CN102974350B - Graphene-supported metallic oxide nanometer material as well as preparation method and application thereof - Google Patents
Graphene-supported metallic oxide nanometer material as well as preparation method and application thereof Download PDFInfo
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- CN102974350B CN102974350B CN201210489612.2A CN201210489612A CN102974350B CN 102974350 B CN102974350 B CN 102974350B CN 201210489612 A CN201210489612 A CN 201210489612A CN 102974350 B CN102974350 B CN 102974350B
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Abstract
The invention belongs to the field of the material science, and relates to a preparation method of a novel graphene-supported metallic oxide nanometer material and a catalytic application of the novel grapheme-supported metallic oxide nanometer material in a Fischer-Tropsch synthesis reaction. The novel graphene-supported metallic oxide nanometer material is prepared by a one-step reaction of a graphite oxide and an acetylacetone metallic compound under a hydrothermal condition, and has a microstructure characteristic that small-sized nanometer oxides are uniformly dispersed on the surface of grapheme to the maximum extent. When a catalyst prepared by the novel graphene-supported metallic oxide nanometer material is used in the Fischer-Tropsch synthesis reaction, the catalyst has the advantages of higher selectivity in gasoline hydrocarbons (C5-11), high stability and the like compared with an unmodified iron catalyst reported by a current document.
Description
Technical field
The invention belongs to material science, be specifically related to a kind of graphene-supported metal oxide nano-material and its preparation method and application.
Background technology
A kind of method of F-T synthesis to be the carbon monoxide that coal, natural gas, living beings obtained by catalysis and hydrogen gas be liquefied hydrocarbon, synthesized liquid fuel is made up of straight-chain hydrocarbons, alkene substantially, have without sulphur, without nitrogen, without metal, without advantages such as aromatic hydrocarbons, be clean, the fuel oil of environmental protection and chemicals.One of key factor of F-T synthesis develops the catalyst of stability, active good, cheap, wide material sources.For this reason, domestic and international many R&D institutions and oil company have all dropped into huge financial resources and manpower is researched and developed, as (petrochemical technology economy such as Peking University, Xiamen University, Fudan University, Shanxi coalification institute of the Chinese Academy of Sciences, the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences, Shenhua Group, Sasol company, Shell company, Exxon companies, 2004,19:8; Chemical industry is in progress, 2003,22:441).Wherein, the material with carbon element of inertia is adopted to receive the concern of researcher as the catalyst carrier of Fischer-Tropsch synthesis, such as adopt during the carrier of CNT as iron and show good F-T synthesis performance (J. Am. Chem. Soc., 2008,130:9414).But CNT is expensive, catalyst cupport method is also comparatively complicated.Thus, simple, the raw material sources of a kind of preparation method widely iron Pd/carbon catalyst can have a good application prospect in F-T synthesis.The rich reserves of iron, cheap, and to the selective height of low-carbon alkene in Fischer-Tropsch synthesis, tend to generate low catenanes, be conducive to synthesizing the important raw material of industry as ethene, propylene, butylene and the high-octane gasoline of preparation etc.Ferrum-based catalyst has higher activity to water gas shift reaction, is also conducive to low H
2the application of synthesis gas in F-T synthesis of/CO ratio.
Graphene owing to having unique physics and chemistry character, receives increasing concern in fields such as electricity, magnetics, optics, catalysis and drug deliveries as a kind of new carbon.But the preparation of current Graphene is generally carried out under comparatively exacting terms, as expensive in needs high temperature, high pressure, high-energy, the prices of raw and semifnished materials and complicated process of preparation etc.Meanwhile, by its blemish position, impact that functional group is few, the particle diameter of the nano particle of its area load is difficult to be controlled, and is difficult to accomplish dispersed, and particle diameter is large.And large particle diameter means little catalyst activity surface area, the utilization ratio of catalyst activity component is reduced, and in Fischer-Tropsch synthesis, catalytic activity is low.As Wang etc. with Graphene, iron chloride, vitamin C, Macrogol 6000, urea for raw material, adopt hydro-thermal method to prepare iron oxide/graphene composite material, iron oxide particle diameter reaches 2-5 μm (J. Alloys Compd., 2011,509:L216).Wang etc. with Graphene, ferric nitrate, sodium acetate, PEG 20000 for raw material, ethylene glycol solvent by the use of thermal means is adopted to prepare iron oxide/graphene nanocomposite material, ferric oxide nanometer particle high aggregation (Mater. Chem. Phys., 2011,128:336).Zhou etc. adopt graphene-supported iron hydroxide, and under an ar atmosphere 600
othe iron oxide material of Graphene parcel has been prepared in C reduction, and not only preparation temperature is high, and the iron oxide particle diameter obtained is also very large, reaches 196 nm(Chem. Mater., 2010,22:5306).Wu etc. adopt ferric acetate, polypyrrole, graphite oxide to be raw material, and in the aerogel material prepared by hydro-thermal method, the particle diameter of iron oxide reaches 20 – 80 nm(J. Am. Chem. Soc., 2012,134:9082).In Graphene/ferric oxide composite material that Zhu etc. adopt precipitation from homogeneous solution-hydrazine reduction two-step method to prepare, the particle diameter of iron oxide reaches 60 nm(ACS Nano, 2011,5:3333).Su etc. adopt one-step method to prepare iron oxide-graphene nanocomposite material, iron oxide particle diameter about 7.1 nm, and its source of iron is iron chloride, and in water-heat process, add hydrazine reducing agent (J. Phys. Chem. C, 2011,115:14469).From the above results, the usual more complicated of method of graphene-supported oxide material is prepared in document, graphite oxide is first reduced to Graphene by general needs, or at comparatively complicated chemical environment or comparatively load oxide under exacting terms, and oxide particle particle diameter is comparatively large, more the preparation method of the material of small particle diameter has to be developed.Thus, develop a kind of simple and easy, energy consumption is low, environmental protection, efficient graphene-supported metal oxide nano-material preparation method, and the metal oxide nano-material of institute's load has, and size is little, the feature of high dispersive, has very important using value undoubtedly in the fields such as catalysis.
