CN110078751A - A kind of porous crystalline material and preparation method thereof with NaCl type - Google Patents
A kind of porous crystalline material and preparation method thereof with NaCl type Download PDFInfo
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- CN110078751A CN110078751A CN201910281240.6A CN201910281240A CN110078751A CN 110078751 A CN110078751 A CN 110078751A CN 201910281240 A CN201910281240 A CN 201910281240A CN 110078751 A CN110078751 A CN 110078751A
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- Prior art keywords
- porous crystalline
- crystalline material
- zinc
- nacl type
- secondary building
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims abstract description 61
- 239000002178 crystalline material Substances 0.000 title claims abstract description 61
- 239000011780 sodium chloride Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- 239000013110 organic ligand Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 8
- 238000010537 deprotonation reaction Methods 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 230000005595 deprotonation Effects 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- LGDUFVRMPIUMNT-UHFFFAOYSA-N C(=O)N(CC)CC.[N].[N] Chemical compound C(=O)N(CC)CC.[N].[N] LGDUFVRMPIUMNT-UHFFFAOYSA-N 0.000 claims description 3
- UNZSJASIKFONPS-UHFFFAOYSA-N C(C)(=O)N(C)C.[N].[N] Chemical compound C(C)(=O)N(C)C.[N].[N] UNZSJASIKFONPS-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- -1 oxygen anion Chemical class 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 2
- OUYLXVQKVBXUGW-UHFFFAOYSA-N 2,3-dimethyl-1h-pyrrole Chemical compound CC=1C=CNC=1C OUYLXVQKVBXUGW-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 abstract description 10
- 238000003860 storage Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 238000001994 activation Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 2
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000640 hydroxylating effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000000232 gallbladder Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- CHSMNMOHKSNOKO-UHFFFAOYSA-L zinc;dichloride;hydrate Chemical compound O.[Cl-].[Cl-].[Zn+2] CHSMNMOHKSNOKO-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/28014—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 form
-
- 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
- B01J20/28054—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 surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
Abstract
The present invention relates to a kind of porous crystalline material and preparation method thereof with NaCl type, contain four oxygen of zinc and vehicle two kinds of secondary building units of auxiliary formula in the skeleton structure of the porous crystalline material simultaneously, and two kinds of secondary building unit alternate links are built into the three-dimensional net structure of NaCl type jointly, preparation method is by zinc salt and organic ligand H2L1 and H1L1 is prepared through step dissolution thermal response.Preparation method is simple for porous crystalline material provided by the invention, structural stability is high, and the regulation of duct size and channel surfaces functional group can derive the porous crystalline material of serial isomorphism, is with a wide range of applications in Molecular Adsorption separation, storage.
Description
Technical field
The present invention relates to porous material technical fields, and in particular to a kind of porous crystalline material with NaCl type and its
Preparation method.
Background technique
Porous material, which separates the field of engineering technology such as absorption and storage, Industrial Catalysis, molecular recognition and sensing in gas, to be had
Extensive use.Therefore, novel porous materials are the motive power for pushing technological innovation, synthesis, structure and property research by
More and more attention of researcher.
From the end of the nineties in last century, two kinds of novel porous crystalline materials, MOF-5 based on Zn4O secondary building unit and
HKUST-1 based on the auxiliary formula secondary building unit of vehicle is taught by U.S. Omar Yaghi in Nature periodical and Hong Kong University of Science and Technology respectively
Ian D.WILLIAMS has been taught since Science periodical is reported to, and has started the novel porous crystalline state based on coordinate bond assembling
The research boom of material.This kind of material has the characteristics that be clearly distinguishable from conventional molecular sieve and porous carbon materials, comprising: according to several
The designability of what topological structure, unlimited structure possibility are easy to functionalization etc..Based on the porous of Zn4O secondary building unit
Crystalline material and porous crystalline material based on the auxiliary formula of vehicle are in all the time in parallel study development, with the depth of application study
Enter, respective disadvantage is also gradually found.
