CN110273181A - A kind of more molybdenum oxygen hydrochlorate crystalline materials of the cupric of hybrid inorganic-organic and preparation method thereof - Google Patents
A kind of more molybdenum oxygen hydrochlorate crystalline materials of the cupric of hybrid inorganic-organic and preparation method thereof Download PDFInfo
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- CN110273181A CN110273181A CN201910689136.0A CN201910689136A CN110273181A CN 110273181 A CN110273181 A CN 110273181A CN 201910689136 A CN201910689136 A CN 201910689136A CN 110273181 A CN110273181 A CN 110273181A
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- hydrothermal synthesis
- oxygen hydrochlorate
- cupric
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- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002178 crystalline material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims abstract description 13
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 12
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 12
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 12
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000011368 organic material Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000009396 hybridization Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- -1 MoO2 anion Chemical class 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 235000016768 molybdenum Nutrition 0.000 description 3
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910017299 Mo—O Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003759 clinical diagnosis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of more molybdenum oxygen hydrochlorate crystalline materials of the cupric of hybrid inorganic-organic and preparation method thereof, belong to hybrid inorganic-organic materials, polyoxometallate Material Field.Its chemical formula is (C4H6N2)8Cu4[Mo8O26]；Anorthic system, space group P-1, cell parameter areα=73.297 (8)o, β=70.196 (8)o, γ=76.896 (8)o.More molybdenum oxygen hydrochlorate crystalline materials are prepared using hydrothermal synthesis method, and ammonium molybdate, 1- methylimidazole, copper sulphate and water are placed in synthesis in enclosed system and are made.More molybdenum oxygen hydrochlorate crystalline materials can play catalytic action when hydrogen peroxide oxidation cyclopentene prepares glutaraldehyde, products collection efficiency can be made to reach 62%, show preferable catalytic activity.
Description
Technical field
The invention belongs to hybrid inorganic-organic materials, polyoxometallate Material Field, be specifically related to it is a kind of it is organic-
More molybdenum oxygen hydrochlorate crystalline materials of the cupric of inorganic hybridization and preparation method thereof.
Background technique
Certain transition metal, such as niobium, tantalum, molybdenum and tungsten are capable of forming polyoxometallate under its high oxidation state, this kind of
Material have unique electronic structure, often show some excellent characteristics, as electric conductivity, magnetism, oxidation-reduction quality, catalytic and
Optical nonlinearity etc., analysis, clinical diagnosis, catalysis (include photocatalysis), biochemical, medicine and in terms of have
It is widely applied.Therefore this kind of polyoxometallate with specific composition and function is prepared increasingly by the weight of people
Depending on.
With going deep into for polyoxometallate investigation of materials, people start organic ingredient and inorganic multi-metal oxygen list
First hydridization forms the material of hybrid inorganic-organic.Special emphasis is a little that catalytic activity is that this kind of material one is important
General character.Compared with other catalysis materials, catalytic activity is high, the small toxicity of itself, and catalysis by-product is few, thus designs and prepare
Such material is the work for having very much realistic meaning.It is how that selection is suitable in the newest challenge of this research field at present
Method, construct the crystal for wishing structure using basic construction unit (module), and how to make the catalysis of such material
Performance is further promoted.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defect of the prior art, a kind of hybrid inorganic-organic is proposed
More molybdenum oxygen hydrochlorate crystalline materials of cupric and preparation method thereof.
To solve technical problem of the invention, a kind of used technical solution are as follows: more molybdenums of the cupric of hybrid inorganic-organic
Oxygen hydrochlorate crystalline material is made of more molybdenum oxygen hydrochlorate crystal, and chemical formula is (C4H6N2)8Cu4[Mo8O26], structural formula such as Fig. 1
It is shown.
