CN108927130A - A kind of fluorinated nano diamond material and its preparation method and application - Google Patents
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Abstract
The invention belongs to technical field of nanometer material preparation, be related to a kind of fluorinated nano diamond material and preparation method thereof and its thermocatalytic field application.This method is with Nano diamond, after perfluorinated butyl iodide is raw material and is fluorinated several hours under Xenon light shining, form the Nano diamond of Fluorin doped (0.3 wt% of Fluorin doped amount is most ratio of greater inequality), the reaction that styrene is then prepared applied to the oxidative dehydrogenation of ethylbenzene, shows excellent thermocatalytic performance.Preparation method safety and environmental protection provided by the invention, mild condition is controllable, simple process.Resulting fluorinated nano diamond physics, stable chemical performance, and there is good thermocatalytic performance, there is more extensive application in other Industrial Catalysis fields.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, it is related to a kind of fluorinated nano diamond material and preparation method thereof
With its application in thermocatalytic field.
Background technique
Styrene (styrene, ST) is a kind of industrial important monomer, is widely used in polymer, copolymer, production
The raw material of plastics and synthetic rubber.Such as modified rubber impact-resistant polystyrene, acrylonitrile-butadiene-styrene (ABS) tripolymer
(ABS), styrene-acrylonitrile copolymer (SAN) and butadiene-styrene rubber (SBR) etc. (ChemSusChem 2016,9,662-
666; ACS Catal. 2015, 5, 6426-6435;).The method for industrially preparing styrene is mainly the side in catalyst
It helps down, styrene (Appl. Catal. A:Gen. 1994,112,117-124 is made in the direct thermocatalytic dehydrogenation (DH) of ethylbenzene;
Appl. Catal. A:Gen. 1995, 133, 219-239; Chem. Commun. 2014, 50, 7810-7812;
Angew. Chem. Int. Ed. 2010,49,8640-8644).However this method conversion of ethylbenzene is low (< 50%), needs
Reaction temperature it is higher (600 DEG C of >), and kinetically belonging to the endothermic reaction (Δ Hο = +117.6 kJ·mol-1), it urges
Agent easy in inactivation is unfavorable for the progress of reaction.Based on this, the reaction new route of a kind of new catalyst and styrene preparation is found
Become the research topic of most of researchers, and the exploitation of oxidative dehydrogenation of ethylbenzene (ODH) reaction is exactly on this basis
It is evolved, the conversion ratio of the reaction ethylbenzene is generally higher (> 50%), and required reaction temperature is lower (600 DEG C of <), and in heat
Belong to exothermic reaction (Δ H on mechanicsο =-124.3 kJ·mol-1) (J. Catal. 1981,71,257-269; J.
Catal. 1982, 75, 66-77; Chem. Asian J. 2009, 4, 1108-1113; ChemSusChem 2016,
9, 662-666; Catal. Today 2018, 301, 32-37; Angew. Chem. Int. Ed. 2017, 56,
8231-8235).Nevertheless, oxidative dehydrogenation of ethylbenzene still still has several drawbacks because of the not perfect of catalyst, such as ethylbenzene
Excessive oxidation generates carbon dioxide under the action of catalyst, causes its selectivity lower；The formation of coke in ethylbenzene conversion process
Accumulation causes subsequent transformation rate and stability to reduce；The coke being deposited on catalyst reaction site easily causes the mistake of catalyst
(ChemSusChem 2016,9,662-666) living.Therefore, designing and develop a kind of novel can overcome the above problem
Catalyst is particularly important to the development in thermocatalytic field, also specifies direction to the preparation of the following industrially styrene.