Based on the porous crystalline material of Zn4O secondary building unit, although showing high thermal stability, this kind of material exists
It is extremely easy in decomposition in air atmosphere environment, has seriously affected performance.The main reason for decomposition is that Zn4O secondary building unit is easy to by water
Molecule attack, causes coordinate bond to be broken.Although relatively preferable based on air atmosphere stability under its room temperature of the structural unit of the auxiliary formula of vehicle,
But low thermal stability and special structural flexibility cause this kind of porous crystalline material to receive great limit in the application
System.Therefore, although the porous crystalline material of both types shows excellent performance in laboratory environments, in practical work
It applies in condition environment and is but greatly challenged.
Summary of the invention
The purpose of the present invention is to solve the above-mentioned problems and provides one kind by four oxygen of zinc and the auxiliary formula secondary structure list of vehicle
The series multiwell crystalline material and preparation method thereof with NaCl type that member is constructed, novel porous crystalline state provided by the present invention
Material uses for reference the theory of mutual supplement with each other's advantages in structure design, can construct chlorine respectively with four oxygen of zinc and the auxiliary formula secondary building unit of vehicle
Change sodium form network structure as Theory Fulcrums, above two classical secondary building unit is dissolved into a NaCl type network knot
In structure, novel porous crystalline material is constructed, is provided for application study and has high thermal stability and air environment or even high humidity environment concurrently
The porous crystalline material of stability.
The purpose of the present invention is achieved through the following technical solutions:
A kind of porous crystalline material with NaCl type contains zinc four in the skeleton structure of the porous crystalline material simultaneously
Oxygen and vehicle two kinds of secondary building units of auxiliary formula, and two kinds of secondary building unit alternate links are built into the three-dimensional of NaCl type jointly
Network structure.
Further, the skeleton structure general molecular formula of the porous crystalline material is [Zn6(O)(L1)4(L2)2], in which:
L1 is the linear acids class ligand of complete deprotonation, and L2 is that the azole with triangle coordination geometric configuration of complete deprotonation is matched
Body, O are the oxygen anions of negative divalent state.
Four oxygen of zinc and vehicle two kinds of secondary building units of auxiliary formula form one-dimensional chain, one-dimensional chain is again by L2 alternate links
Four oxygen secondary building unit of zinc is linked by the one end L1, other end chain picks up auxiliary formula secondary building unit, and being finally linked into has
The three-dimensional porous crystalline material of sodium chloride type structure, wherein the auxiliary formula of vehicle is classical structure type, four oxygen secondary facility unit of zinc
It is the third form (table 1) in four oxide structure unit of zinc set forth below, that is, has and occupy the equatorial plane by 4 carboxyls, two nitrogenous
Azole occupies axial position.
The structural formula of 1 zinc of table, four oxygen secondary building unit
Linear dicarboxylic acid H of the L1 from complete deprotonation in structure2L1, and at least containing one kind listed by table 2 in structure.
The H of the present invention of table 22The structural formula of L1
The containing n-donor ligand H of triangle coordination geometric configuration of the L2 from complete deprotonation in structure1L2, and at least contain in structure
The one kind for having table 3 set forth below.
The H of the present invention of table 32The structural formula of L2
Type realization of the duct size control of the porous crystalline material by change L1 and/or L2, the porous crystalline substance
The channel surfaces functional group regulation of state material is realized by the structure of selection L1 and/or L2.
The duct size control of porous crystalline material can be by three kinds of approach reality.First, if L1 in initial porous material
It is the structural formula that serial number is 1 in table 2, L2 is the structural formula that the serial number in table 3 is 1, and it is appointing in 9-16 that serial number in table 2, which may be selected,
A kind of to replace original L1, new material shows as the increase of A pore size size shown in FIG. 1 relative to original material；Second,
Opposite, the L2 for selecting any replacement of serial number 9-12 in table 3 original, new material shows as Fig. 1 institute relative to original material
The regulation for the duct the B size shown；Third, corresponding, serial number is that any one of 9-16 replacement is original in simultaneous selection table 2
L1, the original L2 of any replacement of serial number 9-12, new material show as A and B shown in FIG. 1 relative to original material in table 3
Regulate and control while pore size.
