CN107262107B - The preparation method of interlayer type nickel substitution silicon tungsten oxygen cluster catalyst - Google Patents
The preparation method of interlayer type nickel substitution silicon tungsten oxygen cluster catalyst Download PDFInfo
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- CN107262107B CN107262107B CN201710578117.1A CN201710578117A CN107262107B CN 107262107 B CN107262107 B CN 107262107B CN 201710578117 A CN201710578117 A CN 201710578117A CN 107262107 B CN107262107 B CN 107262107B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 20
- 239000011229 interlayer Substances 0.000 title claims abstract description 18
- SKKJKSIXKUSLIE-UHFFFAOYSA-N oxotungsten;silicon Chemical compound [Si].[W]=O SKKJKSIXKUSLIE-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000006467 substitution reaction Methods 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000011734 sodium Substances 0.000 claims abstract description 30
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 12
- 238000001914 filtration Methods 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- FVIZARNDLVOMSU-UHFFFAOYSA-N ginsenoside K Natural products C1CC(C2(CCC3C(C)(C)C(O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O FVIZARNDLVOMSU-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000001907 polarising light microscopy Methods 0.000 description 7
- 229920006324 polyoxymethylene Polymers 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- BSFODEXXVBBYOC-UHFFFAOYSA-N 8-[4-(dimethylamino)butan-2-ylamino]quinolin-6-ol Chemical compound C1=CN=C2C(NC(CCN(C)C)C)=CC(O)=CC2=C1 BSFODEXXVBBYOC-UHFFFAOYSA-N 0.000 description 1
- 229910014142 Na—O Inorganic materials 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- CVORJJBFHWXCFW-UHFFFAOYSA-N [P].[Mo]=O Chemical compound [P].[Mo]=O CVORJJBFHWXCFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KLCQXXAKURQDOV-UHFFFAOYSA-N chlorobenzene methanol Chemical compound CO.CO.ClC1=CC=CC=C1 KLCQXXAKURQDOV-UHFFFAOYSA-N 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 flavouring Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 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
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation methods that interlayer type nickel replaces silicon tungsten oxygen cluster catalyst, this kind of method is by K8[γ‑SiW10O36]·12H2O, nickel chloride, sodium acetate-hac buffer are placed in a beaker reaction, and after completion of the reaction, filtering, filtrate are slowly volatilized, and obtain the crystal that interlayer type nickel replaces silicon tungsten oxygen cluster catalyst.The method of the present invention has the product purity height that reaction speed is fast, reaction process is simple, obtains, and post-processes the features such as simple.In the selective oxidation of aromatic alcohol, Transformation efficiency is up to 90 .8%, selectivity up to 95.1%.
Description
Technical field
The invention belongs to catalyst material preparation technical field, the interlayer type nickel being directed to replaces the catalysis of silicon tungsten oxygen cluster
The technology of preparing of agent, the present invention in novel clamp cardioid nickel replace silicon tungsten oxygen cluster have preferable catalytic activity.
Background technique
Multi-metal oxygen cluster (Polyoxometalates is condensed to POMs) is in a kind of skeleton structure rich in Mo, W, V, Nb
With polymeta- oxygen cluster (Metal-Oxygen Clusters) compound of the transition elements such as Ta.The composition of POMs is determined with structure
Determining it, excellent catalysis is presented in multi-metal oxygen cluster with highly acid and strong oxidizing property, therefore in many type organic synthesis
Characteristic.Since 1970s, many catalysis scholars have set foot in POMs research field, either also from fundamental research
It is that industrial applications exploitation all has been achieved for remarkable achievement.POMs catalytic chemistry has become POMs scientific domain at present
In one of most promising research direction, the extensive concern by domestic and foreign scholars.
It is organic synthesis and industrial important reaction that alcohol, which is oxidized to corresponding carbonyls, especially by benzene first
Alcohol prepares benzaldehyde, is a kind of important organic reaction.Benzaldehyde is simplest, is also industrial most important aromatic aldehyde.
It is mainly used as the raw material of the important intermediates such as manufacture dyestuff, medicine, fragrance, flavouring, pesticide.Early stage once uses MnO2Equal oxidants
It aoxidizes toluene and benzaldehyde is made, industrial production mostly uses benzyl chloride oxidizing process at present.In recent years, the method for synthesizing benzaldehyde is not
It is disconnected to be modified, the useful chromium compound reported recently and in the presence of a phase transfer catalyst hypochlorite catalysis oxidation benzyl chloride with
CrO in the presence of medium and ligand3Oxybenzene methyl alcohol etc., although these methods improve the conversion ratio of reactant to some extent
Presence with the selectivity of benzaldehyde, but halide and high state metallic compound brings serious environmental problem, does not meet green
The principle of colour chemistry development.From atomic economy reaction and it is environmental-friendly from the perspective of, use hydrogen peroxide generation as oxidant be solve
The certainly preferred approach of problem.Wherein crucial problem is the suitable catalyst system of selection into emphasis to solve this problem.