Summary of the invention
The object of the invention is to propose that a kind of utilization of materials is high, preparation method is simple, catalytic efficiency is high, the graphene-supported metal oxide nano-material of good stability and its preparation method and application.
The preparation method of the graphene-supported metal oxide nano-material that the present invention proposes, its concrete steps are as follows:
1) 30
oc ~ 50
oin the temperature range of C, graphite oxide ultrasonic disperse is made suspension in distilled water;
2) 60
oc ~ 80
oin the temperature range of C, acetylacetone metallic compound is added in above-mentioned suspension; After stirring 1 ~ 4h at such a temperature, be transferred in band teflon-lined water heating kettle;
3) water heating kettle is placed in 140
oc ~ 180
ohydrothermal treatment consists 12 ~ 48 h in the baking oven of C; Then take out water heating kettle, naturally cool, filter, wash, dry obtained required nano material.
Wherein, graphite oxide quality is 0.5 ~ 2 g preferably, and distilled water volume is 100 ~ 400 mL preferably, hydrothermal temperature preferably 160 ~ 180
oc, the hydro-thermal time is 12 ~ 24 h preferably.
The mass ratio of described graphite oxide and acetylacetone metallic compound is 1:1 ~ 1:5.
Described acetylacetone metallic compound is soluble metallic salt, is the one in ferric acetyl acetonade, acetylacetone cobalt, nickel acetylacetonate.
In the present invention, graphite oxide further hydrothermal reduction together with acetylacetone metallic compound is adopted to be Graphene, be formed in the homodisperse metal oxide nanoparticles of graphenic surface simultaneously, the metal oxide particle diameter obtained can be less than 3 nm, not only high dispersive, and can keep stable in high temperature reduction and macrocyclic Fischer-Tropsch synthesis.
In the present invention, the raw material of employing is only graphite oxide and acetylacetone metallic compound, and adding without other reducing agents, dispersant or precipitating reagent, raw material is single.The oxy radical utilizing graphite oxide surface abundant and the coordination of acetylacetone,2,4-pentanedione, namely achieve high dispersive and the firmly grappling of metal oxide nanoparticles easily.
In the present invention, it adopts the aqueous solution containing graphite oxide and cetylacetone metallic to prepare target material through a step Hydrothermal Synthesis, utilize graphite oxide can be reduced to Graphene under hydrothermal conditions, acetylacetone metallic compound can be hydrolyzed to oxide under hydrothermal conditions, gentleness preparation condition next step achieve the reduction of graphene oxide and the load of metal oxide nanoparticles.
According to graphene-supported metal oxide nano-material prepared by the inventive method, active component nano particle is dispersed on Graphene.It is very high that transmission electron microscope photo shows the nanoparticulate dispersed degree be carried on graphenic surface, and uniform particle diameter, can be used as the presoma of catalyst in Fischer-Tropsch synthesis.Be applied to the reduction activation before Fischer-Tropsch synthesis to carry out in tube furnace, reducing condition is as follows: H
2/ Ar flow velocity is 20 ~ 60 ml/min, preferably 30 ~ 50 ml/min; Reduction temperature is 300 ~ 600
oc, preferably 400 ~ 500
oc; Recovery time is 180 ~ 2880 min, preferably 300 ~ 1440 min.