The channel surfaces functional group regulation of porous crystalline material is real by any structure formula in selection table 2 and/or table 3
It is existing, such as: if initial porous crystalline material is by serial number in table 2 be 1 L1 ligand and table 3 in serial number be 1 L2 ligand
Composition can be realized then being the L1 ligand that serial number is 1 in any replacement initial configuration of 2-16 using the serial number in table 2
The function modulation of the single functional group such as hydroxylating, fluorination, amination, the phenylating of A channel surfaces shown in Fig. 1；Correspondingly, also
It can be 1 L1 ligand using the original single serial number of combination replacement of any 2,3,4 L1 of serial number 1-8 in table 2, i.e.,
The Complex Function tune of the polyfunctional groups such as hydroxylating, fluorination, amination, the phenylating of A channel surfaces shown in Fig. 1 combination can be achieved
Control.It is similar, if initial porous crystalline material be by be in table 2 serial number be 1 L1 and table 3 in serial number be that 1 L2 is constituted, then
Single functional group regulation can be that serial number is 1 in any replacement serial number initial configuration of 2-12 using the serial number in table 3
L2 ligand obtains the new material of the single functional group's functionalization of B channel surfaces in Fig. 1；It can also be using times of serial number 1-8 in table 3
The original single serial number of combination replacement of 2,3,4 L2 of meaning is 1 L2 ligand, obtains B channel surfaces complex function in Fig. 1
The new material of change.
Novel porous crystalline material provided by the present invention, has shown porous structure under high thermal stability and ambient humidity
Stability.High thermal stability refers to that significant heat occurs after the activation of duct, under the conditions of nitrogen atmosphere for porous crystalline material to weight
Measure temperature >=350 degree Celsius of loss；The stability of porous structure refers under ambient humidity occurs significantly at ambient conditions
Temperature >=200 degree Celsius of crystal phase variation.
A kind of preparation method of the porous crystalline material with NaCl type, by zinc salt and organic ligand H2L1、H1L1 and have
Solvent in 100~180 DEG C progress solvent thermal reaction 8-72 hours, through cooling, be filtered, washed, dry, obtain the porous crystalline substance
State material.
The zinc salt and organic ligand H2L1、H1The molar ratio of L1 is 2-4.5:1.5-2:1, optimal with 3:2:1.
The zinc salt is selected from one of zinc nitrate, zinc sulfate, zinc acetate, zinc chloride or its water-containing crystal salt, described to have
Solvent is selected from N,N-Dimethylformamide, nitrogen nitrogen diethylformamide, nitrogen nitrogen dimethyl acetamide, dimethyl sulfoxide or diformazan
The combination of one or both of base pyrrolidones, zinc salt concentration are that 0.02~0.05M is optimal.
The zinc salt be one of zinc nitrate, zinc sulfate, zinc acetate, zinc chloride or their water-containing crystal salt or
Any two kinds of combinations, wherein optimal with zinc nitrate or its water-containing crystal salt.
When solvent thermal reaction, magnetic force or mechanical stirring, revolving speed 200-600r/min, time 5-15 minute, with 500r/min,
10 minutes optimal.Reaction solution, which is sealed in, to be had outside the stainless steel not less than 0.5cm thickness in gallbladder reactor, reaction temperature 100~180
Degree Celsius, optimal with 140 degrees Celsius, the reaction time is 8~72 hours, optimal with 24 hours.