In recent years, document report Zn-Sb replace more tungsten oxygen clusters (Chem. Eur. J., 2012,13293.), phosphorus molybdenum
Oxygen cluster (Datlon, 2011,8414) and oxidation alcohol molecule, but there is noble metal dosages in the above reaction big, reaction condition
Not mild, reaction not enough green, the problems such as catalytic activity is unsatisfactory.On the basis of document above, according to Green Chemistry
Idea of development, it is very necessary for designing the oxidation of aromatic alcohol and generating the environmental-friendly efficient catalytic system of aromatic aldehyde.
By retrieval, patent document related with the present patent application is not found not yet.
Summary of the invention
Present invention aim to address simple multi-metal oxygen cluster catalysts to be catalyzed work during the selective oxidation of alcohol
Property problem to be improved, the preparation method that a kind of synthesis interlayer type nickel replaces silicon tungsten oxygen cluster catalyst is provided, in alcohol
Play the role of catalysis in selective oxidation.
Object of the present invention is to what is realized by following technical measures:
It synthesizes to obtain the crystal of interlayer type nickel substitution silicon tungsten oxygen cluster by conventional solution reaction, experimental method is as follows:
K is sequentially added in a clean beaker8[γ-SiW10O36]·12H2O (1.5 ~ 2.5g) and 20 ~ 50 mL
In sodium acetate-hac buffer, 15 ~ 30 min are stirred strongly at 40 ~ 50 DEG C, be added nickel salt (0.2 ~ 0.5g), reaction 2 ~
5h is cooled to room temperature after completion of the reaction, filtering, and filtrate slow evaporation at room temperature obtained bulk-shaped monocrystal after 5 ~ 7 days.Yield is about
32~57%。
Preferably, the interlayer type nickel replaces the preparation method of silicon tungsten oxygen cluster catalyst, and the interlayer type nickel replaces silicon
The molecular formula of tungsten oxygen cluster catalyst 1: K4(H2O)8Na8(H2O)8Ni4Si2W18O68。
Preferably, the interlayer type nickel replaces the preparation method of silicon tungsten oxygen cluster catalyst, and the nickel salt is nickel chloride,
Middle K8[γ-SiW10O36]·12H2O: the mass ratio (g/g) of nickel chloride is 1.5 ~ 2.5:0.2 ~ 0.5.
Preferably, the interlayer type nickel replaces the preparation method of silicon tungsten oxygen cluster catalyst, the K8[γ-SiW10O36]·
12H2O and sodium acetate-hac buffer mass volume ratio (g/ml) are 1.5 ~ 2.5:20 ~ 50.
Product is characterized by single crystal X diffraction, powder x-ray diffraction, obtains the accurate information about crystal structure.Tool
The result of body is as follows:
The molecular formula of crystal is K4(H2O)8Na8(H2O)8Ni4Si2W18O68, wherein cationic portion is K+, Na+And
Ni2+Cation, anion are POM polyanionic, and the two is incorporated in one by K-O, the interaction of Na-O and Ni-O chemical bond
It rises.Pass through structural analysis, it has been found that this catalyst activated centre containing there are two, one is transition metal sites, and one is
The site POMs, the two all contribute the oxidation reaction of alcohol, it is desirable to can play the role of concerted catalysis.
This invention has mainly synthesized an interlayer type nickel and has replaced silicon tungsten oxygen cluster catalyst, has been applied to alcohols
The selective oxidation of compound.This invention relates to the preparation method that interlayer type nickel replaces silicon tungsten oxygen cluster catalyst.It is this kind of to urge
Agent can be selectively up to the selective oxidation of realization aromatic alcohol under relatively mild reaction condition, Transformation efficiency is up to 90 .8%
95.1%.The preparation method reaction process of such catalyst is simple.
The purpose of the present invention is what is be achieved through the following technical solutions:
Its molecular structure is as shown in Figure 1；
Molecular formula is respectively as follows: 1 K of compound4(H2O)8Na8(H2O)8Ni4Si2W18O68。
Above-mentioned aromatic alcohol be benzyl alcohol, to methylbenzyl alcohol, P-methoxybenzyl alcohol, to chlorobenzene methanol etc., solvent is selected
DMSO, methanol, ethyl alcohol etc., conversion ratio selectively pass through gas chromatographic detection.
The present invention provides one-component double activity center catalyst and has the advantage that
1, preparation method is simple and catalyst all has specific molecular structure, is conducive to research reaction mechanism；
2, catalyst has transition metal, multi-metal oxygen cluster activated centre, can have the oxidation to alcohol molecule to play collaboration and urge
Change effect；
3, catalyst is convenient for can be easily separated, and can be used for multiple times after processing, and be still able to maintain good catalytic activity,
Be conducive to industrialized production.
