CN107383386A - Method for preparing two-dimensional metal organic framework material and application thereof - Google Patents
Method for preparing two-dimensional metal organic framework material and application thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 26
- 239000013384 organic framework Substances 0.000 claims description 13
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 10
- 229940043267 rhodamine b Drugs 0.000 claims description 10
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 claims description 8
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229940109262 curcumin Drugs 0.000 claims description 4
- 235000012754 curcumin Nutrition 0.000 claims description 4
- 239000004148 curcumin Substances 0.000 claims description 4
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000013207 UiO-66 Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000013206 MIL-53 Substances 0.000 claims description 2
- 239000013132 MOF-5 Substances 0.000 claims description 2
- 239000013208 UiO-67 Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000013341 scale-up Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 235000000983 citronellal Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229930003633 citronellal Natural products 0.000 description 6
- ZYTMANIQRDEHIO-KXUCPTDWSA-N isopulegol Chemical compound C[C@@H]1CC[C@@H](C(C)=C)[C@H](O)C1 ZYTMANIQRDEHIO-KXUCPTDWSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- 239000001871 (1R,2R,5S)-5-methyl-2-prop-1-en-2-ylcyclohexan-1-ol Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 229940095045 isopulegol Drugs 0.000 description 3
- ZYTMANIQRDEHIO-UHFFFAOYSA-N neo-Isopulegol Natural products CC1CCC(C(C)=C)C(O)C1 ZYTMANIQRDEHIO-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- 239000013177 MIL-101 Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 240000004784 Cymbopogon citratus Species 0.000 description 1
- 235000017897 Cymbopogon citratus Nutrition 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001861 citronellal derivatives Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- -1 nitrogen-containing heterocycle compound Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
-
- 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
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a two-dimensional MOFs material, which comprises the following steps: mixing organic molecules with the metal organic framework material at normal temperature, then grinding or ball milling, washing, centrifuging and drying to obtain the two-dimensional metal organic framework material. The reaction condition for preparing the two-dimensional MOFs is mild, the reaction is rapid, the yield is high, no solvent is required to be added, the reaction process is simple, the required equipment is simple, and the ball mill can be used for realizing scale-up production.
Description
Technical field
The present invention relates to the field of metal-organic framework materials, more particularly to one kind prepares two-dimensional metallic organic framework material
Method and its application.
Background technology
Metal organic framework compound (metal organic frameworks, MOFs) is by metal ion or metal cluster
With organic ligand (binary or polybasic carboxylic acid, nitrogen-containing heterocycle compound etc.) self assembly and formed there is periodic network structure
The advantages that porous compounds, it has, and specific surface area is big, and porosity is high, and structure is adjustable, and symmetry is good, is widely used in gas
The fields such as storage, separation, drug delivery, catalysis and sensing.
Research to two-dimensional materials such as graphenes further triggered people to similar structure other are organic, metal is organic
The great interest of two-dimensional layer nano material.These two-dimensional materials have due to its excellent chemical tailorability, the long-range of structure
Sequence, ultra-thin property and attract attention, in terms of can be applied to bio-identification, catalysis, separation of small molecuies and purifying and electricity.
For three-dimensional MOFs, two-dimentional metal-organic framework materials have many good qualities, such as the more avtive spots in surface, more
Add flexibility etc., can apply to the fields such as electronics, photoelectron, molecule separation, catalysis.At present, two-dimensional metallic organic backbone material is prepared
Material has two major class method from top to bottom and from bottom to top.Top-to-bottom method is the MOFs of liquid phase stripped laminar, stratiform MOFs
Hydrogen bond or Van der Waals interaction between layers be present.Bottom-to-top method is directly synthesized in soft template or interface
Two-dimentional MOFs crystal.These method generally existing processes are complicated, and reaction speed is slow, low yield, the problems such as being not suitable for industrializing.
The content of the invention
It is an object of the invention to provide a kind of method for preparing two-dimensional metallic organic framework material, solves above-mentioned existing skill
One or more in art problem.
The present invention provides a kind of method for preparing two-dimentional MOFs materials, comprises the following steps：At normal temperatures by organic molecule
Mix, be then ground or ball milling with metal-organic framework materials, it is scrubbed, centrifuge, be dried to obtain the organic bone of two-dimensional metallic
Frame material.
