CN109847749A - The high performance catalyst and preparation method thereof of nitro-aromatic reduction at room temperature - Google Patents
The high performance catalyst and preparation method thereof of nitro-aromatic reduction at room temperature Download PDFInfo
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- CN109847749A CN109847749A CN201811630801.0A CN201811630801A CN109847749A CN 109847749 A CN109847749 A CN 109847749A CN 201811630801 A CN201811630801 A CN 201811630801A CN 109847749 A CN109847749 A CN 109847749A
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Abstract
The invention discloses the high performance catalysts and preparation method thereof of nitro-aromatic reduction at room temperature, catalyst is using polydivinylbenezene microballoon as raw material, in such a way that silicon hydrogenation is to its surface chemical modification, obtain presoma microballoon, then it is pyrolyzed, final obtained surface is rich in the Si-C-Fe hybrid microspheres of Zero-valent Iron.Operation of the present invention is simple, and step is few, and experiment condition requirement is low, and gained hybrid microspheres regular shape, surface is smooth, and prepared hybrid microspheres have excellent catalytic properties.
Description
Technical field
The present invention relates to catalysis material fields, more particularly, to a kind of nitro-aromatic reduction high performance catalyst at room temperature
And preparation method thereof.
Background technique
Nitro-aromatic has been widely used in chemical industry, such as is used as explosive, insecticide, solvent, in addition, in bullet
The production of medicine, nitro-aromatic can also be generated by storing and discarding.Nitro-aromatic is that have carcinogenesis, genetoxic and interior to the mankind
The chemical substance for secreting chaff interferent, can also cause the diseases such as methemoglobinemia.Wherein, p-nitrophenol (4-NP) due to
Strong carcinogenesis, it is artificial caused by destructive and toxicity and primary pollutant is chosen as by Environmental Protection Agency USA, and its reduction
Product 4-aminophenol (4-AP) is widely used in synthesis analgesic drug product such as acamol, photographic developer, corrosion suppression
The chemical intermediate of preparation and dyestuff.Most of catalyst about 4-NP reduction research at present concentrates on noble metal nano grain
Son is such as Au, Pd, and on Pt and Ag, therefore it is still challenging to develop cheap and efficient catalyst.
It is an object of that present invention to provide a kind of new method for preparing nitro-aromatic catalyst for reduction under novel Room Temperature, this hairs
Bright to have the microballoon of metal small organic molecule as presoma using surface modification, being suitably pyrolyzed preparation, nitro-aromatic restores at room temperature
With catalyst, there is excellent catalytic activity in a series of reduction of nitrobenzene compounds and easily recycle and can be recycled
Performance.
Summary of the invention
In order to solve the problems in the existing technology, the present invention is by providing a kind of reduction of nitro-aromatic at room temperature use
High performance catalyst and preparation method thereof.
Specifically, the first purpose of the invention is to provide the high performance catalyst of nitro-aromatic reduction at room temperature, institute
Catalyst is stated with polydivinylbenezene microballoon (PDVB microballoon) for raw material, by silicon hydrogenation to PDVB microsphere surface
Modified mode is learned, presoma microballoon is obtained, then 500 DEG C~650 DEG C are pyrolyzed, and final obtained surface is rich in Zero-valent Iron
Si-C-Fe hybrid microspheres.
Wherein, prepared catalyst main component is carbon, and content is divided in 60%-80% range, and in Raman spectrum
I in analysisD/IG≤1.3。
A second object of the present invention is to provide the preparations of the high performance catalyst of the above-mentioned reduction of nitro-aromatic at room temperature
Method specifically comprises the following steps:
S1: presoma microballoon is prepared
Polydivinylbenezene microballoon, siliceous hydrogen ferrocene-containing compound and catalyst are added to toluene under an inert atmosphere
In, 60~100 DEG C of heating are reacted 8~16 hours after ultrasonic disperse, are then removed toluene using vacuum plant, are then washed
And vacuum drying；
The mass ratio that feeds intake of the polydivinylbenezene microballoon, siliceous hydrogen ferrocene-containing compound and catalyst is 1:4~5:
0.01, the dosage of toluene is 20 times of siliceous hydrogen ferrocene-containing compound volume；
S2: the pyrolysis in situ of presoma microballoon
Presoma microballoon after drying is placed in tube furnace, under an inert atmosphere, is warming up to 500 DEG C~650 DEG C sintering 3
~8h is subsequently cooled to environment temperature to get Si-C-Fe hybrid microspheres.
