CN105693506A - Synthesis method of porous titanium crystal metal organic framework material - Google Patents
Synthesis method of porous titanium crystal metal organic framework material Download PDFInfo
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- CN105693506A CN105693506A CN201610072923.7A CN201610072923A CN105693506A CN 105693506 A CN105693506 A CN 105693506A CN 201610072923 A CN201610072923 A CN 201610072923A CN 105693506 A CN105693506 A CN 105693506A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 55
- 239000010936 titanium Substances 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 45
- 239000013078 crystal Substances 0.000 title abstract description 5
- 238000001308 synthesis method Methods 0.000 title abstract 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012046 mixed solvent Substances 0.000 claims abstract description 20
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000013110 organic ligand Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 38
- 238000010189 synthetic method Methods 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- WWECJGLXBSQKRF-UHFFFAOYSA-N n,n-dimethylformamide;methanol Chemical compound OC.CN(C)C=O WWECJGLXBSQKRF-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- 238000011160 research Methods 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- MPDGHEJMBKOTSU-YKLVYJNSSA-N 18beta-glycyrrhetic acid Chemical compound C([C@H]1C2=CC(=O)[C@H]34)[C@@](C)(C(O)=O)CC[C@]1(C)CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@H](O)C1(C)C MPDGHEJMBKOTSU-YKLVYJNSSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910002661 O–Ti–O Inorganic materials 0.000 description 1
- 229910002655 O−Ti−O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/26—1,4 - Benzenedicarboxylic acid
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- B01J31/223—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
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
Abstract
The invention discloses a synthesis method of a porous titanium crystal metal organic framework material. According to the method, dimethylformamide and methanol are used as a mixed solvent, terephthalic acid is used as an organic ligand, and isopropyl titanate is used as a titanium source. The method comprises the following steps: mixing terephthalic acid and isopropyl titanate to obtain a mixture, adding the mixture into a dimethylformamide-methanol solution mixed solvent, stirring at room temperature until all the solids are completely dissolved, transferring into a reaction kettle, and reacting at 120-180 DEG C for 12-20 hours; and after the reaction finishes, cooling the white floccule to room temperature to obtain a white precipitate, filtering, drying in a drying oven, washing with acetone, airing at room temperature, and roasting at 150-250 DEG C for 10-25 hours. The appropriate solvent and organic ligand are selected, and the reaction conditions are controlled to improve the existing method, thereby obtaining a synthesis method which is performed under refined technological conditions but is easy to popularize.
Description
Technical field
The present invention relates to the synthetic technology of a kind of metal-organic framework materials, be specifically related to the synthetic method of a kind of POROUS TITANIUM crystalline substance metal-organic framework materials。
Background technology
Metal-organic framework materials (Metal-OrganicFrameworks, MOFs) is utilize metal-ligand complex effect between organic ligand and metal ion by MOFs material and a kind of class zeolite (organic zeolite analog) material having much future of supermolecule microporous network structure of being self-assembly of。This stephanoporate framework crystalline material, can connecting organic ligand by different metal ion and various rigid bridges and carry out complexation, the metallic organic framework designing with synthesizing different pore size, so that the structure of MOFs is with countless changes, and such as-Br ,-NH can be brought on organic ligand2,-OC3H7,-OC5H11Deng some functional modification groups, make this MOFs microporous polymer can according to the performance requirement such as catalytic reaction or absorption functionalization。Owing to MOFs has tempting application prospect in fields such as gas storage, catalysis, obtain fast development in recent years, become an emerging field of material science research。