The available following method evaluation of activity of catalyst provided by the invention:
Fischer-Tropsch synthesis carries out in high-pressure flow fixed-bed micro-reactor.Stainless steel reaction bore is 10 mm, and length is 470 mm, and beds is positioned at electric tube furnace flat-temperature zone, and thermocouple is placed in the middle part of beds by sleeve pipe.Reacting gas or pretreatment gas are by the accurate adjust flux of mass flowmenter, and Fischer-Tropsch synthetic adopts gas-chromatography to analyze.
Accompanying drawing explanation
Fig. 1 is the microscopic appearance of the embodiment of the present invention 1 gained nano particle.
Fig. 2 is the microscopic appearance of the embodiment of the present invention 2 gained nano particle.
Fig. 3 is the microscopic appearance of the embodiment of the present invention 3 gained nano particle.
Fig. 4 is the microscopic appearance of the embodiment of the present invention 4 gained nano particle.
Detailed description of the invention
The invention is further illustrated by the following examples, but therefore do not limit the present invention.
Embodiment 1: the preparation of novel graphite alkene load iron nano particle catalysis material
Added by 1 g graphite oxide in 200 mL distilled water, ultrasonic disperse makes suspension in 2 hours.2 g ferric acetyl acetonades are added in above-mentioned suspension under magnetic stirring.Mixed solution is 80
ostir 2 hours under C, proceed to afterwards in band teflon-lined water heating kettle.Water heating kettle is placed in 160
ohydrothermal Synthesis certain hour in C baking oven, then takes out nature cooling, filters, washing, in air atmosphere 50
odrying 10 hours under C.In this example, Fig. 1 is shown in by the TEM photo of the microscopic appearance of graphene-supported iron nano-particle, and the average grain diameter of iron nano-particle is only 2.4 nm, and even particle size distribution.
Embodiment 2: the preparation of novel graphite alkene Supported Co nano particle catalysis material
Added by 1 g graphite oxide in 200 mL distilled water, ultrasonic disperse makes suspension in 2 hours.5 g acetylacetone cobalts are added in above-mentioned suspension under magnetic stirring.Mixed solution is 80
ostir 2 hours under C, proceed to afterwards in band teflon-lined water heating kettle.Water heating kettle is placed in 160
ohydrothermal Synthesis certain hour in C baking oven, then takes out nature cooling, filters, washing, in air atmosphere 50
odrying 10 hours under C.In this example, Fig. 2 is shown in by the TEM photo of the microscopic appearance of graphene-supported cobalt nano-particle, and the average grain diameter of cobalt nano-particle is only 8.1 nm, and even particle size distribution.
Embodiment 3: the preparation of novel graphite alkene nickel-loaded nano particle catalysis material
Added by 1 g graphite oxide in 200 mL distilled water, ultrasonic disperse makes suspension in 2 hours.5 g nickel acetylacetonates are added in above-mentioned suspension under magnetic stirring.Mixed solution is 80
ostir 2 hours under C, proceed to afterwards in band teflon-lined water heating kettle.Water heating kettle is placed in 160
ohydrothermal Synthesis certain hour in C baking oven, then takes out nature cooling, filters, washing, in air atmosphere 50
odrying 10 hours under C.In this example, Fig. 3 is shown in by the TEM photo of the microscopic appearance of graphene-supported nano nickel particles, and the average grain diameter of nano nickel particles is only 7.5 nm, and even particle size distribution.
Comparative example 1: the preparation of the graphene-supported iron nano-particle catalysis material reduced in advance
Added by 1 g graphite oxide in 200 mL distilled water, ultrasonic disperse makes suspension in 2 hours.Then in suspension, add 5 mL concentration is the hydrazine hydrate solution of 85%, 50
oc lower magnetic force stirs reduction 12 hours.Gained black Graphene solid after filtration, distilled water washing after, ultrasonic disperse makes Graphene suspension in 200 mL distilled water again.Added under magnetic stirring in Graphene suspension by 2 g ferric acetyl acetonades, mixed solution is 80
ostir 2 hours under C, proceed to afterwards in band teflon-lined water heating kettle.Water heating kettle is placed in 160
ohydrothermal Synthesis certain hour in C baking oven, then takes out nature cooling, filters, washing, then in air atmosphere 50
odrying 10 hours under C.Fig. 4 is shown in by the TEM photo of the microscopic appearance of the graphene-supported iron nano-particle reduced in advance in this example, and the average grain diameter of iron nano-particle reaches 32.7 nm.
