CN103301868B - Core-shell structural nano catalyst as well as preparation method and application thereof - Google Patents

Core-shell structural nano catalyst as well as preparation method and application thereof Download PDF

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CN103301868B
CN103301868B CN201310289467.8A CN201310289467A CN103301868B CN 103301868 B CN103301868 B CN 103301868B CN 201310289467 A CN201310289467 A CN 201310289467A CN 103301868 B CN103301868 B CN 103301868B
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nanocatalyst
nucleocapsid structure
sio
catalyst
fe3o4
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CN103301868A (en
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白国义
兰兴旺
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Hebei University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/584—Recycling of catalysts

Abstract

The invention provides a core-shell structural nano catalyst as well as a preparation method and an application thereof. The catalyst comprises a component Fe3O4.SiO2.(NH4)6Mo7O24, wherein Fe3O4 is positioned at a core, SiO2 is positioned on the outer layer of the Fe3O4, and (NH4)6Mo7O24 is positioned on the outermost layer. The catalyst is prepared according to the following steps: firstly, dispersing the Fe3O4 particles into deionized water so as to obtain a suspension, then adding a stronger ammonia water ethanol solution into the suspension, gradually dripping tetraethyl orthosilicate, and stirring 10-14h so as to obtain Fe3O4.SiO2 particles; and finally, gradually dripping a (NH4)6Mo7O24 aqueous solution into the Fe3O4.SiO2 particles and drying so as to obtain Fe3O4.SiO2.(NH4)6Mo7O24. The invention further provides an application of the catalyst in preparation of a 2-substituted benzo imidazole compound. The core-shell structural nano catalyst provided by the invention has a good catalytic effect and is convenient to recycle; when the catalyst can be used for catalytically synthesizing the 2-substituted benzo imidazole compound, the catalyst is moderate in reaction conditions and high in product yield.

Description

Nanocatalyst of a kind of nucleocapsid structure and its production and use
Technical field
The present invention relates to environmental protection catalyst and its preparation method and application, specifically relate to a kind of catalyst of 2-substituted benzimidazole compounds and preparation method of this catalyst of being particularly useful for making.
Background technology
2-substituted benzimidazole compounds is a kind of important organic intermediate, and it has excellent architectural characteristic, physiologically active and reactivity.It can be used for the synthesis of anticancer, antirheumatic, antimycotic, the medicine such as anti-inflammatory analgesic, anti-hypertension, also can be used for ligand complex, simulate the biologically active of natural superoxide dismutase (SOD), in addition, epoxy resin catalyst, curing agent and some metallic surface inorganic agent can also be used as.Therefore, the study on the synthesis of 2-substituted benzimidazole compounds is more and more subject to people's attention.The method of current synthesis 2-substituted benzimidazole compounds mainly carries out cyclisation, dehydration with organic carboxyl acid or derivatives thereof and o-phenylenediamine.The method needs to carry out in strong acid, hot environment, and side reaction is many, product yield is low.For addressing this problem, utilizing o-phenylenediamine and the aldehyde compound method of synthesizing benzimidazole compounds under the effect of different catalysts or oxidant to obtain researcher and more favoring.But these methods existing exist that catalyst is expensive, product separation is difficult usually, the new problem such as yield is low, catalyst can not be recycled.Such as Journal of Molecular CatalysisA:Chemical245 (2006) 8-11 reports one and utilizes trifluoro sulfonate solid acid as catalyst, solvent-free, under the condition of room temperature, by the method that o-phenylenediamine and aromatic aldehyde compound are Material synthesis benzimidazoles compound, the method yield is low, catalyst price is partially expensive; Synthetic Communications38 (2008) 1128-1136 reports a kind of iodobenzene diacetate (IBD) that utilizes under the condition of room temperature and has synthesized the method for benzimidazoles compound as oxidant, although the method improves product yield, but produce iodobenzene accessory substance in course of reaction, make product be difficult to be separated; Synthetic Communication40 (2010) 2686-2695 reports a kind of in room temperature, by the method for novel ferric trichloride doped polyaniline nano composition as catalyst synthesizing benzimidazole compounds under the solvent of absolute ethyl alcohol, although the method also improves in product yield, the catalyst environmental pollution adopted is more serious;
Summary of the invention
The object of this invention is to provide a kind of good stability and the nanocatalyst of nucleocapsid structure with low cost, adopt this catalyst to synthesize 2-substituted benzimidazole compounds, can make that its reaction condition is gentle, yield is high, environmental friendliness.The present invention also provides a kind of preparation method and purposes of above-mentioned nuclear shell structure nano catalyst simultaneously.