MOFs has several advantage: first, and MOFs preparation is simple。The reactivity of carboxylic acid and Nitrogen-Containing Heterocyclic Ligand and metal ion is significantly high, and therefore the synthesis of MOFs adopts one-step method more, and namely metal ion and organic ligand self assembly form；Secondly, coordination ability can change。Due to the electrostatic effect of lewis acid and metal ion, functional group and coordination property in part can change neatly；It addition, metal ion has two effects, the summit as skeleton not only can provide maincenter but also can form branch at maincenter, and by the two effect, skeleton is extended, thus forming multidimensional structure。
The advantage of these several respects of MOFs determines its Some features having as solid material: (1) porous。The MOFs great majority of bibliographical information all had permanent hole in recent years, and the scope in aperture existsSmaller hole diameter Cu2(PZDC)2(DPYG) suitable with the diameter of typical zeolite, the representative MOFs of diameter macropores is Zn4O(TPDC)3。MOFs not only has porous, and the shape in hole also has multiformity, and this is mainly by the structure of organic ligand and what shape determined。By selecting the organic ligand of structure and the shape being suitable for just can control the structure in hole of MOFs and the size of synthesis, thus controlling porosity and the specific surface area of skeleton, obtain being suitable for the porous material that different application requires。
At present, mainly there are Univ Michigan-Ann Arbor USA Yaghi research group and the Ferey research group of France's Antoine Lavoisier institute in the mechanism abroad carrying out MOFs investigation of materials。Univ Michigan-Ann Arbor USA design of material headed by Yaghi and research group have done substantial amounts of basic work in the synthesis of MOFs material。The domestic research also having some computer MSR Information system to have begun to this respect。2002, trip was imitated once academician's research group and is utilized Co (II) and imidazoles to synthesize the molecular sieve analog structure [Co of a rare 3 D pore canal5(im) 10 2MB]。Although being at present no matter at home or abroad, there is the multiple method preparing MOFs material；But, these methods there is also many limitations for design and the exploitation of this kind of material function。
Along with high speed development and the progress of human civilization of science and technology, various environmental pollutions are increasingly severe, and utilizing photocatalysis elimination and degradation of contaminant is one of the research field of current most active, and people have researched and developed many photocatalysts, wherein, and nano-TiO2Inexpensive with it, nontoxic, stability is high, catalytic performance good, can the advantage such as recycling, get the attention。But due to Detitanium-ore-type TiO2Energy gap wider, need to could show catalysis activity under entering the exciting of ultraviolet light of < 387 5nm, and the energy in sunlight medium ultraviolet light district only accounts for the 6% of gross energy, and the relatively low visible ray of energy accounts for the 43% of gross energy。Due to Key Scientific And Technical difficult problems such as its quantum yield are low, solar energy utilization ratio is low, greatly constrain its extensive use industrially。Also utilize at present and obtain the method relative complex that POROUS TITANIUM is brilliant, it is difficult to extensive use。
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide the synthetic method of a kind of POROUS TITANIUM crystalline substance metal-organic framework materials, by selecting suitable solvent and organic ligand and controlling reaction condition existing method is improved, it is thus achieved that the refinement of a kind of process conditions but the synthetic method easily promoted。
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of synthetic method of POROUS TITANIUM crystalline substance metal-organic framework materials, this synthetic method with dimethylformamide be solvent, p-phthalic acid be organic ligand, isopropyl titanate for titanium source, comprise the following steps:
1) first p-phthalic acid and isopropyl titanate are mixed to get mixture, mixture joins in dimethylformamide and methanol solution mixed solvent, at room temperature stirring is until solids is completely dissolved, and is then transferred in reactor at 120-180 DEG C of temperature and reacts 12-20 hour；
2), after reaction terminates, obtain White Flocculus, then White Flocculus is cooled to room temperature, obtain white precipitate；
3) by step 2) precipitation of white that obtains dries in an oven after filtering, afterwards with washing with acetone, at room temperature dries, obtain powder, then roasting 10-25 hour at 150-250 DEG C；Namely POROUS TITANIUM crystalline substance metal-organic framework materials is obtained。