For porous crystalline material of the present invention before the applications such as gas absorption separation storage, duct activation step includes: will be porous
200 degrees Celsius are heated in the environment of the vacuum outgas of crystalline material configuration, activates certain time.Extremely by the vacuum outgas of material elder generation
20 μm of Hg, the external heating packet that then heats up is to 200 degrees Celsius, and the time of vacuum outgas activation process, it is small to be no less than 8 during being somebody's turn to do
When.
Compared with prior art, the invention has the following advantages that
(1) secondary building unit linked simultaneously containing four oxygen of zinc and the auxiliary two kinds of 6- of formula of vehicle in structure, by two kinds of classics two
Level structure unit is dissolved into a NaCl type network structure, is constructed novel porous crystalline material, is provided and have high heat stability concurrently
The porous crystalline material of property and air environment or even high humidity environment stability.
(2) two kinds of secondary building unit ordered fabrications are at the porous crystalline material with typical sodium chloride structure；
(3) duct size and hole surface functional group are easy to regulate and control by ligand L 1 and L2；
(4) the system porous crystalline material preparation method and use front activating processing step are simple, easy.
Detailed description of the invention
Fig. 1 is the skeleton structure schematic diagram of porous crystalline material of the present invention；
Fig. 2-5 is four kinds of skeleton structure diagrams of porous crystalline material of the present invention, it is shown that the tune of duct size and functional group
Become；
Fig. 6-8 is respectively high thermal stability, environment thermal stability and porosity the test knot of porous crystalline material of the present invention
Fruit.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Sample preparation: weighing zinc nitrate hexahydrate 0.104g, terephthalic acid (TPA) 0.033g, 3,5- dimethyl -1H-1, and 2,4-
Triazole 0.010g is added in 10mL nitrogen nitrogen diethylformamide, room temperature magnetic agitation 10 minutes, is made homogeneous and transparent molten
The solution is transferred in stainless steel cauldron by liquid, and 140 DEG C of heating are reacted 24 hours, cooling, is centrifuged, washing, then be centrifuged, do
It is dry, obtain the porous crystalline material with sodium chloride type structure that a kind of four oxygen of zinc and the auxiliary formula secondary building unit of vehicle are constructed.
Embodiment 2
Sample preparation: weighing four chloride hydrate zinc 0.086g, biphenyl dicarboxylic acid 0.048g, 3,5- diethyl -1H-1, and 2,4-
Triazole 0.012g is added in 10mL N,N-Dimethylformamide, and room temperature magnetic agitation 20 minutes, uniform solution is made,
The solution is transferred in stainless steel cauldron, 180 DEG C of heating are reacted 48 hours, and it is cooling, it is centrifuged, washing, then be centrifuged, dry,
The porous crystalline material with sodium chloride type structure that a kind of four oxygen of zinc and the auxiliary formula secondary building unit of vehicle are constructed is obtained, relative to
Embodiment 1, the duct the A size of the made material of embodiment 2 increases about 0.6nm and hole surface functional group is transformed into second from methyl
Base.
Embodiment 3
Sample preparation: weighing zinc nitrate hexahydrate 0.154g, biphenyl dicarboxylic acid 0.048g, and the number of table 3 is that 10 L2 matches
Body 0.181g is added in 10mL nitrogen nitrogen dimethyl acetamide, room temperature magnetic agitation 15 minutes, uniform solution is made, by this
Solution is transferred in stainless steel cauldron, and 100 DEG C of heating are reacted 72 hours, cooling, is centrifuged, washing, then be centrifuged, dry, is obtained
The porous crystalline material with sodium chloride type structure that a kind of four oxygen of zinc and the auxiliary formula secondary building unit of vehicle are constructed.Relative to implementation
The duct the A size of example 1, the made material of embodiment 3 increases about 0.6nm, and the duct B size also increases about 0.6nm.