Preferably, the inert atmosphere is argon gas or nitrogen atmosphere.
Preferably, the residual double bonds of the polydivinylbenezene microballoon are measured through HBr addition process, and content is more than or equal to
2mmol/g。
Preferably, the siliceous hydrogen ferrocene-containing compound is 1,1 '-bis- (dimetylsilyl) ferrocene.
Preferably, in S1, the catalyst is hydrosilylation catalyst.
Preferably, the hydrosilylation catalyst is platinum catalyst.
Preferably, in S1, vacuum drying temperature is 40~60 DEG C, drying time 12-24h.
Preferably, in S1, washing is specifically referred to successively using tetrahydrofuran, and acetone and ether wash 3 times respectively.
Preferably, in S2, the presoma microballoon after drying is placed in tube furnace, under an inert atmosphere, is warming up to 600 DEG C
It is sintered 6h.
Preferably, prepared catalyst main component is carbon, and content is in 60%-80% range, and in Raman spectrum
I in analysisD/IG≤1.3。
Compared with prior art, the beneficial effects of the present invention are:
1) easy to operate, step is few, and experiment condition requires low；2) gained hybrid microspheres regular shape, surface are smooth；3) institute
The hybrid microspheres of preparation have excellent catalytic properties.
The present invention has the microballoon of metal small organic molecule as presoma using surface modification, is suitably pyrolyzed preparation at room temperature
Nitro-aromatic catalyst for reduction.Pass through the residual ethylene base and 1,1 '-on PDVB microballoon (i.e. polydivinylbenezene microballoon) surface
Silicon hydrogenation between bis- (dimetylsilyl) ferrocene realizes the ferrocene chemical modification to PDVB microsphere surface, so
By pyrolysis under felicity condition to get the Si-C hydridization magnetic microsphere for arriving the novel nanocrystal containing Fe.Since it has typically
Micro- meso-hole structure, large specific surface area, richness sp2Hydridization carbon and the good feature of ferromagnetic property, therefore in a series of nitrobenzene chemical combination
Performance is recycled and can be recycled in the reduction of object with excellent catalytic activity and easily.The present invention is that synthesis has catalysis
Low cost magnetic hybrid microspheres material provide convenience, can be widely applied to sustainable conversion and the chemistry of environmental contaminants
Intermediate production.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the TEM figure for the Si-C-Fe hybrid microspheres that the embodiment of the present invention 1 synthesizes, wherein (a) is low power TEM figure, (b)
It is high-resolution TEM figure, is (c) partial enlarged view of (b)；
The enlarged drawing of (c) in Fig. 2 Fig. 1.
Specific embodiment
In order to enable those skilled in the art to more fully understand, technical solution of the present invention is practiced, below with reference to specific
The invention will be further described for embodiment, but illustrated embodiment is not as a limitation of the invention.
Unless otherwise defined, the hereinafter used all technical terms for being and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.Unless otherwise specified, it the various raw materials used in the following embodiment of the present invention, reagent, instrument and sets
It is standby to be commercially available by market or be prepared by existing method.