Nano-sized carbon (nanocarbon, NC) material is a kind of inorganic non-metallic material emerging in recent years, such as Nanowire
Dimension, nanometer carbon line, Nano diamond, nano-onions carbon and fullerene etc. occupy a tiny space in thermocatalytic field,
Compared to common metallic catalyst, these C catalysts have it is cheap and easy to get, preparation process is simple, safety and environmental protection, stability
A series of advantages (Chem. Rev. 2013,113,5782-5816) such as good.Wherein Nano diamond (nanodiamond,
ND) with its unique structure and performance, people is caused widely to pay close attention to (Nature Nanotech. 2011,7,11-23).
Carbon atom in Nano diamond is all with sp3Hybridized orbit and other 4 carbon atoms of surrounding form covalent bond, it was reported that single
The ball-like diamond particle of 4.3 nm contains 7200 carbon atoms, has nearly 1100 carbon atoms to be located in its surface, therefore logical
Overdoping regulates and controls diamond surface structure, can effectively change its chemical property, and then regulates and controls oxidative dehydrogenation of ethylbenzene and prepare benzene second
The reaction of alkene.It reports multiple Modified Diamonds in succession in recent years and is applied to the example in thermocatalytic field, such as P, B member
The Nano diamond of element modification is used for propane anaerobic dehydrogenation and oxidative dehydrogenation (ACS Catal. 2015,5,2436-2444;
ACS Appl. Mater. Interfaces 2017,9,27638-27648) and sp2-sp3The diamond of mixed structure
For ethylbenzene anaerobic dehydrogenation and oxidative dehydrogenation (Carbon 2007,45,2145-2151; Chem. Eur. J. 2014,
20,6324-6331) need, however also the Nano diamond for further increasing these modifications to preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene
Performance.It is fluorinated as a result, and also receives extensive pass in recent years as a kind of technology that diamond surface structure is effectively transformed
Infuse (J. Mater. Chem. 2001,11,879-886; J. Am. Chem. Soc. 2005, 127, 3712-3713;
Carbon, 2000, 38, 241-267).However fluorinated nano diamond process is both not environmentally or dangerous now, such as benefit
With the fluorine gas (F of severe toxicity2), hydrogen fluoride (HF), xenon difluoride (XeF2) and ammonium acid fluoride (NH4HF2) etc. fluorine-containing presoma, in height
Be fluorinated under the critical conditions such as temperature, plasma, laser, X-ray (Diamond Relat. Mater. 1996,5,
1021-1025; J. Chem. Soc. Faraday Trans. 1993, 89, 3105-3109; ACS Nano 2018,
12, 1083-1088;Science 1996,271,193-195).Therefore, it develops a kind of green, convenient, safely controllable
The method of fluorinated nano diamond (fluorine-naonodiamond, F-ND) and be applied to ethylbenzene oxidative dehydrogenation prepare benzene
Ethylene is extremely important.In addition, fluorinated nano diamond material is in other necks such as photoelectricity, catalysis, energy storage and load medicines
Domain also would indicate that huge application potential.
Summary of the invention
The purpose of the present invention is to provide a kind of fluorinated nano diamond (F-ND) material and preparation method thereof with it in heat
The application of catalytic field.Safety and environmental protection of the present invention, simple process, condition is controllable, meets actual production demand.
To achieve the above object, the present invention adopts the following technical scheme:
1) take 40 ~ 80 mg Nano diamonds in magneton 25 mL round-bottomed flasks in, and be added 1 ~ 5 mL perfluor iodo
Butane.
It 2), can with Xenon light shining 1 ~ 5 hour by the resulting mixed system of step 1) under 30 DEG C of constant temperature of water-bath
Enough fluorinations are complete.
3) the mixed system centrifugation of step 2), washing, and dried overnight at 80 DEG C, gained is fluorinated nano Buddha's warrior attendant
Stone, wherein Fluorin doped amount is 0.1-0.5wt%, and 0.3 wt% is optimal.
Using: application of the fluorinated nano diamond material in thermocatalytic preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene.
Remarkable advantage of the invention is:
(1) synthetic method safety and environmental protection of the present invention, preparation process is simple, and mild condition is controllable.