Embodiment 4
The confirmation of structure: gained porous crystalline material, which meets monocrystalline test request, is, can be directly true by monocrystalline test result
Card is a kind of porous structure of NaCl type constructed by four oxygen of zinc and the auxiliary formula secondary building unit of vehicle.It operates as follows: picking one
Monocrystalline, is measured, using Mo/Ka ray on the SMART APEX CCD single crystal diffractometer of Bruker companyDiffraction data is collected with ω scanning mode.Cell parameter and Orientation Matrices are obtained by least square refinement
It arrives, crystal structure is parsed by direct method or Patterson method, obtains initial configuration, then through least square amendment and poor Fourier side
Method obtains all non-hydrogen atom coordinates, and the hydrogen atom on organic group is obtained using theoretical plus hydrogen, and hydrogen atom waterborne then leads to
Poor Fourier methods are crossed to determine.And be modified through complete matrix least square method, all non-hydrogen atoms all use anisotropic thermal
Parameter carries out refine.Using the structure of serial number 1 in serial number 1 in table 2 and table 3 as example, the molecular formula of crystallography measurement is:
C40H28O17N6Zn6；Molecular weight is: 1257g/mol；Crystallographic system is: four directions；Space group is: I4/m；Unit cell size: Unit-cell volume:Fig. 2-5 is four kinds of porous crystalline material of the present invention
Skeleton structure diagram, it is shown that the modulation of duct size and functional group.
Embodiment 5
The confirmation of thermal stability: with one kind prepared by the combination of serial number 1 in serial number 1 in table 2 and table 3 by four oxygen of zinc and vehicle
For the NaCl type porous crystalline material that auxiliary formula secondary building unit is constructed, thermal stability is implemented as follows: weighing 10mg brand-new
Sample, as on thermal-analysis instrumentation, nitrogen stream, temperature programming is from room temperature to 800 degrees Celsius, by instrument record during this
Weight loss.In the same manner, 10mg sample after activation is weighed, the sample weight loss figure after duct activation can be obtained.Test result
Same or similar with Fig. 3, temperature deviation is no more than 5 degrees Celsius.Similarly, the thermal stability of all samples can pass through this method
It is confirmed, Fig. 6 is the high thermal stability test result of porous crystalline material.
Embodiment 6
The confirmation of environment crystal phase stability:
With one kind prepared by the combination of serial number 1 in serial number 1 in table 2 and table 3 by four oxygen of zinc and the auxiliary formula secondary structure list of vehicle
For the NaCl type porous crystalline material that member is constructed, the embodiment of environment crystal phase stability is as follows: the sample after weighing activation,
The sample cell of powder diffraction instrument is filled up into compacting, is placed on test platform.It is with Bruker D8X- ray powder diffractometer device
Example, test condition are as follows: copper targetTest voltage 40Kv, electric current 40Ma, 2 θ angular scan ranges are 5~50 degree, are swept
Retouching speed is 0.02 degrees second, 0.02 degree of step-length.Obtaining characteristic diffraction peak includes: 2 θ=7.44 (main Qiang Feng), and 10.3,10.5,
12.7,14.9,16.7,18.2o.Then, under environmental damp condition, In Situ Heating to 60,90,140,200 degrees Celsius of difference
At 5~50 degree of 2 angles θ of scanning, data are recorded.Test result is same or like with Fig. 3, and 2 θ angular displacement do not surpass 0.2 degree.Similarly,
The environment crystal phase stability of all samples can be confirmed by this method, noticeable: as duct increase regulates and controls, 2 θ
It contends and is gradually deviated to low-angle, bias size can be calculated according to Bragg equation, and Fig. 7 is the environment thermostabilization of porous crystalline material
Property test result.
