CN104860967A - Zn(II)-triacid complex with nanopores and application thereof - Google Patents
Zn(II)-triacid complex with nanopores and application thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 238000010583 slow cooling Methods 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 36
- 239000001257 hydrogen Substances 0.000 abstract description 36
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 description 19
- 239000012621 metal-organic framework Substances 0.000 description 12
- 238000011160 research Methods 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000011161 development Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 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 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229920001795 coordination polymer Polymers 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- -1 metals hydride Chemical class 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C07F3/06—Zinc compounds
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a Zn(II)-triacid complex with nanopores and a synthesis method and application thereof. The Zn(II)-triacid complex with nanopores is mainly used in the aspects of new energy gas adsorption. The results show that the porous complex shows huge 1886.8 angstrom<3> solvent molecules holes, so that the Zn(II)-triacid complex with nanopores is mainly used in the aspects of new energy gas adsorption, and especially has a broad application prospect in hydrogen energy gas adsorption application.
Description
Statement about subsidizing research or exploitation: the present invention carries out under the subsidy of Tianjin application foundation and cutting edge technology research plan Tianjin Nsfc Projects (Grant no. 14JCQNJC05900) and project of national nature science fund project (Grant No. 21301128).
Technical field
The invention belongs to organic synthesis and Organometallic Chemistry technical field, relate to the synthesis of the sour title complex of Zn (II)-three with nano pore, terphenyl-3 in particular, the synthesis of 4'', 5-tricarboxylic three-dimensional Zn (II) nanoporous title complex and in energy gas adsorption applications.
Background technology
As a kind of pollution-free, clean renewable energy source, the development and application of hydrogen energy source has obtained the extensive concern of various countries, and it comprises four processes: produce, transport, store, use.Wherein, hydrogen storage technology is the key link of Application and Development.Traditional hydrogen storage method has two kinds, one method utilizes high-pressure cylinder (hydrogen cylinder) to carry out storage of hydrogen, but the volume of steel cylinder storage of hydrogen is little, even if the hydrogen in bottle is pressurized to 150 normal atmosphere, fill the quality of hydrogen also less than 1% of hydrogen cylinder quality, and also have blast danger; Another kind method is storing liquid hydrogen, and gaseous hydrogen is cooled to-253 DEG C and become liquid and store, but liquid storage tank is very huge, energy consumption is high, needs fabulous adiabatic apparatus heat insulation, just can prevent liquid hydrogen from can not to seethe with excitement vaporization.Therefore hydrogen storage technology and the efficient hydrogen storage material of development of new are the task of top priority safely and efficiently.According to the development target of USDOE, its gravimetric hydrogen storage density of practical hydrogen storage material will reach 6.0 wt% in 2010; Within 2015,9.0 wt% to be reached.For reaching this target, many researchers have carried out deeply and widely studying in a large number and striving to find a kind of economy, safe and practical and convenient storage hydrogen mode to the storage of hydrogen for many years.
Absorption is considered to most promising hydrogen storage technology, and metal-organic framework (Metal-Organic Frameworks, be called for short MOFs) hydrogen storage technology becomes 21st century international emerging research frontier gradually.The synthesis of metal organic frame and character research be nineteen nineties the inorganic chemistry that gets up of Later development and materials chemistry in one of important field of research.Because open metal-organic coordination polymer density is little, be only 1/3rd of conventional metals hydride, adopt MOFs greatly can reduce the weight of storage hydrogen device as hydrogen storage media.This feature especially meets the hydrogen-feeding system requirement of hydrogen cell automobile.In addition such material also has the feature that specific surface area is large, pore volume is large, is therefore a kind of novel high-capacity light hydrogen occluding material, has become a kind of novel easy hydrogen storage method in recent years and has arisen at the historic moment.People just recognize from the beginning, and not only the composition of MOFs is adjustable, and the content of its pore volume is also variable [2].In order to prove the accesibility of these holes, people have studied the exchange of ion and solvent molecule.A series of micromolecular quantitative exchange research has identified some MOFs with specific function (if holding MOFs of the guest molecule of specified shape).Relative to traditional porous material such as zeolite, metal-organic coordination polymer (MOFs) has good snappiness and controllability, especially MOFs has relatively low density (1.00-0.20 g/cm3) and high-specific surface area (500-4500 m2/g), make them can as good gas adsorption carrier and gas delivery device (N2, Ar, CO2, CH4 and H2).