For realizing the object of the invention, the invention provides a kind of composition is Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24the nanocatalyst of nucleocapsid structure, wherein, Fe 3o 4be positioned at core, SiO 2be positioned at Fe 3o 4skin, (NH 4) 6mo 7o 24be positioned at outermost layer.
Above-mentioned (NH 4) 6mo 7o 24in amorphous state and high degree of dispersion.
Present invention also offers the preparation method of the nanocatalyst of described nucleocapsid structure, comprise the following steps:
A, by Fe 3o 4microparticulate, in deionized water, obtains suspension, described Fe 3o 4the particle diameter of particulate is 15-20nm;
B, in suspension, add containing concentrated ammonia liquor ethanolic solution, stir 10-15min, then drip ethyl orthosilicate, dropwise rear stirring 10-14h, then under the effect of external magnetic field, collect magnetic solidfied material, wash solidfied material 4-6 time with ethanol, dry at 70-90 DEG C, obtain Fe 3o 4@SiO 2particulate;
External magnetic field described in the present invention refers to Neodymium-Iron-Boron super magnet, and model is at N38 ~ N48.Separation method is placed in outside reaction vessels mainly through strong permanent magnet, is fully separated by catalyst with reactant liquor.
C, by (NH 4) 6mo 7o 24be dissolved in deionized water, be added drop-wise to Fe described in b step 3o 4@SiO 2in particulate, dipping evenly rear room temperature is air-dry, then dries 1 ~ 3h at 110-130 DEG C, obtains the nanocatalyst Fe of nucleocapsid structure 3o 4@SiO 2@(NH 4) 6mo 7o 24.
In said method, containing the ethanolic solution of concentrated ammonia liquor described in b step, its consumption is preferably 3 ~ 4 times of suspension volume, the wherein said ethanolic solution containing concentrated ammonia liquor, is be that 1.4 ~ 1.8:100 concentrated ammonia liquor and absolute ethyl alcohol mix by volume ratio; Described ethyl orthosilicate, its consumption is preferably Fe 3o 42.6 ~ 2.7 times of particle mass, (NH described in step c 4) 6mo 7o 24, its consumption is preferably Fe 3o 4@SiO 20.20 ~ 0.25 times of particle mass.
Described in the present invention containing the ethanolic solution of concentrated ammonia liquor, it is preferably that 4.0 ~ 5.0:280.0 concentrated ammonia liquor and absolute ethyl alcohol mix by volume ratio;
Present invention also offers the purposes of the nanocatalyst of above-mentioned nucleocapsid structure: namely as catalyst for the synthesis of 2-substituted benzimidazole compounds.
The synthesis of above-mentioned 2-substituted benzimidazole compounds, reactant is o-phenylenediamine and compound of benzaldehyde category.
The nanocatalyst of nucleocapsid structure is as follows for the synthesis of the step of 2-substituted benzimidazole compounds:
O-phenylenediamine and compound of benzaldehyde category being dissolved according to the mass ratio of 1 ~ 1.2:1 is equipped with in the container of ethanol, the concentration of o-phenylenediamine is 50 ~ 150mmol/L, then the nanocatalyst of described nucleocapsid structure is added wherein, addition is 0.2 ~ 0.24g/L, adding quality more wherein than concentration is the aqueous hydrogen peroxide solution of 30%, addition is 15 ~ 25mL/L, room temperature reaction 30 ~ 65min, then under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, after remaining liq evaporate to dryness, be separated and obtain 2-substituted benzimidazole compounds.
