CN103433035B - Preparation method of AgNPs/CNFs and AgNPs-Mg/CNFs for catalyzing phenylethylene oxidation reaction - Google Patents
Preparation method of AgNPs/CNFs and AgNPs-Mg/CNFs for catalyzing phenylethylene oxidation reaction Download PDFInfo
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Abstract
The invention relates to a preparation method of a supported catalyst containing silver nanoparticles (AgNPs)/carbon nanofibers (CNFs) and AgNPs-Mg/CNFs and a process of applying the catalyst to catalyze a phenylethylene oxidation reaction. The supported catalyst provided by the invention is characterized in that: carrier CNFs of the catalyst have strong chemical inertness and large specific surface area, a catalyst is nano silver having relatively high activity and uniform dispersion, and in addition, a small amount of alkaline earth metal Mg is added to be used as a cocatalyst to improve the catalytic effect. The preparation method comprises four steps: firstly, preparing AgNO3/polyacrylonitrile (PAN) and AgNO3-MgNO3/PAN nanofibers by an electrospinning technology; secondly, preparing composite fibers containing nano silver by hydrazine hydrate or hydrogen reduction; thirdly, preparing AgNPs/CNFs and AgNPs-Mg/CNFs nano fibers by a high temperature calcination technology; and finally, inspecting the performance of the supported catalyst to catalyze the phenylethylene oxidation reaction by the obtained supported catalyst.
Description
Technical field
The present invention relates to one kind contains with reference to the preparation of electrostatic spinning technique, electronation technology and high-temperature calcination technology
The method of the CNFs loaded catalyst of AgNPs and AgNPs-Mg, and its answering in catalyzed alkene class material oxidation reaction
With.
Background technology
Styryl oxide, also known as styrene oxide, is a kind of important organic synthesis intermediate, is widely used in organic conjunction
One-tenth, medicine preparation, production of flavor are it is also possible to make epoxy resin diluent, UV- absorbent, fumet, stabilizer etc..Styrene
During oxidative synthesis Styryl oxide, accessory substance benzaldehyde can be produced, benzaldehyde is also important organic intermediate, is used for
The industries such as spices, medicine.Therefore, with styrene oxidation synthesizing epoxy vinylbenzene and its co-product benzaldehyde no matter in organic synthesis
Or industrialized production aspect all receives much concern.
Ag catalyst is efficient, the cheap noble metal catalyst of styrene oxidation.There is large surface area
AgNPs is reducing catalyst amount, is improving catalytic reaction efficiency, optimize response path, improve reaction rate etc. as catalyst
Aspect shows its unique distinction.Carbon nano-fiber (CNFs) has stronger chemical inertness, larger specific surface area and is easy to
Reclaim, reuse, therefore it is more suitable as the carrier material of catalyst.In the last few years, Electrospinning had been able to make
Standby polymer (be combined) nanofiber, the nanofiber obtaining is converted to as nano level after pre-oxidation with high-temperature calcination
Carbon fiber.This method is to prepare the important channel of excellent catalysts carrier material-carbon nano-fiber.
By the use of carbon fiber as the carrier of AgNPs catalyst, the presoma of active metal can be made sufficiently to be disperseed, no
The utilization rate that noble metal only can be improved, the consumption reducing Ag, prevent metallic from sintering, and due to carbon fiber and activity gold
Belong to the strong interaction (compound under nanoscale) between Ag, promote active, selectivity and the stability of metallic catalyst.With
When, a small amount of alkaline-earth metal Mg is introduced in AgNPs/CNFs system as secondary catalyst, can effectively improve loaded catalyst
Catalytic efficiency.
Content of the invention
The technical scheme is that providing one kind urges containing catalyst AgNPs and containing catalyst AgNPs and pair
The preparation method of the CNFs loaded catalyst of agent Mg.Described AgNPs/CNFs and AgNPs-Mg/CNFs is to styrene oxygen
Changing reaction has preferable catalytic effect.