Detailed description of the invention
Fig. 1 is 1 K of compound4(H2O)8Na8(H2O)8Ni4Si2W18O68Crystal structure；
Fig. 2 is 1 K of compound4(H2O)8Na8(H2O)8Ni4Si2W18O68RXRD characterization.
Specific embodiment
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is served only for
Invention is further explained, should not be understood as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made to the present invention according to aforementioned present invention content.
1 compound K of embodiment4(H2O)8Na8(H2O)8Ni4Si2W18O68Preparation, synthesis step is as follows:
K is sequentially added in a clean beaker8[γ-SiW10O36]·12H2O (1.5g) and 20mL sodium acetate-
Hac buffer stirs 15min strongly at 40 DEG C, is added nickel chloride (0.2g), and reaction 2h is cooled to after completion of the reaction
Room temperature, filtering, filtrate slow evaporation at room temperature obtained bulk-shaped monocrystal after 5 ~ 7 days.Yield about 35%.
2 compound K of embodiment4(H2O)8Na8(H2O)8Ni4Si2W18O68Preparation, synthesis step is as follows:
K is sequentially added in a clean beaker8[γ-SiW10O36]·12H2O (2g) and 20mL sodium acetate-vinegar
Acid buffering solution stirs 15min strongly at 40 DEG C, is added nickel chloride (0.2g), and reaction 2h is cooled to room after completion of the reaction
Temperature, filtering, filtrate slow evaporation at room temperature obtained bulk-shaped monocrystal after 5 ~ 7 days.Yield about 37%.
3 compound K of embodiment4(H2O)8Na8(H2O)8Ni4Si2W18O68Preparation, synthesis step is as follows:
K is sequentially added in a clean beaker8[γ-SiW10O36]·12H2O (1.5g) and 30mL sodium acetate-
Hac buffer stirs 15min strongly at 40 DEG C, is added nickel chloride (0.25g), and reaction 2h is cooled to after completion of the reaction
Room temperature, filtering, filtrate slow evaporation at room temperature obtained bulk-shaped monocrystal after 5 ~ 7 days.Yield about 38%.
4 compound K of embodiment4(H2O)8Na8(H2O)8Ni4Si2W18O68Preparation, synthesis step is as follows:
K is sequentially added in a clean beaker8[γ-SiW10O36]·12H2O (2.5g) and 30mL sodium acetate-
Hac buffer stirs 30min strongly at 50 DEG C, is added nickel chloride (0.2g), and reaction 2h is cooled to after completion of the reaction
Room temperature, filtering, filtrate slow evaporation at room temperature obtained bulk-shaped monocrystal after 5 ~ 7 days.Yield about 45%.
5 compound K of embodiment4(H2O)8Na8(H2O)8Ni4Si2W18O68Preparation, synthesis step is as follows:
K is sequentially added in a clean beaker8[γ-SiW10O36]·12H2O (1.5g) and 30mL sodium acetate-
Hac buffer stirs 15min strongly at 50 DEG C, is added nickel chloride (0.2g), and reaction 2h is cooled to after completion of the reaction
Room temperature, filtering, filtrate slow evaporation at room temperature obtained bulk-shaped monocrystal after 5 ~ 7 days.Yield about 49%.
6 compound K of embodiment4(H2O)8Na8(H2O)8Ni4Si2W18O68Preparation, synthesis step is as follows:
K is sequentially added in a clean beaker8[γ-SiW10O36]·12H2O (1.5g) and 30mL sodium acetate-
Hac buffer stirs 30min strongly at 40 DEG C, is added nickel acetate (0.25g), and reaction 2h is cooled to after completion of the reaction
Room temperature, filtering, filtrate slow evaporation at room temperature obtained bulk-shaped monocrystal after 5 ~ 7 days.Yield about 52%.
7 compound K of embodiment4(H2O)8Na8(H2O)8Ni4Si2W18O68Preparation, synthesis step is as follows:
K is sequentially added in a clean beaker8[γ-SiW10O36]·12H2O (2g) and 30mL sodium acetate-vinegar
Acid buffering solution stirs 30min strongly at 50 DEG C, is added nickel acetate (0.2g), and reaction 5h is cooled to room after completion of the reaction
Temperature, filtering, filtrate slow evaporation at room temperature obtained bulk-shaped monocrystal after 5 ~ 7 days.Yield about 54%.