(2) the fluorinated nano diamond material crystal structure that the present invention synthesizes is intact, is not destroyed.
(3) the fluorinated nano diamond material (0.3 wt% of Fluorin doped amount is most ratio of greater inequality) that the present invention synthesizes can be used for ethylbenzene
Oxidative dehydrogenation prepare styrene reaction, 120 hours heat catalysis (400 DEG C) long-time test in, conversion of ethylbenzene
Reach 80%, benzene hydrocarbon (benzene and styrene) selectively up to 90% meets Industrial Catalysis demand.
(4) the fluorinated nano diamond material that synthesizes of the present invention can not only be applied to thermocatalytic field, other as photoelectricity,
Also there is potential application power in the fields such as photocatalysis, energy storage and load medicine.
Detailed description of the invention
Fig. 1 is the synthesis process schematic diagram of embodiment 2 resulting fluorinated nano diamond (F-ND) material；
A is the X-ray powder diffraction figure of embodiment 2 resulting fluorinated nano diamond (F-ND) and Nano diamond in Fig. 2
(XRD);B is Raman (Raman) spectrogram of 2 resulting fluorinated nano diamond (F-ND) of embodiment and Nano diamond；
A is the Fourier transform infrared light of fluorinated nano diamond (F-ND) and Nano diamond synthesized by embodiment 2 in Fig. 3
Spectrogram (FT-IR)；B is the x-ray photoelectron spectroscopy of embodiment 2 resulting fluorinated nano diamond (F-ND) and Nano diamond
(XPS)；
A, b, c and d respectively correspond the projection electron microscope (TEM) of the Nano diamond in embodiment 2, Fourier transformation figure in Fig. 4
(FFT), high-resolution projection electron microscope (HRTEM) and structural schematic diagram；
A, b, c and d respectively correspond the projection electron microscope (TEM) of the fluorinated nano diamond (F-ND) in embodiment 2, Fu in Fig. 5
In leaf transformation figure (FFT), high-resolution projection electron microscope (HRTEM) and structural schematic diagram；
A is the heat of fluorinated nano diamond (F-ND) and Nano diamond at the 30th hour synthesized by embodiment 2 in Fig. 6
It is catalyzed (400 DEG C) oxidative dehydrogenation of ethylbenzene activity figure；B is fluorinated nano diamond (F-ND) and nanogold synthesized by embodiment 2
Hard rock is catalyzed (400 DEG C) oxidative dehydrogenation of ethylbenzene activity figure in 120 hours Long Time Thermals.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
It takes 40 mg of Nano diamond in round-bottomed flask of 25 mL with magneton, and 3 mL perfluor butyl iodides is added.In magnetic
30 DEG C of waters bath with thermostatic control are placed under power stirring, and with Xenon light shining 1 hour.It after the completion of fluorination, is centrifuged, washing, and the mistake at 80 DEG C
Night drying is to get fluorinated nano diamond, and wherein Fluorin doped amount is 0.1wt%.
Embodiment 2
It takes 40 mg of Nano diamond in round-bottomed flask of 25 mL with magneton, and 3 mL perfluor butyl iodides is added.In magnetic
30 DEG C of waters bath with thermostatic control are placed under power stirring, and with Xenon light shining 3 hours.It after the completion of fluorination, is centrifuged, washing, and the mistake at 80 DEG C
Night drying is to get fluorinated nano diamond, and wherein Fluorin doped amount is 0.3wt%.
Embodiment 3
It takes 80 mg of Nano diamond in round-bottomed flask of 25 mL with magneton, and 3 mL perfluor butyl iodides is added.In magnetic
30 DEG C of waters bath with thermostatic control are placed under power stirring, and with Xenon light shining 5 hours.It after the completion of fluorination, is centrifuged, washing, and the mistake at 80 DEG C
Night drying is to get fluorinated nano diamond, and wherein Fluorin doped amount is 0.5wt%.