A kind of AgNPs/CNFs and AgNPs-Mg/CNFs catalysis with styrene catalyzed oxidation susceptibility that the present invention provides
Agent, is obtained by the following method, and step includes：
(1)AgNO3/ PAN and AgNO3-MgNO3The preparation of/PAN fiber.In the PAN/DMF solution being 8% to mass fraction
Add a certain amount of AgNO3, lucifuge ice bath stirring 5h, obtain uniform AgNO3Solution before/PAN spinning.The solution obtaining is put into
In spin duct, adjusting spinning distance is 17cm, and voltage 17kV, under room temperature, obtains AgNO using electrostatic spinning technique3/ PAN forerunner
Bluk recombination nanofiber.With similar method, it is simultaneously introduced AgNO to PAN/DMF solution3And MgNO3, prepare AgNO3-MgNO3/
PAN fiber.
(2) AgNPs/PAN fiber film preparation.The AgNO of preparation3/ PAN fiber film uses hydrazine hydrate and H respectively2Reduction preparation
AgNPs/PAN fiber.With the method for hydrazine hydrate reduction it is：By AgNO3/ PAN fiber film is immersed in the water that volume fraction is 1/200
Close in hydrazine solution, after 20min, tunica fibrosa is taken out, and put into and faster clean in distilled water 2 times, then tunica fibrosa is put into glass
On glass surface plate, drying at room temperature, obtain AgNPs/PAN tunica fibrosa.Use H2Reduction method be：AgNO3/ PAN fiber film is put into
In reactor, into reactor, it is passed through N2Make pressure reach 1MPa, then release N2, it is repeated 3 times.By above-mentioned similar operations, to anti-
Answer and be passed through in kettle and release H2Twice.Finally, it is passed through the H of 1MPa in reactor2, set 40 DEG C of temperature of reaction kettle, react 3h.
Reaction obtains AgNPs/PAN tunica fibrosa after terminating.
(3) preparation of AgNPs/CNFs and AgNPs-Mg/CNFs.AgNO3-MgNO3/ PAN and AgNPs/PAN tunica fibrosa
Place in porcelain boat and put in vacuum tube furnace.Under air atmosphere, carry out the pre-oxidizing the stage of tunica fibrosa, tube furnace with 5 DEG C/
Min heating rate rises to 250 DEG C by room temperature, and constant temperature keeps 2h.Then, it is passed through high-purity N into tube furnace2, N2Under atmosphere, pipe
Formula stove rises to 900 DEG C with 3 DEG C/min heating rate by 250 DEG C, and keeps 2h, completes the carbonation stage of tunica fibrosa.Finally, N2Protect
Under shield, treat that tubular type furnace temperature is cooled to room temperature, take out tunica fibrosa, obtain AgNPs-Mg/CNFs and AgNPs/CNFs composite.
In solution before the spinning of described AgNPs-Mg/CNFs, AgNO3Mol ratio with PAN is 1/10, MgNO3With AgNO3
Mol ratio be 1/10.
The styrene catalyzed oxidation activity evaluation method that the present invention provides：Styrene oxidation is carried out at ambient pressure.
0.03g catalyst (AgNPs/CNFs, AgNPs-Mg/CNFs), 1mL styrene, 5mL TBHP, 5mL isopropanol adds
Enter in 25mL round-bottomed flask, magnetic agitation, be heated to reflux 8h.After reaction terminates, question response thing temperature is down to room temperature, with organic
Seperation film separating catalyst and product.Then use Agilent (7890A) chromatographic product, FID hydrogen flame from
Sub- detector, SE-30 quartz capillary chromatographic column, N2For carrier gas.Each component containing in the product is calculated using area normalization method
Amount.Product with GC-MS (Agilent, 5975C) evidence analysis.
The preparation method of AgNPs/CNFs and AgNPs-Mg/CNFs novel supported catalyst of the present invention has letter
Just, easy-operating advantage, the catalyst obtaining has the advantages that high catalytic efficiency, is easily recycled, reuses.Obtain is new
Catalyst has potential using value in catalysis oxidation field.
Brief description
Fig. 1 is (A) SEM and (B) FTIR figure of the AgNPs/CNFs making reducing agent acquisition of hydrazine hydrate.
Fig. 2 is (A) SEM and (B) FTIR figure of the AgNPs/CNFs making reducing agent acquisition of hydrogen.
Fig. 3 is (A) SEM and (B) TEM of AgNPs-Mg/CNFs and (C) XRD obtaining.