Embodiment 1
Under argon gas (purity >=99.999%) atmosphere, 1gPDVB microballoon (i.e. poly- divinyl is sequentially added into dry combustion method bottle
Base benzene microballoon), the 1 of 4g, 1 '-bis- (dimetylsilyl) ferrocene, the Karstedt catalyst and 125mL of 0.01g be anhydrous
Toluene, after abundant ultrasonic disperse, by mixture in 80 DEG C of stirring 12h, isolated by vacuum filtration crude product successively uses tetrahydrofuran,
Acetone and ether wash 3 times, are dried in vacuo at 40 DEG C for 24 hours, after to obtain yellow sample be that target product ferrocene is modified
PDVB (is denoted as Fc-PDVB).Then, dried Fc-PDVB is heated to 600 DEG C of tubular types under argon gas (70mL/min) atmosphere
Pyrolysis 6h is carried out in furnace, is subsequently cooled to environment temperature (5 DEG C/min) and is obtained Si-C-Fe hybrid microspheres.Through Raman spectrum point
Analysis, ID/IG=1.25；Transmission electron microscope (TEM) analysis result is as shown in Figure 1, the TEM image of low power shows prepared sample tool
The spherical characteristic having had observes the rich region Fe (diameter 10nm) of nanoscale in powerful TEM image, in crystalline substance
Lattice striated, spacing of lattice are 2.03 angstroms.
Embodiment 2
Under nitrogen (purity >=99.999%) atmosphere, PDVB microballoon (the i.e. poly- diethyl of 2g is sequentially added into dry combustion method bottle
Alkenyl benzene microballoon), the 1 of 8.5g, 1 '-bis- (dimetylsilyl) ferrocene, the Karstedt catalyst and 200mL of 0.02g
Dry toluene, after abundant ultrasonic disperse, by mixture in 60 DEG C of stirring 8h, isolated by vacuum filtration crude product successively uses tetrahydro furan
Mutter, acetone and ether wash 3 times, be dried in vacuo 12h at 60 DEG C, after to obtain yellow sample be that target product ferrocene is modified
PDVB (is denoted as Fc-PDVB).Then, dried Fc-PDVB is heated to 500 DEG C of tubular types under nitrogen (70mL/min) atmosphere
Pyrolysis 8h is carried out in furnace, is subsequently cooled to environment temperature (5 DEG C/min) and is obtained Si-C-Fe hybrid microspheres.
Embodiment 3
Under nitrogen (purity >=99.999%) atmosphere, PDVB microballoon (the i.e. poly- diethyl of 1g is sequentially added into dry combustion method bottle
Alkenyl benzene microballoon), the 1 of 5g, 1 '-bis- (dimetylsilyl) ferrocene, the Karstedt catalyst and 156mL of 0.01g without
Water-toluene, after abundant ultrasonic disperse, by mixture in 80 DEG C of stirring 12h, isolated by vacuum filtration crude product successively uses tetrahydro furan
Mutter, acetone and ether wash 3 times, be dried in vacuo at 40 DEG C for 24 hours, after to obtain yellow sample be that target product ferrocene is modified
PDVB (is denoted as Fc-PDVB).Then, dried Fc-PDVB is heated to 650 DEG C of tubular types under nitrogen (70mL/min) atmosphere
Pyrolysis 3h is carried out in furnace, is subsequently cooled to environment temperature (5 DEG C/min) and is obtained Si-C-Fe hybrid microspheres.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.Embodiment described above is only to absolutely prove the present invention
And the preferred embodiment lifted, protection scope are without being limited thereto.Those skilled in the art institute on the basis of the present invention
The equivalent substitute or transformation of work, within the scope of the present invention, protection scope of the present invention is subject to claims.
Claims (10)
1. the high performance catalyst of nitro-aromatic reduction at room temperature, which is characterized in that the catalyst is with polydivinylbenezene
Microballoon is raw material, in such a way that silicon hydrogenation carries out chemical modification to its surface, obtains presoma microballoon, then 500 DEG C
~650 DEG C are pyrolyzed, and final obtained surface is rich in the Si-C-Fe hybrid microspheres of Zero-valent Iron.