The more molybdenum oxygen hydrochlorate crystalline materials of the cupric of above-mentioned hybrid inorganic-organic are prepared using hydrothermal synthesis method, by 0.08~
0.12 parts by weight ammonium molybdate, 0.10~0.15 parts sulfuric acid copper, 0.02~0.05 parts by weight 1- methylimidazole and 15~20 weights
Amount part water is uniformly hybridly prepared into reaction substrate, and hybrid inorganic-organic is made in hydrothermal synthesis to reaction substrate in the reaction vessel
The more molybdenum oxygen hydrochlorate crystalline materials of cupric, hydrothermal synthesis temperature are at least 160 DEG C, and the hydrothermal synthesis time is at least 10h.
The beneficial effect of the present invention compared with the existing technology is:
First, detected as single crystal diffractometer target product to made from, as a result, it can be seen that the target product
Crystal-chemical formula is (C4H6N2)8Cu4[Mo8O26], crystal belongs to anorthic system, space group P-1, and cell parameter is α=73.297 (8) °, β=70.196 (8) °, γ=76.896
(8) °,Z=2, Dc=2.417g/cm3.The target product is named as the more molybdenums of cupric of hybrid inorganic-organic
Oxygen hydrochlorate crystalline material.
Second, according to chemical formula (C4H6N2)8Cu4[Mo8O26] calculate the content of H, C, N in compound: H 2.30%, C
18.22%, N 10.63%.By elemental analysis, show that the content of H, C, N in the crystalline material are respectively 2.35%, C
18.18%, N 10.71%, this result are consistent with theoretical calculation.
Third, the more molybdenum oxygen hydrochlorate crystalline materials of the cupric of hybrid inorganic-organic, prepare penta 2 in hydrogen peroxide oxidation cyclopentene
Catalytic action can be played when aldehyde, products collection efficiency can be made to reach 60% or more.
Fourth, the preparation of the more molybdenum oxygen hydrochlorate crystalline materials of the cupric of hybrid inorganic-organic is realized by hydrothermal synthesis method, close
Simple to operation at method, reaction yield is higher.
Fifth, hydrothermal synthesis temperature is extremely in the preparation method of the more molybdenum oxygen hydrochlorate crystalline materials of the cupric of hybrid inorganic-organic
Less it is 160 DEG C, otherwise can not prepares the crystalline material.
Further embodiment as beneficial effect: first, the time of hydrothermal synthesis is 24~48h, the temperature of hydrothermal synthesis
It is 180~200 DEG C, help to obtain the more molybdenum oxygen hydrochlorate crystalline materials of cupric of the hybrid inorganic-organic of more high yield.Second,
Hydrothermal synthesis start before by reaction substrate temperature from room temperature to the rate of hydrothermal synthesis temperature be 1~2 DEG C/min, hydro-thermal close
From hydrothermal synthesis greenhouse cooling to the rate of room temperature it is 6~8 DEG C/h after, help to obtain form preferably more molybdenum oxygen acid
Salt crystal.Fourth, reaction vessel is the autoclave being placed in baking oven, and hydrothermal synthesis start before heating, hydrothermal synthesis process
In heat preservation and the cooling after hydrothermal synthesis be to be regulated and controled by baking oven, hydrothermal synthesis reaction carries out in autoclave
Water can be made to be in subcritical under supercriticality, reaction at this time is improved in molecular level, reactivity, therefore using autoclave
Than can preferably prepare such crystalline material using other equipment.Baking oven adjusts the temperature of hydro-thermal reaction in which can be convenient,
Hydrothermal reaction kettle can be made to keep suitable heating, cooling speed.
Detailed description of the invention
The present invention is made with attached drawing with reference to embodiments and being discussed further.
Fig. 1 is the mono-crystalline structures figure of target product produced by the present invention.
Fig. 2 is the infrared spectrometer carry out table for using target product produced by the present invention model VECTOR22FT-IR
One of result of sign；Wherein, abscissa is wave number/cm-1, ordinate is transmitance/%.
Fig. 3 be result that target product produced by the present invention is characterized using model Q500 thermogravimetric analyzer it
One；Wherein, abscissa be temperature/DEG C, ordinate be weight change/%.
Specific embodiment
Embodiment 1
1., weigh ammonium molybdate 0.08g, 1- methylimidazole 0.02g and copper sulphate 0.10g in 50mL flask, and be added
Flask is placed on magnetic stirring apparatus and is stirred 30 minutes by 18mL water.
