CN103266353A - Sandwich-type bismuth tungstate compound with methylimidazole simultaneously as counter ion and modified group and preparation method and application thereof - Google Patents
Sandwich-type bismuth tungstate compound with methylimidazole simultaneously as counter ion and modified group and preparation method and application thereof Download PDFInfo
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- CN103266353A CN103266353A CN2013100381526A CN201310038152A CN103266353A CN 103266353 A CN103266353 A CN 103266353A CN 2013100381526 A CN2013100381526 A CN 2013100381526A CN 201310038152 A CN201310038152 A CN 201310038152A CN 103266353 A CN103266353 A CN 103266353A
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 36
- 150000002500 ions Chemical class 0.000 title claims abstract description 23
- -1 bismuth tungstate compound Chemical class 0.000 title abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- 239000012634 fragment Substances 0.000 claims abstract description 4
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 230000001699 photocatalysis Effects 0.000 claims abstract description 4
- 238000007146 photocatalysis Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 34
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 34
- 230000004048 modification Effects 0.000 claims description 23
- 238000012986 modification Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 abstract 2
- 229910020350 Na2WO4 Inorganic materials 0.000 abstract 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 abstract 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 8
- 229940043267 rhodamine b Drugs 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000005260 alpha ray Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand 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
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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Abstract
The present invention discloses a sandwich-type bismuth tungstate compound with methylimidazole simultaneously as a counter ion and a modified group and a preparation method and application thereof. The compound is composed of methylimidazole counter cations and methylimidazole sandwich-type heteropolyacid fragments. The compound is a monocrystal, and belongs to the triclinic system, and the space group thereof is P-1. The formula of the compound is Na7(mim)2[{Na(H2O)2}3{CoII(mim)}3(BiIIIWVI9O33)2].9H2O, wherein mim is methylimidazole. The unit cell of the monocrystal has a crystal framework and composition as a formula 1. The structure of the formula 1 is shown as an abstract drawing. The preparation method includes adding an acidified Bi(NO3)3.H2O aqueous solution dropwisely into a Na2WO4.H2O aqueous solution under the protection of nitrogen, adding a methylimidazole aqueous solution containing Co(NO3)2.6H2O, adjusting pH, heating, cooling to room temperature, filtering to obtain a filtrate, slowly evaporating at room temperature to appear crystals, washing, and drying. The compound is useful for photocatalysis field. The compound is a novel monocrystal complex. The invention provides a novel method for synthesizing the monocrystal compound by taking nitrogen-containing aromatic ring as a template.
Description
Technical field
The invention belongs to the chemical material preparing technical field, be specifically related to a kind of Methylimidazole simultaneously as sandwich-like bismuth wolframic acid compound of counter ion and modification group and preparation method thereof and application.
Background technology
At present, because the singularity of polyacid Quito nuclear transition metal cluster compound structure, and at the potential application foreground of aspects such as nano level magnet, catalysis and optical material, receive increasing concern.In the process of constructing polyacid Quito nuclear transient metal cluster, extensively the synthesis strategy that adopts is: by using various omission type polyacid as the multiple tooth oxygen part that contains, by bridging, coordination multi-nuclear metal center to construct different coenocytisms.Up to the present, the novel cpd that obtains by these class methods not only One's name is legion, come in every shape, and on functional performance, also have nothing in common with each other.In the prior art, the compound of constructing as inorganic polydentate ligand with the bismuth wolframic acid of omission seldom.Be the common part of chemical material preparation field with Methylimidazole as coordination, in the synthetic chemistry of polyacid also through being often used as coordination agent and template, also have in recent years many new for the academic paper with the polyacid based compound of Methylimidazole modification group, but Methylimidazole but never appears in the newspapers as counter ion and modification group sandwich-like bismuth wolframic acid compound simultaneously.This class sandwich-like bismuth wolframic acid compound can be widely used in photocatalysis field, and its effect is: organic contamination in the catalyzed degradation water.So, develop a kind of Methylimidazole and be very important as sandwich-like bismuth wolframic acid compound of counter ion and modification group and preparation method thereof simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of Methylimidazole simultaneously as the sandwich-like bismuth wolframic acid compound of counter ion and modification group, second purpose is to provide the preparation method of above-mentioned sandwich-like bismuth wolframic acid compound; The 3rd purpose of the present invention is to provide above-mentioned sandwich-like bismuth wolframic acid application of compound.