In further scheme, step 1 of the present invention) in the ratio of p-phthalic acid and the amount of substance of isopropyl titanate be (1.2-1.8): 1.0。
In further scheme, step 1 of the present invention) in mixed solvent the volume ratio of dimethylformamide and methanol be (8-10): 1。
In further scheme, step 1 of the present invention) temperature of reactor is 150 DEG C, the response time is 15 hours。
In further scheme, step 2 of the present invention) in, the temperature of baking oven is 60-90 DEG C。
In further scheme, step 2 of the present invention) in the temperature of roasting be 200 DEG C, roasting time is 12 hours。
In further scheme, step 3 of the present invention) in by the process of washing with acetone be: the product after oven for drying is distributed in acetone, filters after stirring；Repeat said process 2-4 time。
In further scheme, step 3 of the present invention) obtained POROUS TITANIUM crystalline substance metal-organic framework materials specific surface area is 1200-1800m2/ g, pore volume is 0.2-0.3cm3/ g；Average pore size is 1-1.5nm。
Compared to existing technology, the beneficial effects of the present invention is:
1. synthetic method of the present invention is to have synthesized metal-organic framework materials-POROUS TITANIUM crystalline substance with disc-shaped structure under the pressure itself that reactant self assembly produces, and this material has good heat stability and absorbability；
2. in synthetic method of the present invention, POROUS TITANIUM crystalline substance is formed by layer growth mode, by washing the small solvent molecule and unreacted organic ligand that can avoid attachment on sample；
3. synthetic method of the present invention adopts solvent method synthetic product, and byproduct of reaction is few, it is easy to purify, improve the outward appearance of crystal。
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail。
Accompanying drawing explanation
Fig. 1 is the XRD test result figure of the POROUS TITANIUM crystalline substance metal-organic framework materials described in embodiment 3；
Fig. 2 is the FTIR test result figure of the POROUS TITANIUM crystalline substance metal-organic framework materials described in embodiment 1-3；
Fig. 3 be the POROUS TITANIUM crystalline substance metal-organic framework materials described in embodiment 3 thermogravimetric curve figure；
Fig. 4 is the nitrogen adsorption-desorption curve figure of the POROUS TITANIUM crystalline substance metal-organic framework materials described in embodiment 3；
Fig. 5 is the scanning electron microscope (SEM) photograph of the POROUS TITANIUM crystalline substance metal-organic framework materials described in embodiment 3, and scale is 2 μm；
Fig. 6 is the scanning electron microscope (SEM) photograph of the POROUS TITANIUM crystalline substance metal-organic framework materials described in embodiment 3, and scale is 1 μm。
Detailed description of the invention
The synthetic method of POROUS TITANIUM crystalline substance metal-organic framework materials of the present invention, this synthetic method with dimethylformamide (DMF) and methanol be mixed solvent, p-phthalic acid (BDC) be organic ligand, isopropyl titanate (Ti (OiPr)4) for titanium source, comprise the following steps:
1) first p-phthalic acid and isopropyl titanate are mixed to get mixture, mixture joins in dimethylformamide and methanol solution mixed solvent, at room temperature stirring is until solids is completely dissolved, and is then transferred in reactor at 120-180 DEG C of temperature and reacts 12-20 hour；
2), after reaction terminates, obtain White Flocculus, then White Flocculus is cooled to room temperature, obtain white precipitate；
3) by step 2) precipitation of white that obtains dries in an oven after filtering, afterwards with washing with acetone, at room temperature dries, obtain powder, then roasting 10-25 hour at 150-250 DEG C；Namely POROUS TITANIUM crystalline substance metal-organic framework materials is obtained。
Synthesis mechanism is as follows:
In the present invention, the reaction of reactant and the acquisition of product are had a certain impact by reactant interpolation volume order；In order to prevent the pressed powder BDC adhesion beaker bottom being initially charged, not readily dissolve, therefore first BDC is mixed with isopropyl titanate, be then then added in mixed solvent。