2., mixed solution is transferred in 25mL autoclave.
3., autoclave is put into baking oven, 180 DEG C are heated to since room temperature with the rate of 1.5 DEG C/min, in this temperature
Lower holding for 24 hours, is then down to room temperature with the rate of 6 DEG C/h, obtains having shown in Fig. 2 and Fig. 3 curve as shown in Fig. 1 structural formula
The more molybdenum oxygen hydrochlorate crystalline materials of machine-inorganic hybridization cupric, yield is about 75%.
Crystal structure determination is carried out to target product made from the present embodiment as single crystal diffractometer, as a result as follows:
Crystal data:
Crystal bond distanceData:
| Mo(1)-O(1) | 1.689(2) | Mo(2)-O(7) | 1.899(2) | Mo(3)-O(5) | 2.452(2) |
| Mo(1)-O(3) | 1.745(2) | Mo(2)-O(4) | 1.994(2) | Mo(4)-O(13) | 1.697(2) |
| Mo(1)-O(2) | 1.944(1) | Mo(2)-O(5) | 2.337(1) | Mo(4)-O(12) | 1.698(7) |
| Mo(1)-O(4) | 1.947(1) | Mo(3)-O(9) | 1.701(2) | Mo(4)-O(11) | 1.895(2) |
| Mo(1)-O(5) | 2.131(1) | Mo(3)-O(10) | 1.704(2) | Mo(4)-O(2) | 1.995(2) |
| Mo(2)-O(6) | 1.694(2) | Mo(3)-O(7) | 1.922(2) | Mo(4)-O(5) | 2.345(1) |
| Mo(2)-O(8) | 1.703(2) | Mo(3)-O(11) | 1.923(2) | Cu(1)-N(1) | 1.870(2) |
| N(7)-Cu(2) | 1.873(3) | N(5)-Cu(2) | 1.868(2) | Cu(1)-N(3) | 1.870(2) |
Crystal bond angle (o) data:
| O(1)-Mo(1)-O(3) | 104.34(8) | O(8)-Mo(2)-O(5) | 95.64(7) | O(11)-Mo(3)-O(5) | 74.12(6) |
| O(1)-Mo(1)-O(2) | 101.06(7) | O(7)-Mo(2)-O(5) | 77.11(6) | O(13)-Mo(4)-O(12) | 104.67(9) |
| O(3)-Mo(1)-O(2) | 96.87(7) | O(4)-Mo(2)-O(5) | 73.03(6) | O(13)-Mo(4)-O(11) | 101.71(8) |
| O(1)-Mo(1)-O(4) | 101.56(7) | O(9)-Mo(3)-O(10) | 105.18(1) | O(12)-Mo(4)-O(11) | 101.13(8) |
| O(3)-Mo(1)-O(4) | 95.86(7) | O(9)-Mo(3)-O(7) | 102.07(8) | O(13)-Mo(4)-O(2) | 100.73(8) |
| O(2)-Mo(1)-O(4) | 150.34(6) | O(10)-Mo(3)-O(7) | 98.63(8) | O(12)-Mo(4)-O(2) | 98.27(8) |
| O(1)-Mo(1)-O(5) | 99.49(7) | O(9)-Mo(3)-O(11) | 102.78(8) | O(11)-Mo(4)-O(2) | 145.37(6) |
| O(3)-Mo(1)-O(5) | 156.17(6) | O(6)-Mo(2)-O(8) | 104.91(9) | O(13)-Mo(4)-O(5) | 160.16(7) |
| O(2)-Mo(1)-O(5) | 78.75(6) | Mo(2)-O(5)-Mo(4) | 163.99(7) | O(12)-Mo(4)-O(5) | 94.89(7) |
| O(4)-Mo(1)-O(5) | 78.81(6) | Mo(1)-O(5)-Mo(3) | 164.76(7) | O(11)-Mo(4)-O(5) | 77.25(6) |
| O(6)-Mo(2)-O(8) | 104.91(9) | Mo(2)-O(5)-Mo(3) | 86.19(5) | O(2)-Mo(4)-O(5) | 72.73(6) |
| O(6)-Mo(2)-O(7) | 101.37(8) | Mo(4)-O(5)-Mo(3) | 85.65(5) | Mo(1)-O(2)-Mo(4) | 109.91(7) |
| O(8)-Mo(2)-O(7) | 101.82(8) | O(10)-Mo(3)-O(11) | 98.76(8) | Mo(1)-O(4)-Mo(2) | 109.64(7) |
| O(6)-Mo(2)-O(4) | 100.84(8) | O(7)-Mo(3)-O(11) | 144.58(7) | Mo(1)-O(5)-Mo(2) | 92.16(5) |
| O(8)-Mo(2)-O(4) | 96.86(8) | O(9)-Mo(3)-O(5) | 159.98(8) | Mo(1)-O(5)-Mo(4) | 92.10(5) |