Collect nucleocapsid structure nanocatalyst can in above-mentioned technique recycled.
Catalyst of the present invention when for the synthesis of 2-substituted benzimidazole compounds, described compound of benzaldehyde category be in benzaldehyde, 4-chloro-benzaldehyde, P-methoxybenzal-dehyde, parahydroxyben-zaldehyde, o-chlorobenzaldehyde, piperonal, paranitrobenzaldehyde, m chlorobenzaldehyde any one.
The present invention has prepared a kind of nanocatalyst Fe of new type structure of hud 3o 4@SiO 2@(NH 4) 6mo 7o 24, referred to as Fe 3o 4@SiO 2@Mo, this catalyst is first with SiO 2parcel Fe 3o 4particulate, obtains Fe 3o 4@SiO 2particulate, then at SiO 2skin is load one deck (NH again 4) 6mo 7o 24.Due to Fe 3o 4@SiO 2particulate has magnetic and is nano-scale, and load is at the catalytic active component (NH on its surface 4) 6mo 7o 24dispersed, present higher catalytic activity.Adopt the nanocatalyst of nucleocapsid structure provided by the invention to prepare 2-substituted benzimidazole compounds, reaction condition is gentle, within the shorter reaction time, just can reach desirable reaction yield.In addition, this catalyst magnetic is strong, is easily separated under the effect of externally-applied magnetic field, is easy to reclaim, significantly can reduces production cost; And this catalyst is with low cost, safety non-toxic has good stability, and uses continuously and still keeps higher catalytic activity more than 5 times, reduce further production cost, have good promotional value and application prospect.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of raw material of the present invention and catalyst;
Wherein, a, (NH 4) 6mo 7o 24xRD diffraction spectra, b, Fe 3o 4@SiO 2xRD diffraction spectra; C, Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24xRD diffraction spectra.
Fig. 2 is Fe 3o 4@SiO 2tEM figure;
Fig. 3 is Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24tEM figure;
Detailed description of the invention
Further illustrate content of the present invention with specific embodiment below, but and mean never in any form and limit the invention.In the following example, method therefor is conventional method if no special instructions.
The preparation of embodiment 1 catalyst
Step is as follows:
A, be the 1.4g Fe of 15-20nm by diameter 3o 4microparticulate, in deionized water, obtains suspension;
B, in suspension, add ethanolic solution containing concentrated ammonia liquor 1.4% (v/v), addition is 3 times of suspension volume, and the concentration of concentrated ammonia liquor is 25% (w/w), and stir 10-15min, then dropwise add ethyl orthosilicate, addition is Fe 3o 42.6 times of particle mass, dropwise rear stirring 10h, then under the effect of external magnetic field, collect magnetic retention, wash 4 times with ethanol, dry, obtain Fe at 70 DEG C 3o 4@SiO 2particulate;
C, take Fe 3o 4@SiO 2(the NH that particle mass is 0.20 times 4) 6mo 7o 24, be dissolved in deionized water, be configured to the aqueous solution that concentration is 0.14mol/L, this aqueous solution is dropped to Fe described in b step 3o 4@SiO 2in particulate, dipping evenly rear room temperature is air-dry, then at 110 DEG C, dries 1h, obtains the nanocatalyst Fe of nucleocapsid structure 3o 4@SiO 2@(NH 4) 6mo 7o 24.
To gained Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24carry out BET analysis, the results are shown in Table 1.
Table 1BET analyzes
As shown in Table 1, Fe 3o 4@SiO 2there is microcellular structure and there is larger specific area in surface; Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24specific area reduction compared by catalyst comparatively carrier, proves active component (NH 4) 6mo 7o 24load or be scattered in carrier Fe 3o 4@SiO 2on.