At present, metal-organic framework storage hydrogen research work mainly concentrates on the ligand polymer that carboxylic acid is constructed with transition metal, relative transition metal complex, and the synthesis of metal coordinating polymer and the storage of storage hydrogen and correlation energy source material are studied a lot delayed.Due to trivalent lanthanide ion have 8 to 12 high ligancy and also rangeability also very large, after making it and ligand binding, the space structure of product is difficult to Forecast and control, and from the compound that document has been reported, their Space expanding seldom presents high symmetry and very regular pattern.And can differ between not isosteric geometry conformation is very little, the therefore conformation of prioritizing selection not obvious in stereochemistry.These factors make to design and synthesize ligand polymer ideally and face huge challenge.Until within 1984, just obtain the title complex [Ln2 (H2O) 2Ni3 (S2C2O2) 6xH2O] of first structural characterization.Afterwards along with the development of NdFeB permanent magnet material and YBaCuO superconductor, such title complex was subject to great attention as the presoma preparing superconducting material.
In general, selecting ratio and the temperature of reaction of suitable polyacid part, adjustment part and many kinds of metal ions, is the effective means of synthesizing new porous material.Attempt different reaction conditionss, measured, to the porous material with absorption property can be filtered out by monocrystalline parsing, adsorption property.Therefore by exploring the inner link of the aperture of Porous materials, specific surface area, hole occupation rate and absorption property, there is in searching system the porous material of using value, not only contribute to the development of coordination chemistry, also all there is important Research Significance for novel porous materials in the research in the fields such as gas adsorption, ion-exchange, catalysis.
Summary of the invention
For achieving the above object, the invention provides following technical scheme:
Have the sour title complex of Zn (II)-three of nano pore, this compound is new, does not have this material of bibliographical information by scifinder inquiry; Its chemical general formula is as follows:
[Zn (L)] (DMF) (1); The structural formula of L is
L refers to terphenyl-3,4'', 5-tricarboxylic acid (Terphenyl-3,4'', 5-tricarboxylic acid).
The present invention further discloses [Zn (L)] (DMF) monocrystalline, the BRUKER SMART 1000 X-ray single crystal diffraction instrument of triclinic(crystalline)system wherein, adopt the Mo of graphite monochromator
kα radiation (λ=0.071 073 nm) as diffraction light sources, at 173 (2) K temperature, with
scan mode, measures predominant crystal data as follows:
The present invention further discloses the method for the sour complex monocrystal of Zn (II)-three with nano pore, it is characterized in that: take 106.84 mg (0.03 mmol) Zn (ClO
4)
3by 5 mL water dissolution, take ligand L 22.8 mg g(0.063 mmol) dissolve with 5mL water and 5mLDMF, by above two kinds of solution mixing, be then put in the water heating kettle of 15 mL and keep three days at 120 DEG C, after slow cooling, obtain colourless transparent crystal.
The present invention further discloses the absorption aspect of Zn (II) the title complex energy gas adsorption applications of three-D nano-porous skeleton construction, particularly has a wide application prospect with the application of hydrogen as energy source gas adsorption.Described new forms of energy gas is a kind of potential clean energy, in future source of energy structure, there is important strategic location, to socio-economic development+Improvement of Ecological Environment, (aspect such as energy structure optimizing and national security will produce great strategic effect, therefore the research and development of gas hydrate are very necessary, also very urgent, be one to have perspective and strategic key subjects and comprise, new forms of energy gas comprises CO, CO
2, CH
4, H
2s, H
2deng gas.