| O(7)-Mo(2)-O(4) | 146.05(6) | O(10)-Mo(3)-O(5) | 94.83(8) | N(1)-Cu(1)-N(3) | 169.85(9) |
| O(6)-Mo(2)-O(5) | 159.20(7) | O(7)-Mo(3)-O(5) | 73.86(6) | N(5)-Cu(2)-N(7) | 176.11(1) |
Crystal structure analysis:
Refering to fig. 1, crystal structure includes MoO2 anion [Mo more than one8O26]4-With four 1- methylimidazoles and copper ion
The composite cation [(C of coordination4H6N2)2Cu]+.More MoO2 anion [Mo8O26]4-Two identical { Mo can be regarded as4O13}2-
The combination of structural unit, total is by eight similar { MoO6Polyhedron composition, these polyhedrons are again in the form of total side
It connects.Eight molybdenum atoms can be divided into two groups, wherein four molybdenum atoms are in the same plane.In more MoO2 anions
[Mo8O26]4-In, Mo-O key can be divided into four classes: (i) Mo-Ot(end oxygen), distance existsBetween；(ii)
Mo-Oμ-2(bridging oxygen), distance existsBetween；(iii)Mo-Oμ-3(bridging oxygen), distance existsBetween；(iv)Mo-Oμ-4(bridging oxygen), distance existsBetween.
As shown in Figure 2,3133,3107cm in infrared spectroscopy-1Peak is that C-H stretching vibration absorbs on imidazole ring；2920cm-1The stretching vibration that peak is the C-H on methyl absorbs；1542-1024cm-1Peak is the absorption of vibrations of imidazole ring.931,893,795,
745、668、565cm-1Range of absorbent peak be Mo=O and Mo-O-Mo feature stretching vibration peak.By infrared spectroscopy it is found that inhaling
The vibration position for receiving peak is consistent with the structural analysis of target product.
As shown in Figure 3, this crystalloid keeps stablizing before 220 DEG C, starts fast decoupled at 310 DEG C.
Embodiment 2
1., weigh ammonium molybdate 0.09g, 1- methylimidazole 0.03g and copper sulphate 0.12g in 50mL flask, and be added
Flask is placed on magnetic stirring apparatus and is stirred 30 minutes by 18mL water.
2., mixed solution is transferred in 25mL autoclave.
3., autoclave is put into baking oven, 190 DEG C are heated to since room temperature with the rate of 1.5 DEG C/min, in this temperature
Lower holding for 24 hours, is then down to room temperature with the rate of 8 DEG C/h, obtains having shown in Fig. 2 and Fig. 3 curve as shown in Fig. 1 structural formula
The more molybdenum oxygen hydrochlorate crystalline materials of machine-inorganic hybridization cupric, yield is about 73%.
Embodiment 3
1., weigh ammonium molybdate 0.10g, 1- methylimidazole 0.04g and copper sulphate 0.12g in 50mL flask, and be added
Flask is placed on magnetic stirring apparatus and is stirred 30 minutes by 18mL water.
2., mixed solution is transferred in 25mL autoclave.