First purpose of the present invention is to realize like this, described Methylimidazole is made up of Methylimidazole counter cation and Methylimidazole sandwich-like heteropolyacid fragment as counter ion and modification group sandwich-like bismuth wolframic acid compound simultaneously, monocrystalline, triclinic(crystalline)system, spacer is P-1, unit cell parameters is a=13.356 (3), b=17.292 (4), c=26.648 (5), α=98.28 (3), β=101.01 (3)
γ=107.93 (3), V=5610 (2)
3, Z=2; Its molecular formula is: Na
7(mim)
2[{ Na (H
2O)
2}
3{ Co
II(mim) }
3(Bi
IIIW
VI 9O
33)
2] 9H
2O, mim are Methylimidazole; The structural formula of Methylimidazole is:
Crystalline framework and composition that the unit cell of described sandwich-like bismuth wolframic acid compound monocrystal has formula 1, formula 1 structure as shown in Figure 1.
Second purpose of the present invention is achieved in that and comprises the steps:
A, with Na
2WO
4H
2O is dissolved in distilled water, is prepared into Na
2WO
4H
2The O aqueous solution;
B, with the Bi (NO that speed slowly splashes into acidifying that drips of 1/s
3)
3H
2The O aqueous solution at room temperature continues to stir 50 ~ 70min;
C, the slow adding contain Co (NO
3)
26H
2The Methylimidazole aqueous solution of O is regulated pH value to 7 ~ 9, continues 25 ~ 35min after being heated to 35 ~ 45 ℃, leaves standstill to be cooled to the room temperature after-filtration and to obtain filtrate;
D, filtrate the red-purple crystal occurs after at room temperature slowly volatilizing 5 ~ 9 days, clean with 95% ethanol, dry in air, can obtain described sandwich-like bismuth wolframic acid compound.
The 3rd purpose of the present invention is achieved in that the described Methylimidazole while is as the application of sandwich-like bismuth wolframic acid compound on photocatalysis field of counter ion and modification group.
The Methylimidazole that the present invention synthesizes is the monocrystalline title complex as the sandwich-like bismuth wolframic acid compound of counter ion and modification group simultaneously, Methylimidazole is not only as on the transition metal atoms that modification group directly is coordinated to polyanionic is connected, be free in around the polyanionic as counter cation and template simultaneously, novel structure, be a kind of novel monocrystalline title complex, for the crystal data storehouse has increased new data.This compound is not only the first Methylimidazole simultaneously as counter ion and modification group sandwich-like bismuth wolframic acid compound, also provides a kind of with the completely new approach of nitrogenous aromatic ring as template synthetic single crystal compound.
Description of drawings
Fig. 1 is the unit cell crystalline framework of sandwich-like bismuth wolframic acid compound monocrystal and forms structure iron;
Fig. 2 is the single crystal diffraction figure of sandwich-like bismuth wolframic acid compound of the present invention;
Fig. 3 is the figure as a result of ultraviolet catalytic degraded rhodamine B.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples, but never in any form the present invention is limited, and any conversion or improvement based on training centre of the present invention is done all fall into protection scope of the present invention.
The Methylimidazole while of the present invention is as the sandwich-like bismuth wolframic acid compound of counter ion and modification group, formed by Methylimidazole counter cation and Methylimidazole sandwich-like heteropolyacid fragment, monocrystalline, triclinic(crystalline)system, spacer is P-1, unit cell parameters is a=13.356 (3), b=17.292 (4), c=26.648 (5), α=98.28 (3), β=101.01 (3)
γ=107.93 (3), V=5610 (2)
3, Z=2; Its molecular formula is: Na
7(mim)
2[{ Na (H
2O)
2}
3{ Co
II(mim) }
3(Bi
IIIW
VI 9O
33)
2] 9H
2O, mim are Methylimidazole; The structural formula of Methylimidazole is:
；
Crystalline framework and composition that the unit cell of described sandwich-like bismuth wolframic acid compound monocrystal has formula 1, formula 1 structure as shown in Figure 1.