In some embodiments, metal-organic framework materials are by metal ion or metal cluster and organic ligand self assembly
And a kind of porous compounds material formed.Wherein, in metal ion Zr, Cu, Al, Fe, Zn, Cr, Ti, Mn, Ni, Ag extremely
Few one kind, preferably at least one of Zr, Cu, Al, Fe, Zn, part are 2- amino terephthalic acid (TPA), terephthalic acid (TPA),
At least one of benzenetricarboxylic acid, 4,4 '-biphenyl dicarboxylic acid are preferred.
In some embodiments, the metal-organic framework materials are preferably
UiO-66 is (referring to document doi:10.1002/chem.200903526),
UiO-66-NH2(referring to document doi:10.1002/chem.200903526),
UiO-67 is (referring to document doi:10.1002/chem.201003211),
HKUST-1 is (referring to document doi:10.1021/ja056639q),
CuBDC is (referring to document doi:10.5012/bkcs.2004.25.12.1955),
MIL-53 is (referring to document doi:10.1021/ja0276974),
MIL-88 is (referring to document doi:10.1021/ja054900x),
MIL-101 is (referring to document doi:10.1016/j.progsolidstchem.2005.11.047),
MIL-101-NH2(referring to document doi:10.1039/c2dt30672g),
MOF-5 is (referring to document doi:10.1007/BF02700632).
Wherein, most preferably UiO-66, UiO-66-NH2, HKUST-1, MIL-101, MIL-101-NH2。
In some embodiments, organic molecule is excellent for the molecule of coordination can occur with metal-organic framework materials
Select rhodamine B, curcumin, p-methylbenzoic acid, 2- amino terephthalic acid (TPA)s, benzoic acid, 1,3,5-Benzenetricarboxylic acid, two pyridine carboxylic acids.
The common ground of these organic molecular structures is that have carboxyl or carbonyl.
In some embodiments, the mass ratio of the organic molecule of the addition and metal-organic framework materials is 1:1~
1:11.Wherein preferably 1:4~1:6, when mass ratio is higher or lower than this ratio, two-dimentional MOFs yield is all relatively low.
In some embodiments, the milling time is 1min~2h, preferably 8min~30min.
In some embodiments, the rotating speed of ball milling is 50r/min~1000r/min, preferably 100r/min~300r/
min；Ratio of grinding media to material is 15:1~30:1, the time is 30min~4h.
In some embodiments, application of the two-dimensional metallic organic backbone that prepared by described method in catalytic field,
For the catalyst reacted as acidic site.
Beneficial effect：
1st, the advantage of the invention is that the reaction condition for preparing two-dimentional MOFs is gentle, rapid reaction, yield height, it is not necessary to add
Enter solvent.
2nd, the advantage of the invention is that the course of reaction for preparing two-dimentional MOFs is simple, required device simple, ball mill can be used
Realize amplification production.
Brief description of the drawings
Fig. 1 is to grind UiO-66-NH in embodiment 12Front and rear XRD comparison diagrams；
Fig. 2 is the UiO-66-NH prepared in embodiment 12With the two-dimentional MOFs of preparation electron scanning micrograph
(SEM), wherein (a) is the UiO-66-NH prepared2；(b) the two-dimentional MOFs to prepare；
Fig. 3 is to grind UiO-66-NH in comparative example 32The SEM of product afterwards.
Embodiment
With reference to embodiment, the invention will be further described.Following examples are only intended to clearly illustrate this
The performance of invention, and the following examples can not be limited only to.
Embodiment 1：
Prepare metal-organic framework materials UiO-66-NH2
0.1864g zirconium chloride and 0.07246g 2- amino terephthalic acid (TPA) are dissolved in 40mL DMF respectively,
Zirconium chloride DMF solution and 10mL acetic acid are added into the DMF solution of 2- amino terephthalic acid (TPA)s, is put into after ultrasonic mixing is uniform
In baking oven, 120 DEG C of reaction 24h.Centrifugation, is washed 3 times with DMF, is exchanged and activated with methanol, soaks 12h, totally 2 times, again with methanol washes 3
It is secondary, it is dried to obtain UiO-66-NH2。
It is 1 in mass ratio by rhodamine B and UiO-66-NH2 under normal temperature:6 is well mixed, 8min is ground, by products therefrom
Washed, centrifuged, being dried, obtaining two-dimentional MOFs nanometer sheets.Then XRD is carried out to gained sample, SEM is characterized, such as Fig. 1 and figure
Shown in 2.