3., autoclave is put into baking oven, be heated to 180 DEG C since room temperature with the rate of 2 DEG C/min, at this temperature
It keeps for 24 hours, being then down to room temperature with the rate of 6 DEG C/h, obtaining as shown in Fig. 1 structural formula, organic shown in Fig. 2 and Fig. 3 curve-
The more molybdenum oxygen hydrochlorate crystalline materials of the cupric of inorganic hybridization, yield is about 69%.
Embodiment 4
1., weigh ammonium molybdate 0.11g, 1- methylimidazole 0.04g and copper sulphate 0.14g in 50mL flask, and be added
Flask is placed on magnetic stirring apparatus and is stirred 30 minutes by 18mL water.
2., mixed solution is transferred in 25mL autoclave.
3., autoclave is put into baking oven, 180 DEG C are heated to since room temperature with the rate of 1.5 DEG C/min, in this temperature
Lower holding for 24 hours, is then down to room temperature with the rate of 7 DEG C/h, obtains having shown in Fig. 2 and Fig. 3 curve as shown in Fig. 1 structural formula
The more molybdenum oxygen hydrochlorate crystalline materials of machine-inorganic hybridization cupric, yield is about 71%.
Embodiment 5
1., weigh ammonium molybdate 0.12g, 1- methylimidazole 0.02g and copper sulphate 0.13g in 50mL flask, and be added
Flask is placed on magnetic stirring apparatus and is stirred 30 minutes by 18mL water.
2., mixed solution is transferred in 25mL autoclave.
3., autoclave is put into baking oven, 180 DEG C are heated to since room temperature with the rate of 1.5 DEG C/min, in this temperature
Lower holding for 24 hours, is then down to room temperature with the rate of 6 DEG C/h, obtains having shown in Fig. 2 and Fig. 3 curve as shown in Fig. 1 structural formula
The more molybdenum oxygen hydrochlorate crystalline materials of machine-inorganic hybridization cupric, yield is about 72%.
Embodiment 6
1., weigh ammonium molybdate 0.11g, 1- methylimidazole 0.03g and copper sulphate 0.12g in 50mL flask, and be added
Flask is placed on magnetic stirring apparatus and is stirred 30 minutes by 20mL water.
2., mixed solution is transferred in 25mL autoclave.
3., autoclave is put into baking oven, 180 DEG C are heated to since room temperature with the rate of 1.5 DEG C/min, in this temperature
Lower holding 30h, is then down to room temperature with the rate of 8 DEG C/h, obtains having shown in Fig. 2 and Fig. 3 curve as shown in Fig. 1 structural formula
The more molybdenum oxygen hydrochlorate crystalline materials of machine-inorganic hybridization cupric, yield is about 78%.
Embodiment 7
1., weigh ammonium molybdate 0.11g, 1- methylimidazole 0.03g and copper sulphate 0.12g in 50mL flask, and be added
Flask is placed on magnetic stirring apparatus and is stirred 30 minutes by 20mL water.
2., mixed solution is transferred in 25mL autoclave.
3., autoclave is put into baking oven, 200 DEG C are heated to since room temperature with the rate of 1.5 DEG C/min, in this temperature
Lower holding 30h, is then down to room temperature with the rate of 6 DEG C/h, obtains having shown in Fig. 2 and Fig. 3 curve as shown in Fig. 1 structural formula
The more molybdenum oxygen hydrochlorate crystalline materials of machine-inorganic hybridization cupric, yield is about 81%.
Embodiment 8
1., weigh ammonium molybdate 0.11g, 1- methylimidazole 0.03g and copper sulphate 0.12g in 50mL flask, and be added
Flask is placed on magnetic stirring apparatus and is stirred 30 minutes by 20mL water.
2., mixed solution is transferred in 25mL autoclave.
3., autoclave is put into baking oven, 190 DEG C are heated to since room temperature with the rate of 1.5 DEG C/min, in this temperature
Lower holding 36h, is then down to room temperature with the rate of 8 DEG C/h, obtains having shown in Fig. 2 and Fig. 3 curve as shown in Fig. 1 structural formula
The more molybdenum oxygen hydrochlorate crystalline materials of machine-inorganic hybridization cupric, yield is about 83%.
