CN105153243B - Cluster base heteronuclear N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline and preparation method thereof - Google Patents
Cluster base heteronuclear N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of cluster base heteronuclear N (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline and preparation method thereof, the molecular formula of the porous crystalline is [Mg8Ni12(OH)12(PMIDA)4(BTC)4(H2O)16]·9H2O, wherein BTC represent the 1 of trivalent, 3,5 trimesic acid roots, and PMIDA represents N (phosphonomethyl) iminodiacetic acid (salt) acid group of 4 valencys, and molecular weight 3298.102, belongs to rhombic system, Cmca space groups, cell parameter a=28.0134 (7), b=17.8914 (4), c=12.7629 (3), α=90 °, β=90 °, γ=90 °, unit cell volume is 6396.8 (3) 3, duct size is 10.81×11.398
Description
Technical field
The invention belongs to crystalline material technical field, and it is sub- to be related to a kind of cluster base heteronuclear N- (phosphonomethyl) with adsorptivity
Aminodiacetic acid trimesic acid magnesium nickel metal-organic framework porous crystalline material and preparation method thereof.
Background technology
Metal-organic framework (MOFs) is a kind of new crystalline state porous material, mainly by metal ion or metal cluster
It is formed by connecting with organic ligand self assembly coordination.Since it is with many excellent characteristics, such as fluorescence property, magnetism, catalysis work
Property, ion exchangeable and adsorptivity etc., have important application in fields such as petrochemical industry, fine chemistry industries.This kind of material is also dividing
Son identification, the assembling of host-guest functional material etc. show wide application prospect.So far, on novel structure and
Design synthesis and the exploitation of the MOFs porous materials of different chemical compositions are still very active research frontier.
Different metal complex refers to that the organic ligand metal ion different from two or more carries out collaboration and match somebody with somebody
The Heteronu clear metal complex with finite structure and unlimited continuous structure that position is constructed, compared to mononuclear complex, they
Show many special physical property, chemism and physiological actions.Because different metal ions and organic ligand is mutual
Effect, make its possess novel changeable topological structure, excellent magnetic property, superior catalytic activity, novel reactivity worth, compared with
High selectivity and sensitivity, therefore different metal complex all has wide practical use in many fields, for example, molecule is known
Not, selective catalysis, absorption, optical material, magnetic material, chemical sensor etc..So the synthesis of different metal complex, structure
And property research becomes one of research hotspot of field of coordinative chemistry in recent years.Main synthesis strategy is by transition metal and mistake
Metal is crossed to be mixed (d-d) and transition metal is mixed (d-f) with rare earth metal.Currently, based on alkaline-earth metal and
The different metal complex of transition metal also result in people's due to its novel changeable topological structure and excellent performance
Research interest.
Organic carboxyl acid is to construct the common multi-functional ligand of one kind during metal-organic framework, with multi-carboxylic acid's bridging
The MOFs materials with novel structure that ligand is constructed achieve obvious progress and significant achievement, largely with organic carboxyl acid
It is designed to be synthesized for the MOFs materials of ligand.In recent years, it has been found that be used in mixed way two kinds of organic carboxyl acids, be such as used in mixed way
Phosphonic acids and carboxylic acid are also a kind of effective method for synthesizing metal complex.However, on using phosphonic acids and carboxylic acid conduct
Mixed ligand is also fewer to construct the report of different metal cluster polymerization of olefin using catalyst compound, with phosphonic acids and carboxylic acid as mixed ligand
Composite variety base different metal MOFs materials or a challenging job, are of great significance.
The content of the invention
It is equal that the technical problems to be solved by the invention are to provide a kind of cluster base heteronuclear N- (phosphonomethyl) iminodiacetic acid
Benzenetricarboxylic acid magnesium nickel porous crystalline, and the method that the porous crystalline material is prepared using hydro-thermal reaction.
Technical solution is used by solving above-mentioned technical problem：The equal benzene of N- (phosphonomethyl) iminodiacetic acid
The molecular formula of tricarboxylic acid magnesium nickel porous crystalline is [Mg8Ni12(OH)12(PMIDA)4(BTC)4(H2O)16]·9H2O, wherein
1,3,5- trimesic acid roots of BTC representatives-trivalent, PMIDA represent N- (phosphonomethyl) iminodiacetic acid of -4 valencys
Root；The molecular weight of the porous crystalline is 3298.102, belongs to rhombic system, Cmca space groups, cell parameter α=90 °, β=90 °, γ=90 °, unit cell volume
ForDuct size isZ=2.