Embodiment 2-5：
Metal-organic framework materials UiO-66-NH is prepared as described in Example 12
Under normal temperature, by rhodamine B and UiO-66-NH2It is 1 in mass ratio respectively:1、1:4、1:5、1:11 is well mixed, grinds
8min is ground, products therefrom is washed, centrifuged, is dried, obtains two-dimentional MOFs nanometer sheets.
Embodiment 6-12：
Metal-organic framework materials UiO-66-NH is prepared as described in Example 12
Under normal temperature, by several different organic molecules and UiO-66-NH2It is 1 in mass ratio:5 is well mixed, grinding
8min, organic molecule include curcumin, p-methylbenzoic acid, 2- amino terephthalic acid (TPA)s, benzoic acid, 1,3,5-Benzenetricarboxylic acid, two
Pyridine carboxylic acid.Products therefrom is washed, centrifuged, is dried, can obtain two-dimentional MOFs nanometer sheets.
Embodiment 13-15：
Metal-organic framework materials UiO-66-NH is prepared as described in Example 12
Under normal temperature, by p-methylbenzoic acid and UiO-66-NH2It is 1 in mass ratio:5 is well mixed, is added to ball grinder
In.The rotating speed of ball milling is respectively 50,300,1000r/min, ratio of grinding media to material 30:1,20:1,15:1, time 4h, 2h, 30min.
Two-dimentional MOFs nanometer sheets can be obtained.When rotational speed of ball-mill is 300r/min, ratio of grinding media to material 20:1, when the time is 30min, two dimension
The yield highest of MOFs nanometer sheets.
Embodiment 16：
Weigh 1.820g Cu (NO3)2﹒ 3H2O and 0.875g H3BTC is dissolved separately in 50ml methanol, ultrasound to solution
Clarification, then by Cu (NO3)2﹒ 3H2O methanol solutions add H3In BTC methanol solutions, 2h is stored at room temperature, goes upper solution, is obtained
To sediment, washed 3 times with methanol, be put into 80 DEG C of baking ovens and dry, obtain HKUST-1.
Under normal temperature, curcumin is 1 in mass ratio with HKUST-1:4 is well mixed, grinds 30min, products therefrom is carried out
Washing, centrifugation, dry, obtain two-dimentional MOFs nanometer sheets.
Comparative example 1-2：
Metal-organic framework materials UiO-66-NH is prepared as described in Example 12
By rhodamine B and UiO-66-NH2Mixed by different mass ratioes, mass ratio is respectively 1:15、2:1, grinding
8min, products therefrom is washed, centrifuged, is dried, obtained two-dimentional MOFs nanometer sheets.
Comparative example 3：
Under normal temperature, organic molecule is added without, directly grinds UiO-66-NH2, 8min is ground, products therefrom is washed,
Centrifugation, dry, it is impossible to prepare two-dimentional MOFs nanometer sheets, products therefrom is the UiO-66-NH of some destructions of pattern2, such as Fig. 3 institutes
Show.So organic molecule has been participated in the two-dimentional MOFs of generation reaction.
Comparative example 4：
Under normal temperature, zirconium chloride and rhodamine B 8min are ground, products therefrom is washed, centrifuged, is dried, is not obtained
Two-dimentional MOFs, products therefrom are cube.2- amino terephthalic acid (TPA) and rhodamine B, products therefrom are ground under the same conditions
For the crystal of three-dimensional, two-dimentional MOFs can not be prepared.So only grinding MOFs and rhodamine B can just prepare two dimension
MOFs。
Following table is rhodamine B and UiO-66-NH2Influence of the mass ratio to two-dimentional MOFs yield.
| Comparative example | Rhodamine B and UiO-66-NH2Mass ratio | Two-dimentional MOFs yield |
| Embodiment 1 | 1:6 | Than 1:5 yield are slightly lower |
| Embodiment 2 | 1:1 | It is relatively low |
| Embodiment 3 | 1:4 | Than 1:5 yield are slightly lower |
| Embodiment 4 | 1:5 | Highest |
| Embodiment 5 | 1:11 | It is relatively low |
| Comparative example 1 | 1:15 | 0 |
| Comparative example 2 | 2:1 | 0 |
As seen from the above table, mass ratio 1:Two dimension MOFs yield highest when 5, the two-dimentional MOFs obtained by other mass ratioes
Yield is all relatively low.