The ratio of metal ion and organic ligand also largely affects the performance of skeleton。When the ratio of metal exceedes the stoichiometric proportion of coordination, part can fully with the coordination of many flute profiles, and metal have unsaturated position exist, the research especially catalytic action for skeleton property is very favorable；Otherwise, part is it is possible to can be all or part of with monodentate type coordination, and the skeleton of formation is likely not to have that the former is stable, and not or only have the unsaturated position of minimal amount of metal。Therefore, in the above-mentioned methods, further scheme, step 1 of the present invention) in the ratio of p-phthalic acid and the amount of substance of isopropyl titanate be (1.2-1.8): 1.0。Wherein preferred mol ratio is p-phthalic acid: isopropyl titanate=1.5: 1.0。
Due to mixed solvent can the polarity of regulation system and solvent-ligand exchange kinetics, affect crystal growth rate；Therefore, in the synthetic method of the present invention, adopt mixed solvent and by controlling the ratio between mixed solvent, make in the scope being grown in examining of POROUS TITANIUM crystalline substance, and solve the problem that reactant at room temperature not readily dissolves。In further scheme, of the present invention rapid 1) in, in mixed solvent, the volume ratio of dimethylformamide and methanol is (8-10): 1。Preferably both volume ratios are 9: 1。
Finding in the research of the present invention, react at different temperatures, the coordination ability of carboxyl is different, thus the framing structure generated is just different, carboxyl is with the coordination of many flute profiles under the high temperature conditions, is easily formed multidimensional structure；And at ambient temperature with monodentate type coordination, it is easily formed one-dimentional structure；Therefore in the present invention, react 120-180 DEG C of temperature by controlling the temperature of reactor, to obtain the product of compound application claims。In preferred scheme, step 1 of the present invention) temperature of reactor is 150 DEG C, the response time is 15 hours。
In further scheme, step 2 of the present invention) in, the temperature of baking oven is 60-90 DEG C。Preferably, oven temperature is 80 DEG C。Within the scope of said temperature, the product after drying is unaffected。Product, after the drying by washing with acetone about 3 times, is specifically disperseed in acetone by product, and agitator treating about 3 times, the little molecule of the free solvent remained in the greatest extent in product can better be washed by sample, makes product can have better catalytic performance。
In further scheme, step 2 of the present invention) in the temperature of roasting be 200 DEG C, roasting time is 12 hours。
In further scheme, step 3 of the present invention) obtained POROUS TITANIUM crystalline substance metal-organic framework materials specific surface area is 1200-1800m2/ g, pore volume is 0.2-0.3cm3/ g；Average pore size is 1-1.5nm。
The following is specific embodiment of the present invention, in following embodiment, the source of reagent and equipment is as follows: isopropyl titanate Ti (OiPr)4(AlfaAesar, 97%), p-phthalic acid BDC (Chemical Reagent Co., Ltd., Sinopharm Group, >=99%), dimethylformamide DMF (Beijing T factory, >=99.5%), methanol (α Cygni friend fine chemicals company limited, 99.9%)；All reagent, without entering purification, are directly used in experiment。The instrument and equipment used has: 85-1 type magnetic stirring apparatus (Medical Instruments factory of Jintan City), AnkeTGL-16c type centrifuge (Anting Scientific Instrument Factory, Shanghai), DZ-1BC type vacuum drying oven (Tianjin Stettlen Instrument Ltd.)。
Embodiment 1
A kind of synthetic method of POROUS TITANIUM crystalline substance metal-organic framework materials, this synthetic method with dimethylformamide (DMF) and methanol be mixed solvent, p-phthalic acid (BDC) be organic ligand, isopropyl titanate (Ti (OiPr)4) for titanium source, comprise the following steps:
1) first p-phthalic acid and isopropyl titanate are mixed to get mixture, mixture joins in dimethylformamide and methanol solution mixed solvent, at room temperature stirring is until solids is completely dissolved, and is then transferred in reactor at 120 DEG C of temperature and reacts 20 hours；
2), after reaction terminates, obtain White Flocculus, then White Flocculus is cooled to room temperature, obtain white precipitate；
3) by step 2) precipitation of white that obtains dries in an oven after filtering, afterwards with washing with acetone, at room temperature dries, obtain powder, then roasting 25 hours at 150 DEG C；Namely POROUS TITANIUM crystalline substance metal-organic framework materials is obtained。
Embodiment 2