Accompanying drawing illustrates:
Fig. 1 is the molecular structure of the sour title complex of Zn (II)-three [Zn (L)] (DMF) with nano pore;
Fig. 2 is the three-dimensional porous structure figure of the sour title complex of Zn (II)-three [Zn (L)] (DMF) with nano pore;
Fig. 3 by the powder diagram of crystal data matching (on) and experimental powder sample powder diagram (under) contrast consistent, show that title complex 1 experimental powder allomeric structure is consistent.
Embodiment
In order to simple and clearly object, the hereafter appropriate description eliminating known technology, in order to avoid the description of those unnecessary details impact to the technical program.Below in conjunction with preferred embodiment, the present invention will be further described, is illustrated especially, prepares the initial substance Zn (ClO of the compounds of this invention
4)
2, diethyl-5-iodine m-phthalic acid, 4-bromophenylboronic acid, two (cyano group benzene) palladium chloride, salt of wormwood, ethyl acetate, DMF, magnesium sulfate can commercially or easily be obtained (reagent prepared used by the compounds of this invention all derives from business and buys, and rank is analytical pure) by known method.
Need in addition to be illustrated: all experimental implementation use Schlenk technology, and solvent is through normal process purifying.All for the synthesis of being all analytical pure with the reagent analyzed, not through further process.Fusing point is measured by Boetius block apparatus.
1h NMR composes by mercury variable V x300 spectrophotometer record, surveying range: 300 MHz.Chemical shift, δ, the TMS with reference to international standard measures.
Embodiment 1
The synthesis of ligand L
Diethyl-5-iodine m-phthalic acid (348 mg are added in 5 mL DMF, 1.0 mmol), then continue to add 4-bromophenylboronic acid (210 mg, 1.05 mmol), two (cyano group benzene) palladium chloride (20 mg, 0.053 mmol) and salt of wormwood (400 mg, 2.90 mmol), reaction is carried out under a nitrogen. and spend the night at 80 DEG C and stirring under a nitrogen, adding water allows reaction stop, utilize ethyl acetate to extract, utilize dried over mgso, the method sub-argument of flash column chromatography is utilized to go out ligand L (302 mg, 0.80 mmol).1H NMR (300 MHz, CDCl3): δ = 8.66 (t, J = 1.5 Hz, 1H), 8.40 (d, J = 1.5 Hz, 2H), 7.64–7.50 (m, 4H), 4.44 (q,J = 7.2 Hz, 4H), 1.43 (t, J = 7.2 Hz, 6H). 13C NMR (75 MHz,CDCl3): δ = 165.7, 140.7, 138.2, 132.2, 131.9, 131.8, 129.6, 128.8, 122.6, 61.5, 14.4.
The synthesis of title complex (1)
Take 106.84 mg (0.03 mmol) Zn (ClO
4)
3by 5 mL water dissolution, take ligand L 22.8 mg g(0.063 mmol) dissolve with 5mL water and 5mLDMF, by above two kinds of solution mixing, be then put in the water heating kettle of 15 mL and keep three days under 120 ° of C, after slow cooling, obtain colourless transparent crystal.
Results of elemental analyses, experimental value (%): C, 57.86%; H, 4.96%; N, 5.27%.
According to C
26h
26n
2o
7the theoretical value (%) that Zn calculates: C, 57.4163%; H, 4.8184%; N, 5.1506%.
FT-IR(cm
?1): 3410(br), 1670(s), 1640(s), 1550(w), 1520(m), 1430(s),1410(w), 1370(s), 1110(m), 780(s).