Methylimidazole of the present invention as the sandwich-like bismuth wolframic acid compounds process for production thereof of counter ion and modification group, is preferably operated under nitrogen protection simultaneously, specifically comprises the steps:
A, with Na
2WO
4H
2O is dissolved in distilled water, is prepared into Na
2WO
4H
2The O aqueous solution;
B, with the Bi (NO that speed slowly splashes into acidifying that drips of 1/s
3)
3H
2The O aqueous solution at room temperature continues to stir 50 ~ 70min;
C, the slow adding contain Co (NO
3)
26H
2The Methylimidazole aqueous solution of O is regulated pH value to 7 ~ 9, continues 25 ~ 35min after being heated to 35 ~ 45 ℃, leaves standstill to be cooled to the room temperature after-filtration and to obtain filtrate;
D, filtrate the red-purple crystal occurs after at room temperature slowly volatilizing 5 ~ 9 days, clean with 95% ethanol, dry in air, can obtain described sandwich-like bismuth wolframic acid compound.
Described nitrogen protection refers to starvation.
Described Na
2WO
4H
2Bi (the NO of the O aqueous solution, acidifying
3)
3H
2The O aqueous solution, contain Co (NO
3)
26H
2The volume ratio of the O Methylimidazole aqueous solution is 10:5:3.
Described Na
2WO
4H
2The O aqueous solution is according to the Na of 2.0mmol
2WO
4H
2O is dissolved in the ratio preparation of 20ml distilled water, cooperates the back with 120 ~ 180r/min vigorous stirring, 8 ~ 12min, filters insolubles, is described Na
2WO
4H
2The O aqueous solution.
Bi (the NO of described acidifying
3)
3H
2Be incorporated as 0.1mmol Bi (NO in the HCl solution of the O aqueous solution according to 10ml, 0.1M
3)
3H
2The ratio preparation of O.
Described Co (the NO that contains
3)
26H
2The preparation of the O Methylimidazole aqueous solution is by the Co (NO that dissolves in 0.2mmol in the 6ml Methylimidazole aqueous solution
3)
26H
2The ratio preparation of O, the concentration of Methylimidazole is 0.007g/ml in the Methylimidazole aqueous solution.
The described mixing speed of B step is 120 ~ 180r/min, and churning time is 60min.
Add in the C step and contain Co (NO
3)
26H
2Behind the Methylimidazole aqueous solution of O, with NaOH or the Na of 1mol/L
2CO
3Regulate pH value to 8, continue 30min after being heated to 40 ℃ then.
Described Na
2WO
4H
2The concentration of the O aqueous solution is 0.1molL
-1, the Bi (NO of acidifying
3)
3H
2The O concentration of aqueous solution is 0.01molL
-1Described Na
2WO
4H
2O, Co (NO
3)
26H
2The mol ratio of O, Methylimidazole is 5:10:2.
The Methylimidazole while of the present invention is as the application of sandwich-like bismuth wolframic acid compound in photochemical catalysis of counter ion and modification group.
Embodiment 1
Preparation Na
2WO
4H
2The O aqueous solution: with the Na of 1.0mmol
2WO
4H
2O(0.33g) be dissolved in the distilled water of 10ml, with 120r/min vigorous stirring 8min, filter insolubles, be prepared into Na
2WO
4H
2The O aqueous solution.
Embodiment 2
Preparation Na
2WO
4H
2The O aqueous solution: with the Na of 3.0mmol
2WO
4H
2O(0.99g) be dissolved in the distilled water of 30ml, with 150 r/min vigorous stirring 12min, filter insolubles, be prepared into Na
2WO
4H
2The O aqueous solution.
Embodiment 3
Preparation Na
2WO
4H
2The O aqueous solution: with the Na of 2.0mmol
2WO
4H
2O(0.66g) be dissolved in the distilled water of 20ml, with 180r/min vigorous stirring 10min, filter insolubles, be prepared into Na
2WO
4H
2The O aqueous solution.
Embodiment 4
Preparation acidifying Bi (NO
3)
3H
2The O aqueous solution: get the HCl solution 10ml of 0.1M, add 0.1mmol(0.05g) Bi (NO
3)
3H
2O, mixing.