Specific embodiment
Embodiment 1, with hydrazine hydrate reduction preparation, there is the AgNPs/CNFs of styrene catalyzed oxidation susceptibility
A certain amount of AgNO is added in the PAN/DMF solution being 8% to mass fraction3, make AgNO3Mol ratio with PAN is
1/10, lucifuge ice bath stirs 5h, obtains uniform AgNO3Solution before/PAN spinning.The solution obtaining is put in spin duct, adjusts
Spinning distance is 17cm, voltage 17kV, and electrospinning obtains AgNO3/ PAN presoma composite nano fiber.The AgNO that will obtain3/PAN
Tunica fibrosa is immersed in the hydrazine hydrate solution that volume fraction is 1/200, takes out tunica fibrosa, and put in distilled water after 20min
Faster clean 2 times, then take out drying at room temperature, obtain AgNPs/PAN tunica fibrosa.Then, AgNPs/PAN tunica fibrosa carries out height
Temperature is fired the stage, under air atmosphere, carries out the pre-oxidizing the stage of tunica fibrosa, and tube furnace is with 5 DEG C/min heating rate by room temperature liter
To 250 DEG C, when reaching 250 DEG C, constant temperature keeps 2h.It is passed through high-purity N into tube furnace again2, N2Under atmosphere, tube furnace is with 3 DEG C/min
Heating rate rises to 900 DEG C by 250 DEG C, and keeps 2h at 900 DEG C, completes carbonation stage, finally, N2Under protection, treat tube furnace
Temperature is cooled to room temperature, takes out tunica fibrosa, obtains AgNPs/CNFs loaded catalyst.The composite fibre being obtained using the method
In, CNFs fiber is that existed with C=C graphite plane stratum reticulare result.It is used for benzene second using the AgNPs/CNFs that the method obtains
In ene oxidation reaction system, cinnamic conversion ratio can reach 40.6%, and the selectivity of Styryl oxide and benzaldehyde is respectively
35.9% and 53.1%.
Embodiment 2, with hydrogen reducing preparation, there is the AgNPs/CNFs of styrene catalyzed oxidation susceptibility
A certain amount of AgNO is added in the PAN/DMF solution being 8% to mass fraction3, make AgNO3Mol ratio with PAN is
1/10, lucifuge ice bath stirs 5h, obtains uniform AgNO3Solution before/PAN spinning.The solution obtaining is put in spin duct, adjusts
Spinning distance is 17cm, voltage 17kV, and electrospinning obtains AgNO3/ PAN presoma composite nano fiber.AgNO3/ PAN fiber film
Put in reactor, into reactor, be passed through N2Make pressure reach 1MPa, then release N2, it is repeated 3 times.By above-mentioned similar operations,
It is passed through in reactor and release H2Twice.Finally, it is passed through the H of 1MPa in reactor2, set 40 DEG C of temperature in the kettle, reaction
3h.Reaction obtains AgNPs/PAN tunica fibrosa after terminating.Then, AgNPs/PAN tunica fibrosa carries out high-temperature firing, under air atmosphere,
Carry out the pre-oxidizing the stage of tunica fibrosa, tube furnace rises to 250 DEG C with 5 DEG C/min heating rate by room temperature, and constant temperature keeps 2h.Again
It is passed through high-purity N into tube furnace2, N2Under atmosphere, tube furnace rises to 900 DEG C with 3 DEG C/min heating rate by 250 DEG C, and keeps
2h, completes carbonation stage, finally, N2Under protection, treat that tubular type furnace temperature is cooled to room temperature, take out tunica fibrosa, obtain AgNPs/
CNFs loaded catalyst.In the composite fibre being obtained using the method, CNFs fiber is with C=C graphite plane stratum reticulare result
Exist.Using the method obtain AgNPs/CNFs be used for styrene oxidation system in, cinnamic conversion ratio up to
To 43.4%, the selectivity of Styryl oxide and benzaldehyde is respectively 38.9% and 54.5%.