Embodiment 2
Choose the monocrystalline BRUKER SMART 1000 X-ray single crystal diffraction instrument that size is 0.26 mm × 0.23, mm × 0.24 mm, adopt the Mo of graphite monochromator
kα radiation (λ=0.071 073 nm) as diffraction light sources, at 173 (2) K temperature, with
scan mode, 1.582 °≤
θ≤ 25.010(-39<=h<=34,-12<=k<=16,-15<=l<=16) in scope, collect 13390 point diffractions, wherein 2256 independent point diffractions altogether
(R
int=0.0288).Crystalline structure is solved by direct method, non-hydrogen atom is obtained by difference Fourier synthesis method, the method determined and revise hydrogen atom is theoretical hydrogenation, adopt isotropy and anisotropy thermal parameter to carry out complete matrix least-squares refinement to structure respectively to hydrogen atom and non-hydrogen atom, all calculating SHELXS-97 and SHELXL-97 routine package complete.The predominant crystal data of title complex list in table 1.
No. CCDC (No. CCDC is cambridge structure database numbering) of title complex 1: 1059658
the monocrystalline data of table 1 title complex 1
2 results and discussion
2.1 infrared spectra
The IR spectrum of title complex 1 is at 3 400 cm
-1there is a medium tenacity absorption peak at place, and its width reaches 200 cm
-1above, owing to the absorption of vibrations of the coordinated water in molecule, the association due to hydrogen bond makes peak broaden.The infrared spectra of title complex 1 is at 800cm
-1strong infrared peak show that the absorption peak of left and right can be designated as the vibration of phenyl ring, and at 1600cm
-1indicate the existence of hydroxy-acid group, the Infrared spectroscopy of title complex [Zn (L)] (DMF) is consistent with its crystal structure analysis result.
2.2 crystalline structure
The crystal of title complex 1 belongs to monoclinic crystallographic system, C
2/ c spacer, main bond distance and bond angle list in table 2, and its crystalline structure as shown in Figure 1 and 2.As seen from Figure 1, there is the structure (Zn1) of Liao Yige center Zn in each complex molecule simultaneously, it should be noted that water molecules exists with the form of coordination simultaneously, part is with bridging coordination mode, in title complex 1, solvent water molecules serves the effect of very important end group coordination, and solvent water molecules participates in coordination and have impact on the coordination that Carboxylic acid ligand participates in center Zn ion.For the basic structural unit of title complex thing 1, Zn1 defines nine coordination ZnO with four Sauerstoffatoms from four ligand moleculars respectively
9coordination configuration.The coordination bond lengths scope of Zn ion and Sauerstoffatom is 0. 19624 (12) nm ~ 0.19995 (12) nm, and these all meet bond distance's scope of bibliographical information.
The time coordinated carbon atoms of the free DMF molecule in title complex, the Sauerstoffatom in ligand L, bridging defines mutually abundant hydrogen bond.Just because of the effect of these hydrogen bonds, the sterie configuration of title complex is made to present stable Magnetic Properties of Three-Dimensional Supramolecular Complex structure.The plane that in molecule, two Benzene Molecules and triazole molecule are formed is parallel to each other, shows to there is stronger pi-pi accumulation effect between the phenyl ring plane of gripping altogether.The three-dimensional structure of these pi-pi accumulation effects and the further stable complex of other weak interactions.By the powder diagram of crystal data matching (on) with the powder diagram of experimental powder sample (under) contrast is consistent, shows that title complex 1 experimental powder allomeric structure unanimously (Fig. 3).Porous coordination shows huge 1886.8
3solvent molecule hole, the sour title complex of Zn (II)-three therefore with nano pore is mainly used in the absorption aspect of new forms of energy gas adsorption application, and particularly applying by hydrogen as energy source gas adsorption has a wide application prospect.
The present invention selects based on the sour title complex of Zn (II)-three with nano pore, and owing to having three-dimensional porous skeleton construction, therefore after processing further and optimizing, energy gas adsorption applications has a wide application prospect.