Embodiment 5
Preparation contains Co (NO
3)
26H
2The O Methylimidazole aqueous solution: the concentration of getting Methylimidazole is the Methylimidazole aqueous solution 6ml of 0.007g/ml, dissolves in 0.2mmol(0.06 g) Co (NO
3)
26H
2O, mixing.
Embodiment 6
A, get the Na of embodiment 1 preparation
2WO
4H
2O aqueous solution 20ml;
B, with the acidifying Bi (NO that speed slowly splashes into embodiment 4 preparations that drips of 1/s
3)
3H
2O aqueous solution 10ml at room temperature is that 200r/min continues to stir 60min with the mixing speed;
C, slowly add embodiment 5 preparation contain Co (NO
3)
26H
2O Methylimidazole aqueous solution 6ml regulates pH value to 8 with the NaOH of 1mol/L, continues 30min after being heated to 40 ℃, leaves standstill to be cooled to the room temperature after-filtration and to obtain filtrate;
D, filtrate the red-purple crystal occurred after at room temperature slowly volatilizing 7 days, used
95% ethanol is cleaned, and dries in air, obtains Methylimidazole simultaneously as counter ion and modification group sandwich-like bismuth wolframic acid compound.
Embodiment 7
A, get the Na of embodiment 2 preparation
2WO
4H
2O aqueous solution 40ml;
B, with the acidifying Bi (NO that speed slowly splashes into embodiment 4 preparations that drips of 1/s
3)
3H
2O aqueous solution 20ml at room temperature is that 220r/min continues to stir 50min with the mixing speed;
C, slowly add embodiment 5 preparation contain Co (NO
3)
26H
2O Methylimidazole aqueous solution 12ml uses Na
2CO
3Regulate pH value to 7, continue 35min after being heated to 35 ℃, leave standstill and be cooled to the room temperature after-filtration and obtain filtrate;
D, filtrate the red-purple crystal occurred after at room temperature slowly volatilizing 5 days, cleaned with 95% ethanol, dried in air, obtained Methylimidazole simultaneously as counter ion and modification group sandwich-like bismuth wolframic acid compound.
Embodiment 8
A, get the Na of embodiment 3 preparation
2WO
4H
2O aqueous solution 10ml;
B, with the acidifying Bi (NO that speed slowly splashes into embodiment 4 preparations that drips of 1/s
3)
3H
2O aqueous solution 5ml at room temperature is that 240r/min continues to stir 50 ~ 70min with the mixing speed;
C, slowly add embodiment 5 preparation contain Co (NO
3)
26H
2O Methylimidazole aqueous solution 3ml regulates pH value to 9 with the NaOH of 1mol/L, continues 25min after being heated to 45 ℃, leaves standstill to be cooled to the room temperature after-filtration and to obtain filtrate;
D, filtrate the red-purple crystal occurs after at room temperature slowly volatilizing 9 days, clean with 95% ethanol, dry in air, obtain the Methylimidazole while as the sandwich-like bismuth wolframic acid compound of counter ion and modification group.
Embodiment 9
Get the compound of embodiment 6,7,8 preparations, adopt following method to measure its molecular formula:
Crystal that size is respectively 0.16 * 0.12 * 0.18 compound is encapsulated in to be collected by Japan R-axis Rapid of science IP monocrystalline x-ray diffractometer under 150K in the kapillary, adopt the IP technology, do x-ray source (λ=0.71073) with the monochromatic Mo target of graphite K alpha-ray.Adopt the rectification of Multi-scan receipts to record.The structure elucidation process of compound is all used SHELXTL-97 crystal software package, adopts direct method to resolve, and by complete matrix method of least squares F2 refine.
After measured, the compound of embodiment 6,7,8 preparations, its molecular formula is: Na
7(mim)
2[{ Na (H
2O)
2}
3
{ Co
II(mim) }
3(Bi
IIIW
VI 9O
33)
2] 9H
2O is the sandwich-like bismuth wolframic acid compound of Methylimidazole while as counter ion and modification group.Fig. 1 is the single crystal diffraction figure of embodiment 6.