A kind of synthetic method of POROUS TITANIUM crystalline substance metal-organic framework materials, this synthetic method with dimethylformamide (DMF) and methanol be mixed solvent, p-phthalic acid (BDC) be organic ligand, isopropyl titanate (Ti (OiPr)4) for titanium source, comprise the following steps:
1) first p-phthalic acid and isopropyl titanate are mixed to get mixture, mixture joins in dimethylformamide and methanol solution mixed solvent, at room temperature stirring is until solids is completely dissolved, and is then transferred in reactor at 180 DEG C of temperature and reacts 12 hours；
2), after reaction terminates, obtain White Flocculus, then White Flocculus is cooled to room temperature, obtain white precipitate；
3) by step 2) precipitation of white that obtains dries in an oven after filtering, afterwards with washing with acetone 2 times, at room temperature dries, obtain powder, then roasting 10 hours at 250 DEG C；Namely POROUS TITANIUM crystalline substance metal-organic framework materials is obtained。
Embodiment 3
A kind of synthetic method of POROUS TITANIUM crystalline substance metal-organic framework materials, this synthetic method with dimethylformamide (DMF) and methanol be mixed solvent, p-phthalic acid (BDC) be organic ligand, isopropyl titanate (Ti (OiPr)4) for titanium source, comprise the following steps:
1) first p-phthalic acid and isopropyl titanate are mixed to get mixture, mixture joins in dimethylformamide and methanol solution mixed solvent, at room temperature stirring is until solids is completely dissolved, and is then transferred in reactor at 150 DEG C of temperature and reacts 15 hours；
2), after reaction terminates, obtain White Flocculus, then White Flocculus is cooled to room temperature, obtain white precipitate；
3) by step 2) precipitation of white that obtains dries in an oven after filtering, afterwards with washing with acetone 3 times, at room temperature dries, obtain powder, then roasting 15 hours at 200 DEG C；Namely POROUS TITANIUM crystalline substance metal-organic framework materials is obtained。
Performance test
1. the POROUS TITANIUM crystalline substance metal-organic framework materials described in pair embodiment 3 carries out X-ray diffraction experiment, it is test between 3.0 °-80 ° at 2 θ, the diffractometer that INSTRUMENT MODEL is RigakuD/max-3a adopted, test voltage is 40kv, electric current 30mA, 8 DEG C/min of scanning speed。
Diffraction patterns shows referring to the result of Fig. 1, Fig. 1: XRD diffraction pattern is completely the same with the diffraction pattern in reference material。Illustrate that POROUS TITANIUM crystalline substance is successfully synthesized。
2. the POROUS TITANIUM crystalline substance metal-organic framework materials that pair embodiment 1-embodiment 3 is obtained carries out FTIR test。
Test result is shown in that the result of Fig. 2, Fig. 2 shows: at 1380cm-1And 1600cm-1The characteristic peak that peak is carboxyl that place occurs。400cm-1And 800cm-1The absorption of vibrations that the absworption peak of the shortwave number occurred is then O-Ti-O causes。This illustrates in prepared material, and the material with carboxyl and the material with Ti occur simultaneously。
3. the POROUS TITANIUM crystalline substance metal-organic framework materials of pair embodiment 3 carries out TGA test。
Test result is shown in Fig. 3, the result of Fig. 3 shows: contained guest molecules is removed, therefore the sign of thermal weight loss is at this moment done again, it finds that, obvious weight-loss curve was not had to occur before 200 DEG C, but start to decompose at 279.7 DEG C, deducibility is to leave away due to the unnecessary terephthaldehyde's acid molecule in system to cause, and second time weightlessness started when 361 DEG C is then the temperature that the skeleton of synthesized metal-organic framework materials starts decomposition。Secondly and metal-organic framework materials decomposes in the temperature relatively document of most Zhongdao higher, about about 550 DEG C, there is good stability。
4. the POROUS TITANIUM crystalline substance metal-organic framework materials of pair embodiment 3 carries out BET test under 77K。
Test result is shown in that the result of Fig. 4, Fig. 4 shows: the adsorption-desorption curve of Fig. 4 is typical typeI type micro-porous adsorption curve, is 1610.510m by BET method calculated specific surface area2/ g, pore volume is 0.297cm3/ g。Pore size distribution result of calculation shows, average pore size is 1.405nm。Isothermal curve shows, when, in the process of desorption, there is a receipt ring, illustrating that POROUS TITANIUM crystalline substance metal-organic framework materials not only can have the performance of gas absorption, also can well be discharged by gas when gas discharges, it is not necessary to too much extraneous ability auxiliary。