To gained Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24carry out XRD analysis, the results are shown in Figure 1.
By the Fe in Fig. 1 3o 4@SiO 2xRD diffraction spectra can find out, SiO 2do not show obvious crystal structure peak shape, SiO is described 2fe is wrapped up in amorphous state 3o 4particle; Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24xRD diffraction spectra in not significantly (NH 4) 6mo 7o 24characteristic peak, active component (NH is described 4) 6mo 7o 24high degree of dispersion or be present in carrier Fe in amorphous state 3o 4@SiO 2on.
To gained Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24carry out XRD analysis, the results are shown in Figure 2, Fig. 3.
As shown in Figure 2, Fe 3o 4@SiO 2structure present SiO 2individual layer wraps up multiple Fe 3o 4core, thus there is stronger magnetic.As seen from Figure 3, load active component (NH 4) 6mo 7o 24after, nucleocapsid structure is not destroyed, but its surface does not exist crystalline structure, thus proves active component (NH 4) 6mo 7o 24carrier Fe is highly dispersed in amorphous state 3o 4@SiO 2on.As calculated, gained Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24in, Fe 3o 4mass fraction be 56-64%, SiO 2mass fraction be 16-24%, (NH 4) 6mo 7o 24mass fraction be 18-20%.
The preparation of embodiment 2 catalyst
Step is as follows:
A, be the 1.4g Fe of 15-20nm by diameter 3o 4microparticulate, in deionized water, obtains suspension;
B, in suspension, add ethanolic solution containing concentrated ammonia liquor 1.8% (v/v), addition is 4 times of suspension volume, and the concentration of concentrated ammonia liquor is 22% (w/w), and stir 10-15min, then dropwise add ethyl orthosilicate, addition is Fe 3o 42.7 times of particle mass, dropwise rear stirring 14h, then under the effect of external magnetic field, collect magnetic retention, wash 6 times with ethanol, dry, obtain Fe at 90 DEG C 3o 4@SiO 2particulate;
C, take Fe 3o 4@SiO 2(the NH that particle mass is 0.25 times 4) 6mo 7o 24, be dissolved in deionized water, be configured to the aqueous solution that concentration is 0.14mol/L, this aqueous solution is dropped to Fe described in b step 3o 4@SiO 2in particulate, dipping evenly rear room temperature is air-dry, then at 130 DEG C, dries 3h, obtains the nanocatalyst Fe of nucleocapsid structure 3o 4@SiO 2@(NH 4) 6mo 7o 24.
To gained Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24carry out BET analysis, to gained Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24carry out XRD analysis, come to the same thing described in its result and embodiment 1.
The synthesis of embodiment 32-substituted benzimidazole compounds
Step is as follows:
A, o-phenylenediamine, compound of benzaldehyde category be dissolved according to the mass ratio of 1.1:1 and be equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 0.1mol/L, then the nanocatalyst of nucleocapsid structure prepared by embodiment 1 is added wherein, addition is 0.22g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 20mL/L, room temperature reaction 30min
B, under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, recycled, after remaining liq evaporate to dryness, be separated and obtain 2-substituted benzimidazole compound.
The reaction equation of the present embodiment is as follows:
Wherein R=hydrogen, halogen or alkoxyl; R'-CHO is substituted aryl.
This synthetic method mild condition, the yield of gained 2-substituted benzimidazole compound is 85-90%.
Embodiment 4
A, o-phenylenediamine and benzaldehyde be dissolved according to the mass ratio of 1:1 and be equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 50mmol/L, then the nanocatalyst of nucleocapsid structure prepared by embodiment 1 is added wherein, addition is 0.2g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 15mL/L, room temperature reaction 30min
B, under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, recycled, after remaining liq evaporate to dryness, be separated and obtain 2-Phenylbenzimidazole.