The part bond distance of table 2 title complex 1 and bond angle
Embodiment 3
The compound with three-dimensional porous skeleton construction is used as nano-porous materials, in the application of the absorption side of energy gas adsorption applications
Concrete instance:
In 1999, Williams research group reported one by cupric ion and trimesic acid (H on Science magazine
3the metal organic framework compound (HKUST-1) of BTC) constructing, this structure has aperture and is about 9 × 9
2square duct, BET specific surface area is 692.2 m
2/ g.The same year, Yaghi research group is again with terephthalic acid (1,4-BDC) be part, synthesize the metal organic framework compound MOF-5 (as Fig. 1) with simple cubic six interconnection network structure, its aperture is about 12.94, spacious Du Keda 55 ~ 61 % of skeleton, Langmuir specific surface area is up to 2900 cm
2g
-1.
Reference:
(1) Li, H.; Eddaoudi, M.; O'Keeffe M.; Yaghi, O. M.
Nature 1999, 402, 276.
Embodiment 4
The hydrogen gas adsorptive power performance study of [Zn (L)] (DMF) prepared by the present invention is as follows:
The solid particle samples (sample of embodiment 1) of 60 mg is filled on the Autosorb-IQ2 gas adsorption analyser of Kang Ta instrument company of U.S. production, uses highly purified H
2as by the gas adsorbed.The recycle of solid particulate product, completes all tests.
Gas adsorption measuring result shows: under a 77K and barometric point, this metal organic frame has huge 1886.8
3solvent molecule hole, metal organic frame aperture is about 9.917 (2) × 18.906 (6)
2rectangle duct, under it is adsorbed as 1.92 wt%(100 kPa condition to hydrogen gas).(wt% is hydrogen as energy source gas adsorption unit, corresponding (by the H adsorbed
2quality)/(quality of sorbent material), be a kind of algorithm of recommendation in newly fixed storage hydrogen target USDOE in April, 2009.See
http://www1.eere.energy.gov/hydrogenandfuelcells/mypp/pdfs/storage.pdf。）。
Conclusion:
The present invention relates to the synthesis of the sour title complex of Zn (II)-three with nano pore, be in particular the sour title complex of the tricarboxylic Zn of terphenyl-3,4'', 5-(II)-three synthesis and in the absorption of new forms of energy gas.Adopt Zn (II) as main body respectively, with terphenyl-3,4'', 5-tricarboxylic acid as part, probe into the impact of a metal-organic complex on new forms of energy gas adsorption, analyze title complex to the influence factor of different new forms of energy gas adsorption difference on effect.Porous coordination shows huge 1886.8
3solvent molecule hole, the sour title complex of Zn (II)-three therefore with nano pore is mainly used in the absorption aspect of new forms of energy gas adsorption application, and particularly applying by hydrogen as energy source gas adsorption has a wide application prospect.
Claims (5)
1. have the sour title complex of Zn (II)-three of nano pore, its chemical general formula is as follows:
[Zn (L)] (DMF) (1); The structural formula of L is
L refers to terphenyl-3,4'', 5-tricarboxylic acid.
2. the sour complex monocrystal of Zn (II)-three with nano pore according to claim 1, the BRUKER SMART 1000 X-ray single crystal diffraction instrument of triclinic(crystalline)system wherein, adopts the Mo of graphite monochromator
kα radiation (λ=0.071 073 nm) as diffraction light sources, at 173 (2) K temperature, with
scan mode, measures predominant crystal data as follows:
。
3. prepare a method for Zn (II)-three sour complex monocrystal described in claim 2 with nano pore, it is characterized in that: take 106.84 mg (0.03 mmol) Zn (ClO
4)
3by 5 mL water dissolution, take ligand L 22.8 mg (0.063 mmol) 5mL water and 5mLDMF dissolving, by above two kinds of solution mixing, be then put in the water heating kettle of 15 mL and keep three days at 120 DEG C, after slow cooling, obtain colourless transparent crystal.
4. there is the application of the sour title complex new forms of energy gas adsorption aspect of Zn (II)-three of nano pore, particularly with the application of hydrogen gas absorption described in claim 1.
5. application according to claim 4, wherein said new forms of energy gas comprises CO, CO
2, CH
4, H
2s, H
2gas.
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