2. the high performance catalyst of the reduction of nitro-aromatic at room temperature according to claim 1, which is characterized in that prepared
Catalyst main component be carbon, content is in 60%-80% range, and the I in Raman spectrum analysisD/IG≤1.3。
3. the preparation method of the high performance catalyst of the reduction of nitro-aromatic at room temperature according to claim 1, feature
It is, specifically comprises the following steps:
S1: presoma microballoon is prepared
Polydivinylbenezene microballoon, siliceous hydrogen ferrocene-containing compound and catalyst are added in toluene under an inert atmosphere, surpassed
60~100 DEG C of heating are reacted 8~16 hours after sound dispersion, then remove toluene using vacuum plant, then carry out washing and very
Sky is dry；
The mass ratio that feeds intake of the polydivinylbenezene microballoon, siliceous hydrogen ferrocene-containing compound and catalyst is 1:4~5:0.01,
The dosage of toluene is 20 times of siliceous hydrogen ferrocene-containing compound volume；
S2: the pyrolysis in situ of presoma microballoon
Presoma microballoon after drying is placed in tube furnace, under an inert atmosphere, be warming up to 500 DEG C~650 DEG C sintering 3~
8h is subsequently cooled to environment temperature to get Si-C-Fe hybrid microspheres.
4. the preparation method of the high performance catalyst of the reduction of nitro-aromatic at room temperature according to claim 3, feature
It is, the inert atmosphere is argon gas or nitrogen atmosphere.
5. the preparation method of the high performance catalyst of the reduction of nitro-aromatic at room temperature according to claim 3, feature exist
In the residual double bonds of the polydivinylbenezene microballoon are measured through HBr addition process, and content is more than or equal to 2mmol/g.
6. the preparation method of the high performance catalyst of the reduction of nitro-aromatic at room temperature according to claim 3, feature
It is, the siliceous hydrogen ferrocene-containing compound is 1,1 '-bis- (dimetylsilyl) ferrocene.
7. the preparation method of the high performance catalyst of the reduction of nitro-aromatic at room temperature according to claim 3, feature
It is, in S1, the catalyst is hydrosilylation catalyst.
8. the preparation method of the high performance catalyst of the reduction of nitro-aromatic at room temperature according to claim 7, feature
It is, the hydrosilylation catalyst is Karstedt catalyst or platinum catalyst.
9. the preparation method of the high performance catalyst of the reduction of nitro-aromatic at room temperature according to claim 3, feature
It is, in S1, vacuum drying temperature is 40~60 DEG C, drying time 12-24h.
10. the preparation method of the high performance catalyst of the reduction of nitro-aromatic at room temperature according to claim 3, feature
It is, in S1, washing is specifically referred to successively using tetrahydrofuran, and acetone and ether wash 3 times respectively.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103342357A (en) * | 2013-07-16 | 2013-10-09 | 安徽理工大学 | Low temperature catalytic graphitization method for polydivinylbenzene resin |
| CN103979965A (en) * | 2014-05-12 | 2014-08-13 | 西北工业大学 | Method for preparing Si-C-N-based ceramic microspheres |
| CN104190359A (en) * | 2014-09-03 | 2014-12-10 | 西北工业大学 | Porous grading Si-C-N hybrid material and preparation method thereof |
| CN106311340A (en) * | 2016-09-28 | 2017-01-11 | 济南大学 | Preparation method of micron motor catalyst based on polydivinylbenzene (PDVB) porous beads |
-
2018
- 2018-12-29 CN CN201811630801.0A patent/CN109847749A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103342357A (en) * | 2013-07-16 | 2013-10-09 | 安徽理工大学 | Low temperature catalytic graphitization method for polydivinylbenzene resin |
| CN103979965A (en) * | 2014-05-12 | 2014-08-13 | 西北工业大学 | Method for preparing Si-C-N-based ceramic microspheres |
| CN104190359A (en) * | 2014-09-03 | 2014-12-10 | 西北工业大学 | Porous grading Si-C-N hybrid material and preparation method thereof |
| CN106311340A (en) * | 2016-09-28 | 2017-01-11 | 济南大学 | Preparation method of micron motor catalyst based on polydivinylbenzene (PDVB) porous beads |
Non-Patent Citations (2)
| Title |
|---|
| XIAOFEI ZHANG ET.AL: ""Constructing magnetic Si–C–Fe hybrid microspheres for room temperature nitroarenes reduction"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| XIAOFEI ZHANG ET.AL: "Novel ferrocene-containing organosilicon polymers and uniform microspheres prepared by free radical copolymerization: Precursors for magnetic Si-C-Fe-(O) nanomaterials", 《MATERIALS AND DESIGN》 * |
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