The reaction equation of the present embodiment is as follows:
IR(KBr,cm -1):3648,3047,2627,1733,1622,1540,1462,1444,1410,1314,1275,969,738; 1H NMR(600MHz,DMSO-d 6)δ12.93(s,1H),8.18-8.20(m,2H),7.49-7.77(m,5H),7.21-7.22(m,2H), 13CNMR(150MHz,DMSO-d 6)δ151.69,130.63,130.31,129.42,126.91,122.58.
This synthetic method mild condition, the yield of gained 2-Phenylbenzimidazole is 90.3%.
Embodiment 5
A, o-phenylenediamine and 4-chloro-benzaldehyde be dissolved according to the mass ratio of 1.1:1 and be equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 0.1mol/L, then the nanocatalyst of nucleocapsid structure prepared by embodiment 1 is added wherein, addition is 0.22g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 20mL/L, room temperature reaction 50min
B, under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, recycled, after remaining liq evaporate to dryness, be separated and obtain 2-(4-chlorphenyl) benzimidazole.
The reaction equation of the present embodiment is as follows:
IR(KBr,cm -1):3648,3142,3051,2958,1733,1652,1571,1429,1272,1089,963,830,745; 1H NMR(600MHz,DMSO-d 6)δ8.22(d,J=8.5Hz,2H),7.55-7.69(m,4H),7.12-7.34(m,2H).
This synthetic method mild condition, gained 2-(4-chlorphenyl) yield of benzimidazole is 94%.
Embodiment 6
A, o-phenylenediamine and p-tolyl aldehyde be dissolved according to the mass ratio of 1.2:1 and be equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 150mmol/L, then the nanocatalyst of nucleocapsid structure prepared by embodiment 1 is added wherein, addition is 0.24g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 25mL/L, room temperature reaction 40min
B, under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, recycled, after remaining liq evaporate to dryness, be separated and obtain 2-(4-aminomethyl phenyl) benzimidazole.
The reaction equation of the present embodiment is as follows:
IR(KBr,cm -1):3648,3051,2854,1733,1647,1499,1273,1121,1043,963,820,745; 1H NMR(600MHz,DMSO-d 6)δ12.83(s,1H),8.06(t,J=11.1Hz,2H),7.58(s,2H),7.36(t,J=11.1Hz,2H),7.10-7.23(m,2H),2.39(s,3H).
This synthetic method mild condition, gained 2-(4-aminomethyl phenyl) yield of benzimidazole is 89.7%.
Embodiment 7
A, o-phenylenediamine and P-methoxybenzal-dehyde be dissolved according to the mass ratio of 1.1:1 and be equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 0.1mol/L, then the nanocatalyst of nucleocapsid structure prepared by embodiment 1 is added wherein, addition is 0.22g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 20 mL/L, room temperature reaction 65min
B, under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, recycled, after remaining liq evaporate to dryness, be separated and obtain 2-(4-methoxyphenyl) benzimidazole.
The reaction equation of the present embodiment is as follows:
IR(KBr,cm -1):3648,2836,1740,1610,1499,1453,1434,1294,1253,1178,1033,964,854,744; 1H NMR(600MHz,DMSO-d 6)δ12.76(s,1H),8.12(d,J=8.8Hz,2H),7.56(s,2H),7.17-7.18(m,2H),7.12(d,J=8.8Hz,2H),3.85(s,3H).
This synthetic method mild condition, gained 2-(4-methoxyphenyl) yield of benzimidazole is 87.3%.
Embodiment 8
A, o-phenylenediamine and parahydroxyben-zaldehyde be dissolved according to the mass ratio of 1.1:1 and be equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 0.1mol/L, then the nanocatalyst of nucleocapsid structure prepared by embodiment 1 is added wherein, addition is 0.22g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 20mL/L, room temperature reaction 65min
B, under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, recycled, after remaining liq evaporate to dryness, be separated and obtain 2-(4-hydroxy phenyl) benzimidazole.