Embodiment 3, preparation have the AgNPs-Mg/CNFs of styrene catalyzed oxidation susceptibility
A certain amount of AgNO is added in the PAN/DMF solution being 8% to mass fraction3And MgNO3, make AgNO3With PAN's
Mol ratio is 1/10, MgNO3And AgNO3Mol ratio be 1/10, lucifuge ice bath stir 5h, obtain uniform AgNO3Before/PAN spins
Solution.The solution obtaining is put in spin duct, adjusting spinning distance is 17cm, voltage 17kV, and electrospinning obtains AgNO3-MgNO3/
PAN presoma composite nano fiber.Then, AgNO3-MgNO3/ PAN fiber film carries out high-temperature firing, under air atmosphere, carries out fibre
The pre-oxidizing the stage of dimension film, tube furnace rises to 250 DEG C with 5 DEG C/min heating rate by room temperature, and constant temperature keeps 2h.Again to tubular type
It is passed through high-purity N in stove2, N2Under atmosphere, tube furnace rises to 900 DEG C with 3 DEG C/min heating rate by 250 DEG C, and keeps 2h, completes
The carbonation stage of tunica fibrosa.Finally, N2Under protection, treat that tubular type furnace temperature is cooled to room temperature, take out tunica fibrosa, obtain AgNPs-
Mg/CNFs loaded catalyst.In the composite fibre being obtained using the method, CNFs fiber is with C=C graphite plane stratum reticulare knot
Fruit exists.It is used in styrene oxidation system using the AgNPs-Mg/CNFs that the method obtains, cinnamic conversion ratio
Can reach 54.6%, the selectivity of Styryl oxide and benzaldehyde is respectively 43.2% and 41.7%.
Claims (3)
1. a kind of support type AgNPs-Mg/CNFs catalyst for styrene catalyzed oxidation is it is characterised in that carrier is to have
Extensive chemical inertia, the CNFs of bigger serface, active component is larger, the finely dispersed AgNPs of activity, in AgNPs/CNFs
Add a small amount of alkaline-earth metal Mg as secondary catalyst, improve catalytic effect；Described catalyst is prepared by electrical spinning method
AgNO3-MgNO3During/PAN precursor, AgNO in solution before spinning3Mol ratio with PAN is 1/10, MgNO3With AgNO3Mol ratio be
1/10.
2. a kind of preparation method of support type AgNPs-Mg/CNFs catalyst according to claim 1 it is characterised in that
The AgNPs-Mg/CNFs of catalytic oxidation performance is had by the combination preparation of Electrospinning and high-temperature calcination technology.
3. the preparation method of support type AgNPs-Mg/CNFs catalyst according to claim 2 is it is characterised in that described
Method comprises the following steps：
(1)AgNO3-MgNO3The preparation of/PAN fiber：It is simultaneously introduced AgNO in the PAN/DMF solution being 8% to mass fraction3With
MgNO3, lucifuge ice bath stirring 5h, obtain uniform AgNO3-MgNO3Solution before/PAN spinning；The solution obtaining is put into spin duct
In, adjusting spinning distance is 17cm, and voltage 17kV, under room temperature, obtains AgNO using electrostatic spinning technique3-MgNO3/ PAN fiber；
(2) preparation of AgNPs-Mg/CNFs：AgNO3-MgNO3/ PAN fiber is placed in porcelain boat and is put in vacuum tube furnace；
Under air atmosphere, carry out the pre-oxidizing the stage of tunica fibrosa, tube furnace rises to 250 DEG C and perseverance with 5 DEG C/min heating rate by room temperature
Temperature keeps 2h；Then, it is passed through high-purity N into tube furnace2, N2Under atmosphere, tube furnace is risen to by 250 DEG C with 3 DEG C/min heating rate
900 DEG C, and keep 2h, complete the carbonation stage of tunica fibrosa；Finally, N2Under protection, treat that tubular type furnace temperature is cooled to room temperature, take out
Tunica fibrosa, obtains AgNPs-Mg/CNFs composite.
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| CN108950260B (en) * | 2018-08-07 | 2019-08-27 | 泉州市康馨化工科技有限公司 | The preparation method of Mg base hydrogen storage nano wire |
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| Preparation and electrochemical properties of carbon nanofiber composite dispersed with silver nanoparticles using polyacrylonitrile and β-cyclodextrin;Bo-Hye Kim et al.,;《Journal of Nanoscience and Nanotechnology》;20111231;第11卷(第8期);7193-7197 * |
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