8 compound K of embodiment4(H2O)8Na8(H2O)8Ni4Si2W18O68Preparation, synthesis step is as follows:
K is sequentially added in a clean beaker8[γ-SiW10O36]·12H2O (1.5g) and 25mL sodium acetate-
Hac buffer stirs 20min strongly at 50 DEG C, is added nickel chloride (0.2g), adjusts pH value between 5 with spirit of vinegar,
Reaction 2h is cooled to room temperature after completion of the reaction, is filtered, and filtrate slow evaporation at room temperature obtained bulk-shaped monocrystal after 5 ~ 7 days.It produces
Rate about 41%.
Compound K4(H2O)8Na8(H2O)8Ni4Si2W18O68Crystallographic data, as shown in table 1:
Table 1
| Compounds | 1 |
| Formula | H32K4Na8Ni4O84Si2W18 |
| M r | 5316.87 |
| Crystal system | Triclinic |
| Space group | P-1 |
| Temperature | 296(2) K |
| a (Å) | 11.9353(9) |
| b (Å) | 13.9814(13) |
| c (Å) | 15.3098(16) |
| α (deg) | 117.122(3) |
| β (deg) | 102.858(2) |
| γ (deg) | 94.1320(10) |
| V (Å3) | 2172.1(3) |
| Z | 1 |
| D calc.(g cm-3) | 4.040 |
| F(000) | 2308 |
| R 1[I>2σ(I)] | 0.1568 |
| wR 2[I>2σ(I)] | 0.3484 |
| R 1(all data) | 0.2728 |
| wR 2(all data) | 0.4096 |
| GOOF | 1.108 |
This compound is characterized by X-ray single crystal diffraction as can be seen from Table 1, and through phenetic analysis, this compound belongs to three
Oblique system, space group P-1, molecular formula H32K4Na8Ni4O84Si2W18, the structure of molecular weight 5316.87 and compound
Just it coincide.
Fig. 1 is 1 K of compound4(H2O)8Na8(H2O)8Ni4Si2W18O68Crystal structure, Fig. 2 be 1 K of compound4(H2O)8Na8(H2O)8Ni4Si2W18O68RXRD characterization.As shown in Figure 1, this compound is the interlayer type SiW that four nickel replaces9Structure,
Two SiW9Cellular construction is placed exactly in the top and the bottom of four nickel ions, the folder replaced by four nickel of formation of chemical bond
Cardioid SiW9Compound.As can be seen from Figure 2, powder diffraction data is consistent with single crystal diffraction data, just coincide, and illustrates that we synthesize
Compound it is consistent with single crystal analysis result.
Test example: the catalysis oxidation application of aromatic alcohol
It takes 0.25mmol aromatic alcohol to be dissolved in 2ml solvent, and catalyst 15mg is added, hydrogen peroxide 0.5mmol is added, adds
Thermal agitation simultaneously maintains temperature at 40 ~ 60 degrees Celsius, after reacting 4-8h, with gas chromatographic detection, the data of specific aromatic alcohol oxidation
It is as shown in table 2:
2 compound 1 of table is to aromatic alcohol selective oxidation the results list
| Entry | alcohols | product | Conv.(%) | Sele. (%)[b] |
| 1 | 87.8 | 93.2 | ||
| 2 | 89.6 | 94.3 | ||
| 3 | 88.5 | 95.0 | ||
| 4 | 90.8 | 95.1 | ||
| 5 | 85.4 | 93.7 |
Benzene first of this compound for the either electrophilic benzyl alcohol replaced or supplied for electronic substitution as can be seen from Table 2
Alcohol all has a good catalyzed conversion effect, but the benzyl alcohol replaced for electron-donating group is due to the influence of electronic effect,
Its conversion ratio is slightly promoted, and up to 90.8%.
Claims (3)
1. the preparation method of interlayer type nickel substitution silicon tungsten oxygen cluster catalyst, which is characterized in that its synthesis step are as follows:
K is sequentially added in a clean beaker8[γ-SiW10O36]·12H2O and sodium acetate-hac buffer,
15 ~ 30 min are stirred at 45 DEG C strongly, nickel salt is added, reaction 4h is cooled to room temperature after completion of the reaction, filters, filtrate is in room temperature
Lower slow evaporation, obtained bulk-shaped monocrystal after 5 ~ 7 days；The interlayer type nickel replaces the molecular formula of silicon tungsten oxygen cluster catalyst: K4(H2O)8Na8(H2O)8Ni4Si2W18O68。
2. the preparation method that interlayer type nickel as described in claim 1 replaces silicon tungsten oxygen cluster catalyst, which is characterized in that the nickel
Salt is nickel chloride, wherein K8[γ-SiW10O36]·12H2O: the mass ratio of nickel chloride is 1.5 ~ 2.5:0.2 ~ 0.5.
3. the preparation method that interlayer type nickel as described in claim 1 replaces silicon tungsten oxygen cluster catalyst, which is characterized in that the K8
[γ-SiW10O36]·12H2O and sodium acetate-hac buffer mass volume ratio are 1.5 ~ 2.5g:20 ~ 50ml.
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