The reaction equation of the present embodiment is as follows:
IR(KBr,cm -1):3648,3307,2927,1733,1623,1500,1472,1455,1276,1252,1069,1002,836,745; 1H NMR(600MHz,DMSO-d 6)δ12.65(s,1H),9.98(s,1H),8.00(d,J=8.7Hz,2H),7.52(s,2H),7.15-7.16(m,2H),6.92(d,J=8.7Hz,2H).
This synthetic method mild condition, gained 2-(4-hydroxy phenyl) yield of benzimidazole is 88.9%.
Embodiment 9
A, o-phenylenediamine and o-chlorobenzaldehyde be dissolved according to the mass ratio of 1.1:1 and be equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 0.1mol/L, then the nanocatalyst of nucleocapsid structure prepared by embodiment 1 is added wherein, addition is 0.22g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 20mL/L, room temperature reaction 35min
B, under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, recycled, after remaining liq evaporate to dryness, be separated and obtain 2-(2-chlorphenyl) benzimidazole.
The reaction equation of the present embodiment is as follows:
This synthetic method mild condition, gained 2-(2-chlorphenyl) yield of benzimidazole is 90.4%.
Embodiment 10
A, o-phenylenediamine and piperonal be dissolved according to the mass ratio of 1.1:1 and be equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 0.1mol/L, then the nanocatalyst of nucleocapsid structure prepared by embodiment 1 is added wherein, addition is 0.22g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 20mL/L, room temperature reaction 60min
B, under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, recycled, after remaining liq evaporate to dryness, be separated and obtain 2-(3,4-methylenedioxyphenyl) benzimidazole.
The reaction equation of the present embodiment is as follows:
IR(KBr,cm -1):3648,2877,2644,1732,1618,1500,1471,1451,1245,1227,1037,932,815,748; 1H NMR(600MHz,DMSO-d 6)δ12.76(s,1H),7.72-7.73(m,1H),7.67-7.70(m,1H),7.45-7.64(m,2H),7.18(d,J=3.3Hz,2H),7.11(d,J=8.1Hz,1H),6.13(s,2H).
This synthetic method mild condition, gained 2-(3,4-methylenedioxyphenyl) yield of benzimidazole is 91.7%.
Embodiment 11
A, o-phenylenediamine and paranitrobenzaldehyde be dissolved according to the mass ratio of 1.1:1 and be equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 0.1mol/L, then the nanocatalyst of nucleocapsid structure prepared by embodiment 1 is added wherein, addition is 0.22g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 20mL/L, room temperature reaction 35min
B, under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, recycled, after remaining liq evaporate to dryness, be separated and obtain 2-(4-nitrobenzophenone) benzimidazole, yield is 90.9%.
Embodiment 12
A, o-phenylenediamine and m chlorobenzaldehyde be dissolved according to the mass ratio of 1.1:1 and be equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 0.1mol/L, then the nanocatalyst of nucleocapsid structure prepared by embodiment 1 is added wherein, addition is 0.22g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 20mL/L, room temperature reaction 30min
B, under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, recycled, after remaining liq evaporate to dryness, be separated and obtain 2-(3-chlorphenyl) benzimidazole, yield is 93.0%.
Embodiment 13 catalyst circulation is applied mechanically
A, o-phenylenediamine and benzaldehyde be dissolved according to the mass ratio of 1.1:1 and be equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 0.1mol/L, then the nanocatalyst of nucleocapsid structure prepared by embodiment 1 is added wherein, addition is 0.22g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 20mL/L, room temperature reaction 30min
B, under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, after remaining liq evaporate to dryness, be separated and obtain 2-Phenylbenzimidazole, yield is 90.1%.
C, catalyst circulation is applied mechanically 5 times, adopt and the present embodiment a, reaction condition that b step is identical, gained 2-Phenylbenzimidazole yield is respectively 89.1%, 90.8%, 88.5%, 89.7%, 87.5%.