The preparation method of N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline of the present invention is：Will
Four hydration nickel acetates, six hydrated basic magnesium carbonates, N- (phosphonomethyl) iminodiacetic acid, the equal benzene tricarbonic acids of 1,3,5- by mole
Than for 1:(1.5~2.5):(0.2~1.2):(0.1~0.6) is placed in polytetrafluoroethyllining lining, and adds distilled water as molten
Agent, adjusts pH value to 5.0~9.0, isothermal reaction 3~7 days at 140~200 DEG C, obtain N- (phosphonomethyl) imido with ammonium hydroxide
Base oxalic acid trimesic acid magnesium nickel porous crystalline.
Four above-mentioned hydration nickel acetates and six hydrated basic magnesium carbonates, N- (phosphonomethyl) iminodiacetic acid, 1,3,5-
The molar ratio preferably 1 of equal benzene tricarbonic acid:2:0.6:0.4.
In the preparation method of above-mentioned N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline, preferably use
Ammonium hydroxide adjusts pH value to 7.0.
In the preparation method of above-mentioned N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline, into one
Step isothermal reaction 5 days preferably at 190 DEG C.
The present invention is with N- (phosphonomethyl) iminodiacetic acids (H4PMIDA it is) main bridge ligand, 1,3,5- equal benzene three
Formic acid (H3BTC) it is assistant ligand, carries out coordination coordination with two kinds of different metal ions, using hydrothermal synthesis method, construct jointly
Cluster base heteronuclear N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline, the porous crystalline material have good
Absorption property, there is potential application prospect in fields such as petrochemical industry, fine chemistry industries.
Brief description of the drawings
Fig. 1 is [Mg8Ni12(OH)12(PMIDA)4(BTC)4(H2O)16]·9H2The coordination context diagram of O.
Fig. 2 is [Mg8Ni12(OH)12(PMIDA)4(BTC)4(H2O)16]·9H2The double cage figures of cluster base in O.
Fig. 3 is [Mg8Ni12(OH)12(PMIDA)4(BTC)4(H2O)16]·9H2Multinuclear different metal cluster figure in O.
Fig. 4 is [Mg8Ni12(OH)12(PMIDA)4(BTC)4(H2O)16]·9H2Duct three-dimensional framework figures of the O on b directions.
Fig. 5 is [Mg8Ni12(OH)12(PMIDA)4(BTC)4(H2O)16]·9H2The duct three-dimensional framework figures of O in the c-direction.
Fig. 6 is [Mg8Ni12(OH)12(PMIDA)4(BTC)4(H2O)16]·9H2O is to N2And CO2Adsorption isotherm line chart.
Embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
0.125g (0.5mmol) four is hydrated nickel acetate, six hydrated basic magnesium carbonates of 0.485g (1mmol), 0.07g
(0.3mmol) N- (phosphonomethyl) iminodiacetic acid, the equal benzene tricarbonic acids of 0.042g (0.2mmol) 1,3,5-, 4mL distilled water are put
In 10mL polytetrafluoroethyllining linings, it is stirred at room temperature uniformly, its pH value is adjusted to 7.0 with ammonium hydroxide, then by polytetrafluoroethylene (PTFE)
Lining is put into stainless steel reaction shell, in an oven 190 DEG C of isothermal reactions 5 days, is cooled down with the rate of temperature fall of 10 DEG C/min of speed
To 30 DEG C, light green color bulk N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline is obtained, its yield is
75%, molecular formula is [Mg8Ni12(OH)12(PMIDA)4(BTC)4(H2O)16]·9H2O, belongs to rhombic system, and space group is
Cmca, cell parameter β=90 °, unit cell volume
ForDuct size isZ=2.The porous crystalline is by 8 Mg2+, 12 Ni2+、4
A PMIDA4-Ligand, 12 bridging hydroxyls, 4 BTC3-Ligand, 16 waters of coordination and 9 crystalline water molecules compositions.Can by Fig. 1
See there is Mg independent in 2 crystallography in the asymmetric cell of the porous crystalline2+Independent Ni on ion and 1 crystallography2+
Ion.Mg1 atoms and six O atoms (O1, O2, O4, O5, O6, O8) are coordinated, wherein, O1, O5 are bridging oxygen atoms；O2 comes from
PMIDA4-Carboxyl oxygen atom on ligand；O8 comes from BTC3-Carboxyl oxygen atom on ligand and the coordination in the form of monodentate；O4 and O6
From a PMIDA4-Phosphonyl group on ligand.Mg2 atoms and six O atoms (O5, O5A, O6, O7, O9, O2W) are coordinated, its