Embodiment 10
Get the Methylimidazole while of embodiment 6 preparations as the sandwich-like bismuth wolframic acid compound of counter ion and modification group, adopt following method to measure its structure cell: crystal that size is respectively 0.16 * 0.12 * 0.18 compound is encapsulated in to be collected by Japan R-axis Rapid of science IP monocrystalline x-ray diffractometer under 150K in the kapillary, adopt the IP technology, do x-ray source (λ=0.71073) with the monochromatic Mo target of graphite K alpha-ray.Adopt the rectification of Multi-scan receipts to record.The structure elucidation process of compound is all used SHELXTL-97 crystal software package, adopts direct method to resolve, and by complete matrix method of least squares F2 refine.
Below be unit cell parameters (table 1) and the selectivity bond distance bond angle (table 2) of test determination
Table 1 structure cell and measuring parameter
aGoF?(F
2)?=?∑[w(F
o 2?─?F
c 2)
2/(n?─?P)]
1/2,?where?n?=?number?of?reflections?and?p?=?parameters?used;wR
2?=?∑[w(F
o 2─F
c 2)
2]/∑[w(F
o 2)
2]
1/2。
Table 2 selectivity bond distance bond angle
| Bond distance's bond angle | Bond distance's bond angle value |
| Bi(1)-O(36) | 2.088(16) |
| Bi(1)-O(35) | 2.094(15) |
| Bi(1)-O(38) | 2.106(15) |
| Bi(2)-O(8) | 2.108(13) |
| Bi(2)-O(15) | 2.109(14) |
| Bi(2)-O(30) | 2.138(17) |
| Co(1)-O(41) | 2.014(18) |
| Co(1)-O(24) | 2.019(16) |
| Co(1)-N(4) | 2.038(18) |
| Co(1)-O(37) | 2.056(16) |
| Co(1)-O(49) | 2.063(19) |
| Co(2)-O(20) | 2.000(17) |
| Co(2)-O(22) | 2.015(16) |
| Co(2)-O(18) | 2.042(16) |
| Co(2)-O(43) | 2.054(17) |
| Co(2)-N(1) | 2.071(16) |
| Co(4)-O(52) | 1.970(16) |
| Co(4)-O(33) | 2.021(15) |
| Co(4)-N(5) | 2.029(18) |
| Co(4)-O(44) | 2.072(17) |
| Co(4)-O(16) | 2.083(17) |
| Co(4)-Na(6) | 3.499(8) |
| Co(4)-Na(5) | 3.527(8) |
| W(2)-O(58) | 1.706(15) |
| W(2)-O(49) | 1.781(19) |
| W(2)-O(21) | 1.863(14) |
| W(2)-O(13) | 1.964(15) |
| W(2)-O(17) | 1.982(19) |
| W(2)-O(36) | 2.261(15) |
| W(3)-O(53) | 1.724(15) |
| W(3)-O(24) | 1.796(16) |
| W(3)-O(21) | 1.969(15) |
| W(3)-O(9) | 1.981(15) |
| W(3)-O(2) | 1.996(15) |
| W(3)-O(35) | 2.269(15) |
| O(36)-Bi(1)-O(35) | 86.6(6) |
| O(36)-Bi(1)-O(38) | 86.8(6) |
| O(35)-Bi(1)-O(38) | 88.5(6) |
| O(8)-Bi(2)-O(15) | 86.4(5) |
| O(8)-Bi(2)-O(30) | 88.1(6) |
| O(15)-Bi(2)-O(30) | 89.4(6) |
| O(41)-Co(1)-O(24) | 89.9(7) |
| O(41)-Co(1)-N(4) | 99.9(8) |
| O(24)-Co(1)-N(4) | 105.4(7) |
| O(41)-Co(1)-O(37) | 85.2(7) |
| O(24)-Co(1)-O(37) | 149.9(6) |
| N(4)-Co(1)-O(37) | 104.7(7) |
| O(41)-Co(1)-O(49) | 155.0(7) |
| O(24)-Co(1)-O(49) | 85.3(7) |
| N(4)-Co(1)-O(49) | 105.0(7) |
| O(37)-Co(1)-O(49) | 86.7(7) |
| O(52)-Co(4)-O(33) | 147.9(6) |
| O(52)-Co(4)-N(5) | 114.7(7) |
| O(33)-Co(4)-N(5) | 97.4(7) |
| O(52)-Co(4)-O(44) | 86.3(7) |
| O(33)-Co(4)-O(44) | 86.7(6) |
| N(5)-Co(4)-O(44) | 99.4(7) |
| O(52)-Co(4)-O(16) | 86.3(7) |
| O(33)-Co(4)-O(16) | 86.7(6) |
| N(5)-Co(4)-O(16) | 106.0(7) |
| O(44)-Co(4)-O(16) | 154.4(6) |
Embodiment 11
Get the Methylimidazole of embodiment 6 preparations simultaneously as the sandwich-like bismuth wolframic acid compound of counter ion and modification group, carry out in the test of using aspect the photochemical catalysis.
