOH catalysis sulfur dioxide intercalation reaction prepares the production of sulphonic acid ester 5 circulations
Rate
| Reaction times | Reaction time/h | Conversion ratio/%a | Yield/%a | Selectivity/%a |
| 1 | 48 | > 99.0 | > 99.0 | 100 |
| 2 | 48 | > 99.0 | > 99.0 | 100 |
| 3 | 48 | > 99.0 | > 99.0 | 100 |
| 4 | 48 | > 99.0 | > 99.0 | 100 |
| 5 | 48 | > 99.0 | > 99.0 | 100 |
Note: a indicates that yield is measured by nuclear-magnetism in table 1.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of catalyst CuBr2@UiO-66-NH2-CF3COOH, which is characterized in that by CuBr2、UiO-66-NH2And CF3COOH
Composition, wherein the CF3COOH is coordinated in UiO-66-NH2In metal zirconium cluster node on, the CuBr2It is supported on UiO-66-
NH2On.
2. catalyst CuBr as described in claim 12@UiO-66-NH2-CF3COOH, which is characterized in that the CuBr2、UiO-
66-NH2、CF3The ratio of COOH are as follows: 1-2:1:6.
3. catalyst CuBr as claimed in claim 1 or 22@UiO-66-NH2-CF3COOH, which is characterized in that the CuBr2@
UiO-66-NH2-CF3The partial size of COOH are as follows: 100-500nm.
4. a kind of catalyst CuBr2@UiO-66-NH2-CF3The preparation method of COOH, which comprises the steps of:
(1) UiO-66-NH is synthesized2-CF3COOH: by UiO-66-NH2It is placed in CF3Immersion treatment is carried out in the aqueous solution of COOH, it is complete
Reaction solution is separated at rear, obtained solid product is washed, up to UiO-66-NH after drying2-CF3COOH；
(2) CuBr is synthesized2@UiO-66-NH2-CF3COOH: by the UiO-66-NH of step (1)2-CF3It is molten to be placed in copper bromide by COOH
It impregnates in liquid, reaction solution is separated after the completion, obtained solid product is washed, up to CuBr after drying2@UiO-
66-NH2-CF3COOH。
5. catalyst CuBr as claimed in claim 42@UiO-66-NH2-CF3The preparation method of COOH, which is characterized in that step
Suddenly in (1), the UiO-66-NH2Synthetic method are as follows: weigh ZrCl4And CH3COOH is dissolved in DMF solution, ultrasonic disperse, to
After solution clarification, 2- amino terephthalic acid (TPA) is added, re-ultrasonic dispersion is transferred the solution into enclosed high pressure kettle and is reacted,
After reaction, it is centrifugated, washs, is dry, obtaining UiO-66-NH2；
Preferably, the temperature reacted in the autoclave is 110-135 DEG C, reaction time 22-26h, more preferably for 24 hours；
Preferably, the ZrCl4、CH3The molar ratio of COOH and 2- amino terephthalic acid (TPA) is 1:(14-17): 1.
6. catalyst CuBr as claimed in claim 42@UiO-66-NH2-CF3The preparation method of COOH, which is characterized in that step
Suddenly in (1), the CF3The concentration of the aqueous solution of COOH is 5-7mol/L；
Preferably, in step (1) and (2), the condition of the drying process are as follows: treatment temperature is 60-90 DEG C, and the processing time is 8-
16 hours；Further preferably are as follows: treatment temperature is 80 DEG C, and the processing time is 12 hours.
7. catalyst CuBr as claimed in claim 42@UiO-66-NH2-CF3The preparation method of COOH, which is characterized in that step
Suddenly in (2), the copper bromide solution concentration is 3-6mg/mL；
Preferably, in step (2), the bromination copper solution is ethyl alcohol/methanol solution/acetonitrile solution of copper bromide；
Preferably, the UiO-66-NH2-CF3COOH and ethyl alcohol/methanol solution/acetonitrile mass volume ratio are (8-12) mg:
8ml；
Preferably, in step (1) and (2), the washing is to be washed with water or ethyl alcohol.
8. CuBr as described in any one of claims 1-32@UiO-66-NH2-CF3COOH and/or such as claim 4-7 are any
Application of the catalyst of method preparation described in catalysis sulfonic acid ester synthesis reaction.
9. application as claimed in claim 8, which is characterized in that method particularly includes: by p-nitrophenyl diazonium tetrafluoroborate,
DABSO, methanol, methylene chloride and CuBr2@UiO-66-NH2-CF3COOH is reacted after mixing to get p-nitrophenyl sulphur
Sour methyl esters.
10. application as claimed in claim 9, the reaction temperature is 25-29 DEG C；Preferably, the p-nitrophenyl tetrafluoro boron
Sour diazonium salt, DABSO, methanol and CuBr2@UiO-66-NH2-CF3The molar ratio of COOH is sequentially 1:1:245:0.002.
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| CN106378194A (en) * | 2016-08-25 | 2017-02-08 | 山东师范大学 | Transition metal copper loaded UiO-66-NH2 composite catalyst, preparation method and application thereof |
| KR20180036192A (en) * | 2016-09-30 | 2018-04-09 | 한국에너지기술연구원 | Metal-organic framework and preparing method thereof |
| CN108129478A (en) * | 2018-01-12 | 2018-06-08 | 曲阜师范大学 | A kind of copper catalysis synthetic method of organic sulphones and application |
| CN109776363A (en) * | 2019-03-19 | 2019-05-21 | 常州大学 | A kind of synthetic method of aryl sulfinic acid ester compounds |
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| CN106378194A (en) * | 2016-08-25 | 2017-02-08 | 山东师范大学 | Transition metal copper loaded UiO-66-NH2 composite catalyst, preparation method and application thereof |
| KR20180036192A (en) * | 2016-09-30 | 2018-04-09 | 한국에너지기술연구원 | Metal-organic framework and preparing method thereof |
| CN108129478A (en) * | 2018-01-12 | 2018-06-08 | 曲阜师范大学 | A kind of copper catalysis synthetic method of organic sulphones and application |
| CN109776363A (en) * | 2019-03-19 | 2019-05-21 | 常州大学 | A kind of synthetic method of aryl sulfinic acid ester compounds |
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| CN114471731A (en) * | 2022-03-02 | 2022-05-13 | 淮阴师范学院 | Preparation method, product and application of Cu (I) catalyst |
| CN114471731B (en) * | 2022-03-02 | 2022-10-04 | 淮阴师范学院 | Preparation method, product and application of Cu (I) catalyst |
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