Embodiment 7
The porous confirmation of sample after activation:
With one kind prepared by the combination of serial number 1 in serial number 1 in table 2 and table 3 by four oxygen of zinc and the auxiliary formula secondary structure list of vehicle
For the NaCl type porous crystalline material that member is constructed, embodiment is as follows: weighing 120mg brand-new sample and is placed in Merck & Co., Inc
In the sample cell of ASAP2020 adsorption instrument, 200 degrees Celsius of vacuum outgas are heated in de-aeration stage and activate 8 hours, then, be transferred to point
Under the conditions of 77K, program is analyzed using N2 as probe molecule according to the default that instrument provides, is automatically performed sample in analysis station
Porosity test, BET specific surface area 1213m2/ g, HK pore size 0.6nm, different instrument test data are identical as Fig. 3 or class
Seemingly, specific surface area deviation is less than 100m2/ g, pore size deviation are less than 0.2nm.It is noticeable: with using table 2 and table 3
Combination, measure BET specific surface area and there is an apparent difference in aperture, and this species diversity be it is unpredictalbe, Fig. 8 is porous crystalline state
The porosity test result of material.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of porous crystalline material with NaCl type, which is characterized in that same in the skeleton structure of the porous crystalline material
Four oxygen of Shi Hanyou zinc and vehicle two kinds of secondary building units of auxiliary formula, and two kinds of secondary building unit alternate links are built into chlorination jointly
The three-dimensional net structure of sodium form.
2. a kind of porous crystalline material with NaCl type according to claim 1, which is characterized in that the porous crystalline substance
The skeleton structure general molecular formula of state material is [Zn6(O)(L1)4(L2)2], in which: L1 is that the linear acids class of complete deprotonation is matched
Body, L2 are the azole ligands with triangle coordination geometric configuration of complete deprotonation, and O is the oxygen anion of negative divalent state.
3. a kind of porous crystalline material with NaCl type according to claim 2, which is characterized in that four oxygen of zinc
With vehicle two kinds of secondary building units of auxiliary formula by L2 alternate links, one-dimensional chain is formed, one-dimensional chain passes through the one end L1 link zinc four again
Oxygen secondary building unit, other end chain pick up auxiliary formula secondary building unit, are finally linked into the three-dimensional with sodium chloride type structure
Porous crystalline material.
4. a kind of porous crystalline material with NaCl type according to claim 2, which is characterized in that the L1 is
Complete deprotonation linear acids class ligand H2L, molecular structural formula at least contain one kind listed in Table:
5. a kind of porous crystalline material with NaCl type according to claim 2, which is characterized in that the L2 is
The azole ligand H of the triangle coordination configuration of complete deprotonation1L, molecular structural formula at least contain one kind listed in Table:
6. a kind of porous crystalline material with NaCl type according to claim 2, which is characterized in that the porous crystalline substance
Type realization of the duct size control of state material by change L1 and/or L2, the channel surfaces official of the porous crystalline material
Regulation can be rolled into a ball to realize by the structure of selection L1 and/or L2.
7. a kind of porous crystalline material with NaCl type according to claim 1-6, which is characterized in that institute
It states the auxiliary formula secondary building unit of vehicle and uses classical structure type, 4 carboxyls in the structure of the four oxygen secondary building unit of zinc
The equatorial plane is occupied, two nitrogenous azoles occupy axial position.
8. a kind of preparation method of the porous crystalline material with NaCl type as described in claim 1, which is characterized in that will
Zinc salt and organic ligand H2L1、H1L1 and organic solvent in 100~180 DEG C progress solvent thermal reaction 8-72 hours, through cooling, mistake
Filter, washing, drying, obtain the porous crystalline material.
9. a kind of preparation method of porous crystalline material with NaCl type according to claim 8, which is characterized in that
The zinc salt and organic ligand H2L1、H1The molar ratio of L1 is 2-4.5:1.5-2:1.
10. a kind of preparation method of porous crystalline material with NaCl type according to claim 8, feature exist
In the zinc salt is selected from one of zinc nitrate, zinc sulfate, zinc acetate, zinc chloride or its water-containing crystal salt, the organic solvent
Selected from N,N-Dimethylformamide, nitrogen nitrogen diethylformamide, nitrogen nitrogen dimethyl acetamide, dimethyl sulfoxide or dimethyl pyrrole
The combination of one or both of alkanone.
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