From above-mentioned result of the test, the nanocatalyst of the nucleocapsid structure prepared by the present invention has good stability, and reuses 5 times, and its catalytic activity is lost hardly.

Claims (7)

1. a nanocatalyst for nucleocapsid structure, is characterized in that: its composition is Fe 3o 4@SiO 2@(NH 4) 6mo 7o 24, wherein, Fe 3o 4be positioned at core, SiO 2be positioned at Fe 3o 4skin, (NH 4) 6mo 7o 24be positioned at outermost layer; Following steps: a is adopted, by Fe during preparation 3o 4microparticulate, in deionized water, obtains suspension, described Fe 3o 4the particle diameter of particulate is 15 ~ 20 nm;
B, in suspension, add ethanolic solution containing concentrated ammonia liquor, stir 10 ~ 15 min, then drip ethyl orthosilicate, dropwise rear stirring 10 ~ 14h, then under the effect of external magnetic field, collect magnetic retention, with ethanol washing 4 ~ 6 times, dry at 70 ~ 90 DEG C, obtain Fe 3o 4@SiO 2particulate;
C, by (NH 4) 6mo 7o 24be dissolved in deionized water, be then added drop-wise to Fe described in b step 3o 4@SiO 2in particulate, dipping evenly rear room temperature is air-dry, then dries 1-3h at 110-130 DEG C, obtains the nanocatalyst Fe of nucleocapsid structure 3o 4@SiO 2@(NH 4) 6mo 7o 24.
2. the nanocatalyst of nucleocapsid structure according to claim 1, is characterized in that: described (NH 4) 6mo 7o 24in amorphous state and high degree of dispersion.
3. the nanocatalyst of nucleocapsid structure according to claim 1, is characterized in that: the ethanolic solution containing concentrated ammonia liquor described in b step, is be that 1.4 ~ 1.8:100 concentrated ammonia liquor and absolute ethyl alcohol mix by volume ratio; Described ethyl orthosilicate, its consumption is Fe 3o 42.6 ~ 2.7 times of particle mass, (NH described in step c 4) 6mo 7o 24, its consumption is Fe 3o 4@SiO 20.20 ~ 0.25 times of particle mass.
4. the purposes of the nanocatalyst of nucleocapsid structure described in claim 1 or 2, is characterized in that: the nanocatalyst of described nucleocapsid structure is used for the synthesis of 2-substituted benzimidazole compounds.
5. the purposes of the nanocatalyst of nucleocapsid structure according to claim 4, is characterized in that: the synthesis of described 2-substituted benzimidazole compounds, reactant is o-phenylenediamine and compound of benzaldehyde category.
6. the purposes of the nanocatalyst of nucleocapsid structure according to claim 5, it is characterized in that: the synthesis of described 2-substituted benzimidazole compounds, its step is as follows,
O-phenylenediamine and compound of benzaldehyde category being dissolved according to the mass ratio of 1 ~ 1.2:1 is equipped with in the round-bottomed flask of ethanol, the concentration of o-phenylenediamine is 50 ~ 150mmol/L, then the nanocatalyst of described nucleocapsid structure is added wherein, addition is 0.2 ~ 0.24g/L, add the aqueous hydrogen peroxide solution that mass fraction is 30% more wherein, addition is 15 ~ 25mL/L, room temperature reaction 30-65 min, then under external magnetic fields, collect the nanocatalyst of nucleocapsid structure, recycled, after remaining liq evaporate to dryness, is separated and obtains 2-substituted benzimidazole compounds.
7. the purposes of the nanocatalyst of nucleocapsid structure according to claim 5 or 6, is characterized in that: described compound of benzaldehyde category be in benzaldehyde, 4-chloro-benzaldehyde, P-methoxybenzal-dehyde, parahydroxyben-zaldehyde, o-chlorobenzaldehyde, piperonal, paranitrobenzaldehyde, m chlorobenzaldehyde any one.
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