Embodiment 9
1., weigh ammonium molybdate 0.11g, 1- methylimidazole 0.03g and copper sulphate 0.12g in 50mL flask, and be added
Flask is placed on magnetic stirring apparatus and is stirred 30 minutes by 20mL water.
2., mixed solution is transferred in 25mL autoclave.
3., autoclave is put into baking oven, be heated to 200 DEG C since room temperature with the rate of 2 DEG C/min, at this temperature
48h is kept, room temperature is then down to the rate of 7 DEG C/h, is obtained as shown in Fig. 1 structural formula, organic shown in Fig. 2 and Fig. 3 curve-
The more molybdenum oxygen hydrochlorate crystalline materials of the cupric of inorganic hybridization, yield is about 85%.
Embodiment 10
Application Example
The more molybdenum oxygen hydrochlorate crystalline materials of the cupric of hybrid inorganic-organic prepare glutaraldehyde in catalysis hydrogen peroxide oxidation cyclopentene
On application.
It takes 0.07g to be ground into the more molybdenum oxygen hydrochlorate crystalline materials of cupric of the hybrid inorganic-organic of powder, is added to equipped with 20mL
The tert-butyl alcohol and 8mL cyclopentene round-bottomed flask in, control reaction temperature at 36 DEG C, the hydrogen peroxide of 15mL is added dropwise.After reacting 3h,
Solution is filtered, catalyst is removed, carries out chromatography.The result shows that the yield of products therefrom up to 62%, is demonstrated by preferably
Catalytic activity.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Design or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (7)
1. a kind of more molybdenum oxygen hydrochlorate crystalline materials of the cupric of hybrid inorganic-organic, are made of, feature exists more molybdenum oxygen hydrochlorate crystal
In:
The chemical formula of more molybdenum oxygen hydrochlorate crystal is (C4H6N2)8Cu4[Mo8O26]；
The structural formula of more molybdenum oxygen hydrochlorate crystal are as follows:
More molybdenum oxygen hydrochlorate crystal belong to anorthic system, space group P-1, and cell parameter is α=73.297 (8) °, β=70.196 (8) °, γ=76.896 (8) °,Z=2, Dc=2.417g/cm3。
2. a kind of method for the more molybdenum oxygen hydrochlorate crystalline materials of cupric for preparing hybrid inorganic-organic as described in claim 1 uses
Hydrothermal synthesis method, it is characterised in that: by 0.08~0.12 parts by weight ammonium molybdate, 0.10~0.15 parts sulfuric acid copper, 0.02~
0.05 parts by weight 1- methylimidazole and 15~20 parts by weight water are uniformly hybridly prepared into reaction substrate, and reaction substrate is in reaction vessel
The more molybdenum oxygen hydrochlorate crystalline materials of cupric of hybrid inorganic-organic are made in middle hydrothermal synthesis, and hydrothermal synthesis temperature is at least 160 DEG C,
The hydrothermal synthesis time is at least 10h.
3. preparation method as claimed in claim 2, it is characterised in that: the time of hydrothermal synthesis is 24~48h, hydrothermal synthesis
Temperature is 180~200 DEG C.
4. preparation method as claimed in claim 2, it is characterised in that: hydrothermal synthesis start before by reaction substrate temperature from room temperature
The rate for being warming up to hydrothermal synthesis temperature is 1~2 DEG C/min.
5. preparation method as claimed in claim 2, it is characterised in that: after hydrothermal synthesis extremely from hydrothermal synthesis greenhouse cooling
The rate of room temperature is 6~8 DEG C/h.
6. preparation method as claimed in claim 2, it is characterised in that: the reaction vessel is the autoclave being placed in baking oven,
And hydrothermal synthesis start before heating, the heat preservation during hydrothermal synthesis and the cooling after hydrothermal synthesis be to pass through baking oven
Regulated and controled.
7. a kind of more molybdenum oxygen hydrochlorate crystalline materials of the cupric of hybrid inorganic-organic as described in claim 1 are in catalysis dioxygen water oxygen
Change cyclopentene and prepares the application on glutaraldehyde.
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