Embodiment 4
It takes 40 mg of Nano diamond in round-bottomed flask of 25 mL with magneton, and 3 mL perfluor butyl iodides is added.In magnetic
30 DEG C of waters bath with thermostatic control are placed under power stirring, and with Xenon light shining 4 hours.It after the completion of fluorination, is centrifuged, washing, and the mistake at 80 DEG C
Night drying is to get fluorinated nano diamond, and wherein Fluorin doped amount is 0.4wt%.
Embodiment 5
It takes 40 mg of Nano diamond in round-bottomed flask of 25 mL with magneton, and 3 mL perfluor butyl iodides is added.In magnetic
30 DEG C of waters bath with thermostatic control are placed under power stirring, and with Xenon light shining 2 hours.It after the completion of fluorination, is centrifuged, washing, and the mistake at 80 DEG C
Night drying is to get fluorinated nano diamond, and wherein Fluorin doped amount is 0.2wt%.
Fig. 1 is the synthesis process schematic diagram of embodiment 2 resulting fluorinated nano diamond (F-ND) material.Fluorination process hair
Life does not damage overall structure on Nano diamond surface.
A is the X-ray powder diffraction of embodiment 2 resulting fluorinated nano diamond (F-ND) and Nano diamond in Fig. 2
Scheme (XRD), the fluorinated nano diamond structure as can be seen from the figure synthesized changes there is no apparent, Nano diamond
Feature crystal face (111), (220) and (311) in addition to remitted its fury a bit, there is no too big compared to Nano diamond for peak shift
Variation.And fluorinated Nano diamond has apparent enhancing at the crystal face (002) for belonging to graphite, illustrates in fluorination process, gold
Hard rock surface portion sp3The carbon fracture of hydridization generates sp2The carbon of hydridization, the fluorinated success of indirect proof.B is to implement in Fig. 2
Raman (Raman) spectrogram of 2 resulting fluorinated nano diamond (F-ND) of example and Nano diamond, from figure it can also be seen that
There is no apparent displacement occurs and changes compared to Nano diamond spectrogram for fluorinated Nano diamond spectrogram.In conclusion
Fluorination process does not change the entirety of Nano diamond, and crystal structure is intact.
A is red for the Fourier transformation of fluorinated nano diamond (F-ND) synthesized by embodiment 2 and Nano diamond in Fig. 3
External spectrum figure (FT-IR), fluorinated nano diamond has apparent broad peak in 1050 ~ 1200 cm in figure-1Between, this belongs to C-F
The stretching vibration of key, while in 1222 cm-1With 1430 cm-1The peak at place is belonging respectively to C-F2The vibration of symmetrical and asymmetrical stretch
It is dynamic.Thus it can be seen that after fluorination, Nano diamond Surface Creation C-F and C-F2Two kinds of keys, it was demonstrated that be fluorinated successfully.Into
The x-ray photoelectron spectroscopy (b in Fig. 3) of one step can also prove fluorinated success, in conjunction with can be in 684.7 eV and 688.3 eV
It is belonging respectively to C-F and C-F2Key.In conclusion we have successfully synthesized fluorinated nano diamond, and generate C-F and C-F2
Two kinds of key.
A, b, c and d respectively correspond the projection electron microscope (TEM) of the Nano diamond in embodiment 2 in Fig. 4, Fourier becomes
Change figure (FFT), high-resolution projection electron microscope (HRTEM) and structural schematic diagram.The available Nano diamond particle of a from Fig. 4
Uniformly, do not reunite or stack.The crystal face (111) that b can see Nano diamond in Fig. 4 is corresponded to each other with XRD result.Figure
Spacing of lattice in 4 in c is the characteristics of 0.2 nm also complies with Nano diamond.