In, O5, O5A are bridging oxygen atoms；O6 comes from a PMIDA4-Phosphonyl group on ligand；O7 and O9 comes from BTC3-On ligand
Carboxyl oxygen atom and in the form of monodentate be coordinated；O2w is water of coordination molecule.Ni3 atoms and N1, O2A, O2, O1, N1, O1W,
Six Atomic coordinates of O1AW, wherein, O2 and O2A come from two PMIDA4--Carboxyl oxygen atom on ligand；O1 is bridging oxygen original
Son；O1W and O1AW comes from water of coordination molecule.8 Mg atoms pass through PMIDA4-The oxygen atom of organic phospho acid group on ligand and
Bridging O5 atoms, which are connected, forms the double cages (see Fig. 2) of a cluster base, the metal Mg atoms and BTC of the double cage peripheries of cluster base3-, it is organic
Phosphonic acids is interconnected to form a multinuclear different metal cluster (see Fig. 3), and multinuclear different metal cluster passes through BTC3-And PMIDA4-It is connected with each other
Formed one along b, c direction have different structure be orientated 3D ducts skeleton structure, crystalline water molecules be filled in duct (such as Fig. 4,
5).As can be seen from Figure 6, under 77K, the porous crystalline is to N2Adsorbance be 22.3164cm3/ g, and adsorption process substantially can
Inverse, BET specific surface area is 27.6740m2/ g, Langmuir surface area are 60.4661m2/g；Under 273K, the crystal is to CO2
Maximum storage value be 57.8432cm3/ g, illustrates that the porous crystalline has preferable CO2Storage capacity.
Embodiment 2
0.125g (0.5mmol) four is hydrated nickel acetate, six hydrated basic magnesium carbonates of 0.485g (1mmol), 0.07g
(0.3mmol) N- (phosphonomethyl) iminodiacetic acid, the equal benzene tricarbonic acids of 0.042g (0.2mmol) 1,3,5-, 4mL distilled water are put
In 10mL polytetrafluoroethyllining linings, it is stirred at room temperature uniformly, its pH value is adjusted to 7.0 with ammonium hydroxide, then by polytetrafluoroethylene (PTFE)
Lining is put into stainless steel reaction shell, in an oven 170 DEG C of isothermal reactions 5 days, is cooled down with the rate of temperature fall of 10 DEG C/min of speed
To 30 DEG C, light green color bulk N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline is obtained, its yield is
68%, molecular formula, crystal parameters, unit cell volume and duct size are same as Example 1.
Embodiment 3
0.125g (0.5mmol) four is hydrated nickel acetate, six hydrated basic magnesium carbonates of 0.485g (1mmol), 0.07g
(0.3mmol) N- (phosphonomethyl) iminodiacetic acid, the equal benzene tricarbonic acids of 0.042g (0.2mmol) 1,3,5-, 4mL distilled water are put
In 10mL polytetrafluoroethyllining linings, it is stirred at room temperature uniformly, its pH value is adjusted to 6.0 with ammonium hydroxide, then by polytetrafluoroethylene (PTFE)
Lining is put into stainless steel reaction shell, in an oven 190 DEG C of isothermal reactions 5 days, is cooled down with the rate of temperature fall of 10 DEG C/min of speed
To 30 DEG C, light green color bulk N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline is obtained, its yield is
60%, molecular formula, crystal parameters, unit cell volume and duct size are same as Example 1.
Embodiment 4
0.125g (0.5mmol) four is hydrated nickel acetate, six hydrated basic magnesium carbonates of 0.606g (1.25mmol), 0.14g
(0.6mmol) N- (phosphonomethyl) iminodiacetic acid, the equal benzene tricarbonic acids of 0.063g (0.3mmol) 1,3,5-, 4mL distilled water are put
In 10mL polytetrafluoroethyllining linings, it is stirred at room temperature uniformly, its pH value is adjusted to 5.0 with ammonium hydroxide, then by polytetrafluoroethylene (PTFE)
Lining is put into stainless steel reaction shell, in an oven 200 DEG C of isothermal reactions 3 days, is cooled down with the rate of temperature fall of 10 DEG C/min of speed
To 30 DEG C, light green color bulk N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline is obtained, its yield is
52%, molecular formula, crystal parameters, unit cell volume and duct size are same as Example 1.