Catalytic performance test is carried out by the cyclization of citronellal.
The cyclisation experimental procedure of citronellal：5mL toluene and 465 μ L citronellals are added in 50mL round-bottomed flask, are added
The ratio of metal ion is 15 in catalyst, wherein citronellal and catalyst:1, then 10h is reacted at 110 DEG C, it is anti-to complete catalysis
Should.
Experiment 1：By embodiment 1 using it is obtained obtain two-dimentional MOFs nanometer sheets as catalyst be used for citronellal cyclisation it is anti-
Should, the yield for obtaining isopulegol is 23%.
Experiment 2：Embodiment 11 is obtained obtained two-dimentional MOFs nanometer sheets and be used for lemongrass as by obtained catalyst
The cyclization of aldehyde, the yield for obtaining isopulegol are 25%.
Experiment 3：Directly by UiO-66-NH2It is used for the cyclization of citronellal as catalyst, obtains isopulegol
Yield is 7.8%.
Catalytic performance test is understood：The two-dimentional MOFs nanometer sheets that the implementation case obtains are in the cyclization of citronellal
Catalytic activity is far above its catalytic activity of corresponding MOFs materials in itself.
In embodiment provided by the invention, it is gentle to prepare two-dimentional MOFs reaction condition, rapid reaction, and yield is high, no
Need to add solvent, and course of reaction is simple, required device simple, and amplification production can be realized with ball mill.Obtain two-dimentional MOFs
Its catalytic activity has greatly improved in itself compared with MOFs materials.
Presented above is only the preferred embodiment of the present invention, it is noted that to those skilled in the art, not
On the premise of departing from the invention design, various modifications and improvements can be made, these also should be regarded as the protection of the present invention
Within the scope of.
Claims (8)
- A kind of 1. method for preparing two-dimensional metallic organic framework material, it is characterised in that comprise the following steps：To have at normal temperatures Machine molecule mixes with metal-organic framework materials, is then ground or ball milling, scrubbed, centrifuge, be dried to obtain two-dimensional metallic Organic framework material.
- A kind of 2. method for preparing two-dimensional metallic organic framework material according to claim 1, it is characterised in that the gold Category organic framework material is by metal ion or metal cluster and organic ligand self assembly and a kind of porous compounds material for being formed, The metal ion is at least one of Zr, Cu, Al, Fe, Zn, Cr, Ti, Mn, Ni, Ag, and the organic ligand is 2- amino At least one of terephthalic acid (TPA), terephthalic acid (TPA), trimesic acid, 4,4 '-biphenyl dicarboxylic acid.
- A kind of 3. method for preparing two-dimensional metallic organic framework material according to claim 1 or 2, it is characterised in that institute It is UiO-66, UiO-66-NH to state metal-organic framework materials2、UiO-67、HKUST-1、CuBDC、MIL-53、MIL-88、MIL- 101、MIL-101-NH2, at least one of MOF-5.
- 4. a kind of method for preparing two-dimensional metallic organic framework material according to claim 1, it is characterised in that described to have Machine molecule is rhodamine B, curcumin, p-methylbenzoic acid, 2- amino terephthalic acid (TPA)s, benzoic acid, 1,3,5-Benzenetricarboxylic acid, two pyridines At least one of formic acid.
- 5. a kind of method for preparing two-dimensional metallic organic framework material according to claim 1, it is characterised in that described to add The organic molecule and the mass ratio of metal-organic framework materials entered is 1:1~1:11.
- 6. a kind of method for preparing two-dimensional metallic organic framework material according to claim 1, it is characterised in that described to grind Consume time as 1min~2h.
- A kind of 7. method for preparing two-dimensional metallic organic framework material according to claim 1, it is characterised in that the ball The rotating speed of mill is 50r/min~1000r/min, ratio of grinding media to material 15:1~30:1, Ball-milling Time is 30min~4h.
- 8. two-dimensional metallic prepared by a kind of method for preparing two-dimensional metallic organic framework material according to claim 1 is organic Application of the skeleton in catalytic field, for the catalyst reacted as acidic site.
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