A, b, c and d respectively correspond the projection electron microscope of the fluorinated nano diamond (F-ND) in embodiment 2 in Fig. 5
(TEM), Fourier transformation figure (FFT), high-resolution projection electron microscope (HRTEM) and structural schematic diagram.From can be obtained in a in Fig. 5
It is uniform to fluorinated Nano diamond particle, do not reunite or stack, overall structure is without because fluorination process is destroyed.Figure
B can see fluorinated Nano diamond crystal face (111) and correspond to each other with XRD result in 5.Fluorinated nano Buddha's warrior attendant in Fig. 5 in c
The spacing of lattice of stone also demonstrates fluorination process for 0.2 nm and does not destroy its overall structure, and only on surface, " plating " has gone up one layer
The graphite linings of 0.35 nm spacing of lattice.
A was fluorinated nano diamond (F-ND) synthesized by embodiment 2 and Nano diamond at the 30th hour in Fig. 6
Thermocatalytic (400 DEG C, oxygen and ethylbenzene volume ratio are 3 to 1) oxidative dehydrogenation of ethylbenzene activity figure, we are it can be concluded that fluorine from figure
After change, the conversion ratio of oxidative dehydrogenation of ethylbenzene, which has, to be obviously improved, and the yield of styrene also increases about 3 times.Fig. 6
Middle b is that fluorinated nano diamond (F-ND) synthesized by embodiment 2 and Nano diamond were catalyzed in 120 hours Long Time Thermals
(400 DEG C, oxygen and ethylbenzene volume ratio are 3 to 1) oxidative dehydrogenation of ethylbenzene activity figure, from the figure we can see that after fluorination
Nano diamond stability is also good, does not inactivate in subsequent reaction, and reaction conversion ratio selectivity is all very high.It is comprehensive
Upper described, fluorinated Nano diamond has embodied higher conversion of ethylbenzene and benzene in the reaction of thermocatalytic oxidative dehydrogenation of ethylbenzene
The selectivity of hydrocarbon can satisfy actual production demand.
The foregoing is merely presently preferred embodiments of the present invention (wherein 0.3 wt% of Fluorin doped amount be most ratio of greater inequality), Fan Yibenfa
The equivalent changes and modifications that bright claim is done, are all covered by the present invention.
Claims (7)
1. a kind of preparation method of fluorinated nano diamond material, it is characterised in that: the following steps are included:
1) Nano diamond powder is added to the round-bottomed flask for having magneton, and perfluor butyl iodide liquid is added, makes its mixing
Uniformly；
2) the resulting aggregate sample of step 1) is placed in 30 DEG C of constant temperature systems of water-bath and is stirred, and illumination 1 ~ 5 hour under xenon lamp,
Nano diamond is set to be fluorinated completely；
3) aggregate sample for obtaining step 2) is centrifuged, washing, and is dried overnight in 80 DEG C of baking ovens to get fluorinated nano Buddha's warrior attendant
Stone material.
2. the preparation method of a kind of fluorinated nano diamond material according to claim 1, it is characterised in that: step 1)
In, the Nano diamond dosage is 40 ~ 80 mg, and perfluor butyl iodide dosage is 1 ~ 5 mL.
3. the preparation method of a kind of fluorinated nano diamond material according to claim 1, it is characterised in that: step 2)
In, the Xenon light shining time is 1 ~ 5 h.
4. the preparation method of a kind of fluorinated nano diamond material according to claim 1, it is characterised in that: step 3)
In, the sample centrifugation after illumination after washing, is dried overnight at 80 DEG C.
5. a kind of fluorinated nano diamond material of method preparation as described in claim 1.
6. fluorinated nano diamond material according to claim 5, it is characterised in that: Fluorin doped amount is 0.1-0.5wt%.
7. a kind of fluorinated nano diamond as claimed in claim 6 answering in thermocatalytic preparing phenylethylene by oxidation-dehydrogenation of ethyl benzene
With.
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| CN112717971A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Carbon-based catalyst, preparation method and application thereof, and method for preparing styrene by ethylbenzene dehydrogenation |
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