Effect to compound photocatalytic degradation RhB is studied.RhB is the oxa anthracenes ring compound that a class contains four N-ethyl.In the aqueous solution, under radiation of visible light, it is quite stable.Research process in, RhB concentration detects by measuring its absorbancy, further utilizes this data estimation activity of such catalysts: with this compound dissolution in aqueous solution rhodamine B (2.0 * 10
-5Mol L
-1) in the aqueous solution of PH=3.5, use NaOH or HClO
4Regulate its pH value.Magnetic agitation is 10 minutes then, and solution is exposed under the UV125W mercury lamp, keeps the distance of solution and lamp between 4-5cm.Continue to stir, every 30min, from beaker, get 3ml and detect.As Fig. 3, the A/A of rhodamine B
0Value significantly drops to 0 from 1 in 300min.Rhodamine B concentration is situation such as accompanying drawing 3 over time.
The change in concentration situation of rhodamine B can be used K=
(C 0 -C t )/
C 0 Expression, wherein
C 0 Represent the ultraviolet lighting time and be 0 o'clock the concentration of rhodamine B.Calculation result shows that the transformation efficiency of rhodamine B is respectively 100% and 99.6%.This degree of decomposition that also just means RhB is better than the decomposition effect of the polyacid system before most.In addition, after four-wheel repeated to add the photochemical catalysis test of rhodamine B of equivalent, this compound for catalysis activity there is no tangible reduction.This result shows that this compound can be as the potential Photodegradation catalyst of degradating organic dye.
Claims (10)
1. a Methylimidazole is simultaneously as the sandwich-like bismuth wolframic acid compound of counter ion and modification group, it is characterized in that described sandwich-like bismuth wolframic acid compound is made up of Methylimidazole counter cation and Methylimidazole sandwich-like heteropolyacid fragment, monocrystalline, triclinic(crystalline)system, spacer is P-1, unit cell parameters is a=13.356 (3), b=17.292 (4), c=26.648 (5), α=98.28 (3), β=101.01 (3)
γ=107.93 (3), V=5610 (2)
3, Z=2; Its molecular formula is: Na
7(mim)
2[{ Na (H
2O)
2}
3{ Co
II(mim) }
3(Bi
IIIW
VI 9O
33)
2] 9H
2O, mim are Methylimidazole; The structural formula of Methylimidazole is:
Crystalline framework and composition that the unit cell of described sandwich-like bismuth wolframic acid compound monocrystal has formula 1, formula 1 structure as shown in Figure 1.
2. the described Methylimidazole of claim 1 is characterized in that comprising the steps: simultaneously as the sandwich-like bismuth wolframic acid compounds process for production thereof of counter ion and modification group
A, with Na
2WO
4H
2O is dissolved in distilled water, is prepared into Na
2WO
4H
2The O aqueous solution;
B, with the Bi (NO that speed slowly splashes into acidifying that drips of 1/s
3)
3H
2The O aqueous solution at room temperature continues to stir 50 ~ 70min;
C, the slow adding contain Co (NO
3)
26H
2The Methylimidazole aqueous solution of O is regulated pH value to 7 ~ 9, continues 25 ~ 35min after being heated to 35 ~ 45 ℃, leaves standstill to be cooled to the room temperature after-filtration and to obtain filtrate;
D, filtrate the red-purple crystal occurs after at room temperature slowly volatilizing 5 ~ 9 days, clean with 95% ethanol, dry in air, can obtain described sandwich-like bismuth wolframic acid compound.