Embodiment 5
0.125g (0.5mmol) four is hydrated nickel acetate, six hydrated basic magnesium carbonates of 0.364g (0.75mmol), 0.023g
(0.1mmol) N- (phosphonomethyl) iminodiacetic acid, the equal benzene tricarbonic acids of 0.011g (0.05mmol) 1,3,5-, 4mL distilled water
It is placed in 10mL polytetrafluoroethyllining linings, is stirred at room temperature uniformly, its pH value is adjusted to 9.0 with ammonium hydroxide, then by polytetrafluoroethylene (PTFE)
Liner is put into stainless steel reaction shell, in an oven 140 DEG C of isothermal reactions 7 days, is dropped with the rate of temperature fall of 10 DEG C/min of speed
Temperature obtains light green color bulk N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline, its yield to 30 DEG C
For 53%, molecular formula, crystal parameters, unit cell volume and duct size are same as Example 1.
Claims (5)
1. a kind of cluster base heteronuclear N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline, it is special
Sign is：The molecular formula of the porous crystalline is [Mg8Ni12(OH)12(PMIDA)4(BTC)4(H2O)16]·9H2O, its
1,3,5- trimesic acid roots of middle BTC representatives-trivalent, PMIDA represent N- (phosphonomethyl) iminodiacetic acid of -4 valencys
Root；The molecular weight of the porous crystalline is 3298.102, belongs to rhombic system, Cmca space groups, cell parameterα=90 °, β=90 °, γ=90 °, structure cell body
Product isDuct size isZ=2.
2. cluster base heteronuclear N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline described in claim 1
Preparation method, it is characterised in that：By four be hydrated nickel acetates, six hydrated basic magnesium carbonates, N- (phosphonomethyl) iminodiacetic acid,
The equal benzene tricarbonic acids of 1,3,5- are 1 in molar ratio:1.5~2.5:0.2~1.2:0.1~0.6 is placed in polytetrafluoroethyllining lining, and
Distilled water is added as solvent, adjusts pH value to 5.0~9.0 with ammonium hydroxide, isothermal reaction 3~7 days, obtain at 140~200 DEG C
N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel porous crystalline.
3. the porous crystalline substance of cluster base heteronuclear N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel according to claim 2
The preparation method of body, it is characterised in that：The four hydration nickel acetates and six hydrated basic magnesium carbonates, N- (phosphonomethyl) imido
The molar ratio of the equal benzene tricarbonic acid of base oxalic acid, 1,3,5- is 1:2:0.6:0.4.
4. cluster base heteronuclear N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel according to Claims 2 or 3 is more
The preparation method of hole crystal, it is characterised in that：PH value is adjusted to 7.0 with ammonium hydroxide.
5. cluster base heteronuclear N- (phosphonomethyl) iminodiacetic acid trimesic acid magnesium nickel according to Claims 2 or 3 is more
The preparation method of hole crystal, it is characterised in that：Isothermal reaction 5 days at 190 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517625A (en) * | 2011-12-23 | 2012-06-27 | 陕西师范大学 | Boric acid strontium lithium micropore crystal and preparation method thereof and application |
| CN104558061A (en) * | 2015-01-15 | 2015-04-29 | 陕西师范大学 | Hypoboric acid benzene tricarboxylic acid cobalt-indium micro-porous crystal and preparation method thereof |
| CN104844663A (en) * | 2015-04-07 | 2015-08-19 | 山西大学 | Nickel coordination polymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517625A (en) * | 2011-12-23 | 2012-06-27 | 陕西师范大学 | Boric acid strontium lithium micropore crystal and preparation method thereof and application |
| CN104558061A (en) * | 2015-01-15 | 2015-04-29 | 陕西师范大学 | Hypoboric acid benzene tricarboxylic acid cobalt-indium micro-porous crystal and preparation method thereof |
| CN104844663A (en) * | 2015-04-07 | 2015-08-19 | 山西大学 | Nickel coordination polymer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| A Series of Alkaline Earth Metal Ions Doped Cobalt(II) Heterometallic;Ai-Qin Zhang等，;《Z. Anorg. Allg. Chem.》;20150113;第678-683页 * |
| Two Novel Fe7Mg8 and Fe8Co7 Cluster-Based 3D Heterometallic Coordination Polymers with H4PMIDA and H3BTC as the Co-ligands: Synthesis, Structures,and Fluorescent Properties;Ai-Qin Zhang等，;《J. Clust. Sci.》;20141008;第26卷;第1115–1127页 * |
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