5. POROUS TITANIUM crystalline substance metal-organic framework materials electron microscope scanning (SEM) test of pair embodiment 3。
Test result is 2 μm referring to the scale in Fig. 5 and Fig. 6, Fig. 5, and the scale in Fig. 6 is 1 μm。The result of Fig. 5 and Fig. 6 represents that the POROUS TITANIUM crystalline substance metal-organic framework materials of embodiment 3 defines very regular crystal form, and crystallization degree is higher, and becomes roundlet lamellar, and diameter is about 2 μm, and thickness is about 0.8 μm。
Above-mentioned embodiment is only the preferred embodiment of the present invention, it is impossible to limit the scope of protection of the invention with this, and the change of any unsubstantiality that those skilled in the art does on the basis of the present invention and replacement belong to present invention scope required for protection。
Claims (8)
1. the synthetic method of a POROUS TITANIUM crystalline substance metal-organic framework materials, it is characterised in that this synthetic method with dimethylformamide and methanol be mixed solvent, p-phthalic acid be organic ligand, isopropyl titanate for titanium source, comprise the following steps:
1) first p-phthalic acid and isopropyl titanate are mixed to get mixture, mixture joins in dimethylformamide and methanol solution mixed solvent, at room temperature stirring is until solids is completely dissolved, and is then transferred in reactor at 120-180 DEG C of temperature and reacts 12-20 hour；
2), after reaction terminates, obtain White Flocculus, then White Flocculus is cooled to room temperature, obtain white precipitate；
3) by step 2) precipitation of white that obtains dries in an oven after filtering, afterwards with washing with acetone, at room temperature dries, obtain powder, then roasting 10-25 hour at 150-250 DEG C；Namely POROUS TITANIUM crystalline substance metal-organic framework materials is obtained。
2. synthetic method according to claim 1, it is characterised in that step 1) in the ratio of p-phthalic acid and the amount of substance of isopropyl titanate be (1.2-1.8): 1.0。
3. synthetic method according to claim 1, it is characterised in that step 1) in mixed solvent the volume ratio of dimethylformamide and methanol be (8-10): 1。
4. synthetic method according to claim 1, it is characterised in that step 1) temperature of reactor is 150 DEG C, the response time is 15 hours。
5. synthetic method according to claim 1, it is characterised in that step 2) in, the temperature of baking oven is 60-90 DEG C。
6. synthetic method according to claim 1, it is characterised in that step 2) in the temperature of roasting be 200 DEG C, roasting time is 12 hours。
7. synthetic method according to claim 1, it is characterised in that step 3) in by the process of washing with acetone be: the product after oven for drying is distributed in acetone, after stirring filter；Repeat said process 2-4 time。
8. synthetic method according to claim 1, it is characterised in that step 3) obtained POROUS TITANIUM crystalline substance metal-organic framework materials specific surface area is 1200-1800m2/ g, pore volume is 0.2-0.3cm3/ g；Average pore size is 1-1.5nm。
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| CN107335471A (en) * | 2017-08-11 | 2017-11-10 | 哈尔滨工业大学 | A kind of preparation method of the multi-stage porous titanium terephthalic acid metal organic catalyst with efficiently catalyzing and oxidizing activity |
| CN108666573A (en) * | 2018-04-23 | 2018-10-16 | 曲靖师范学院 | A kind of preparation method of titanium-based MOF lithium ion battery negative materials |
| CN109897846A (en) * | 2019-04-03 | 2019-06-18 | 辽宁大学 | A kind of immobilized glucose oxidase and its preparation method and application |
| CN114160102A (en) * | 2020-09-11 | 2022-03-11 | 中国科学院大连化学物理研究所 | Adsorbent and application thereof |
| CN114163650A (en) * | 2020-09-11 | 2022-03-11 | 中国科学院大连化学物理研究所 | Metal organic framework material MIL-125 and preparation method and application thereof |
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| CN114160102B (en) * | 2020-09-11 | 2022-11-01 | 中国科学院大连化学物理研究所 | Adsorbent and application thereof |
| CN115245764A (en) * | 2022-03-14 | 2022-10-28 | 大连理工大学 | Method for preparing titanium-based metal organic framework film by titanium-oxygen cluster |
| CN115245764B (en) * | 2022-03-14 | 2023-11-21 | 大连理工大学 | Method for preparing titanium-based metal organic framework film by using titanium oxide clusters |
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