3. preparation method according to claim 2 is characterized in that described Na
2WO
4H
2Bi (the NO of the O aqueous solution, acidifying
3)
3H
2The O aqueous solution, contain Co (NO
3)
26H
2The volume ratio of the O Methylimidazole aqueous solution is 10:5:3.
4. according to claim 2 or 3 described preparation methods, it is characterized in that described Na
2WO
4H
2The O aqueous solution is according to the Na of 2.0mmol
2WO
4H
2O is dissolved in the ratio preparation of 20ml distilled water, with 120 ~ 180r/min vigorous stirring, 8 ~ 12min, filters insolubles then, is described Na
2WO
4H
2The O aqueous solution.
5. according to claim 2 or 3 described preparation methods, it is characterized in that the Bi (NO of described acidifying
3)
3H
2Be incorporated as 0.1mmol Bi (NO in the HCl solution of the O aqueous solution according to 10ml, 0.1M
3)
3H
2The ratio preparation of O.
6. according to claim 2 or 3 described preparation methods, it is characterized in that the described Co of containing (NO
3)
26H
2The preparation of the O Methylimidazole aqueous solution is by the Co (NO that dissolves in 0.2mmol in the 6ml Methylimidazole aqueous solution
3)
26H
2The ratio preparation of O, the concentration of Methylimidazole is 0.007g/ml in the Methylimidazole aqueous solution.
7. preparation method according to claim 2 is characterized in that the described mixing speed of B step is 120 ~ 180r/min, and churning time is 60min.
8. preparation method according to claim 2 is characterized in that adding contains Co (NO in the C step
3)
26H
2Behind the Methylimidazole aqueous solution of O, with NaOH or the Na of 1mol/L
2CO
3Regulate pH value to 8, continue 30min after being heated to 40 ℃ then.
9. preparation method according to claim 2 is characterized in that described Na
2WO
4H
2The concentration of the O aqueous solution is 0.1molL
-1, the Bi (NO of acidifying
3)
3H
2The O concentration of aqueous solution is 0.01molL
-1Described Na
2WO
4H
2O, Co (NO
3)
26H
2The mol ratio of O, Methylimidazole is 5:10:2.
10. the described Methylimidazole of a claim 1 is simultaneously as the application in photocatalysis field of the sandwich-like bismuth wolframic acid compound of counter ion and modification group.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669778A (en) * | 2016-02-24 | 2016-06-15 | 昆明学院 | High-deficiency arsenomolybdate sandwich type supramolecular compound and synthesis method and application thereof |
| CN106366102A (en) * | 2016-08-08 | 2017-02-01 | 河南大学 | Waugh-type manganese molybdate included in dysprosium-isonicotinic acid, and preparation method and application thereof |
| CN107141259A (en) * | 2017-05-12 | 2017-09-08 | 昆明学院 | A kind of imidazoles with many wolframic acid cocrystallization super molecular compounds and preparation method thereof |
-
2013
- 2013-01-31 CN CN201310038152.6A patent/CN103266353B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| HONG LIU ET AL.: "Sandwich transitional metal complexes with tungstobismuthates and 1-methylimidazole ligands: Syntheses, structures and magnetic properties", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669778A (en) * | 2016-02-24 | 2016-06-15 | 昆明学院 | High-deficiency arsenomolybdate sandwich type supramolecular compound and synthesis method and application thereof |
| CN105669778B (en) * | 2016-02-24 | 2018-04-03 | 昆明学院 | A kind of high vacant arsenic molybdic acid interlayer type super molecular compound and its synthetic method and application |
| CN106366102A (en) * | 2016-08-08 | 2017-02-01 | 河南大学 | Waugh-type manganese molybdate included in dysprosium-isonicotinic acid, and preparation method and application thereof |
| CN106366102B (en) * | 2016-08-08 | 2018-02-16 | 河南大学 | Waugh manganese molybdates that a kind of dysprosium-isonicotinic acid includes and its preparation method and application |
| CN107141259A (en) * | 2017-05-12 | 2017-09-08 | 昆明学院 | A kind of imidazoles with many wolframic acid cocrystallization super molecular compounds and preparation method thereof |
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