Reactivity worth Evaluation operation example 1: novel graphite alkene load iron nanoparticle catalyst
Catalyst after drying is sieved, gets 80 ~ 120 object parts and load in reaction tube, logical H
2/ Ar(volume ratio 5%) gaseous mixture is 450
oin-situ reducing 12 h under C, gas flow is 50 ml/min, and heating rate is 2
oc/min.Gained catalyst is designated as Fe-rGO.Fischer-Tropsch synthesis carries out under the following conditions: P=2.0 MPa, T=270
oc, gas flow rate is 33.3 ml/ min, and feed gas molar consists of H
2/ CO=2, catalyst loading amount is 1 g.Reaction result lists in table 1.
Reactivity worth Evaluation operation example 2: novel graphite alkene Supported Co nanoparticle catalyst
Catalyst after drying is sieved, gets 80 ~ 120 object parts and load in reaction tube, logical H
2/ Ar(volume ratio 5%) gaseous mixture is 450
oin-situ reducing 12 h under C, gas flow is 50 mL/min, and heating rate is 2
oc/min.Gained catalyst is designated as Co-rGO.Fischer-Tropsch synthesis carries out under the following conditions: P=2.0 MPa, T=250
oc, gas flow rate is 33.3 mL/ min, and feed gas molar consists of H
2/ CO=2, catalyst loading amount is 1 g.Reaction result lists in table 2.
As seen from Table 1, graphene-supported iron nano-particle catalyst prepared by the method that this patent proposes shows good stability in Fischer-Tropsch synthesis, in product gasoline section hydrocarbon selective higher than existing bibliographical information without the result on addition agent modified Fe fischer-tropsch synthetic catalyst, show good application prospect.As seen from Table 2, graphene-supported cobalt nano-particle catalyst shows good stability equally in Fischer-Tropsch synthesis, and on its catalyst of what is more important, gasoline section hydrocarbon selective has had and increases substantially.
Reactivity worth evaluates comparative example 1: the preparation of the graphene-supported iron nano-particle catalysis material reduced in advance
Catalyst after drying is sieved, gets 80 ~ 120 object parts and load in reaction tube, logical H
2/ Ar(volume ratio 5%) gaseous mixture is 450
oin-situ reducing 12 h under C, gas flow is 50 mL/min, and heating rate is 2
oc/min.Gained catalyst is designated as Fe/p-rGO.Fischer-Tropsch synthesis carries out under the following conditions: P=2.0 MPa, T=250
oc, gas flow rate is 33.3 mL/ min, and feed gas molar consists of H
2/ CO=2, catalyst loading amount is 1 g.Reaction result lists in table 3.
As seen from Table 3, adopt the Fe/p-rGO catalyst method that graphite oxide hydrazine hydrate reduces in advance prepared, because iron nano-particle particle diameter is excessive, in Fischer-Tropsch synthesis, reactivity worth is very poor.Catalyst initial activity is low, and obvious inactivation occurs in course of reaction.On this catalyst, long-chain products is selective lower simultaneously, constantly reduces at course of reaction medium chain growing ability.
table 1,the catalytic performance of graphene-supported iron nano-particle catalyst in Fischer-Tropsch synthesis
。
table 2,the catalytic performance of graphene-supported cobalt nano-particle catalyst in Fischer-Tropsch synthesis
。
table 3,the catalytic performance of Fe/p-rGO nanoparticle catalyst in Fischer-Tropsch synthesis
。
Claims (6)
1. a preparation method for graphene-supported metal oxide nano-material, is characterized in that concrete steps are as follows:
1) 30
oc ~ 50
oin the temperature range of C, graphite oxide ultrasonic disperse is made suspension in distilled water;
2) 60
oc ~ 80
oin the temperature range of C, acetylacetone metallic compound is added in above-mentioned suspension; After stirring 1 ~ 4h at such a temperature, be transferred in band teflon-lined water heating kettle;
3) water heating kettle is placed in 140
oc ~ 180
ohydrothermal treatment consists 12 ~ 48 h in the baking oven of C; Then take out water heating kettle, naturally cool, filter, wash, dry, be i.e. obtained required nano material;
Described acetylacetone metallic compound is ferric acetyl acetonade, acetylacetone cobalt or nickel acetylacetonate.
2. a preparation method for graphene-supported metal oxide nano-material as claimed in claim 1, it is characterized in that described graphite oxide quality is 0.5 ~ 2 g, distilled water volume is 100 ~ 400 mL, and hydrothermal temperature is 160 ~ 180
oc, the hydro-thermal time is 12 ~ 24 h.
3. a preparation method for graphene-supported metal oxide nano-material as claimed in claim 1, is characterized in that the mass ratio of graphite oxide and acetylacetone metallic compound is 1:1 ~ 1:5.
4. the graphene-supported metal oxide nano-material prepared by the described method of one of claim 1-3.
5. after a graphene-supported metal oxide nano-material reduction activation as claimed in claim 4 in Fischer-Tropsch synthesis as the application of catalyst.
6. application according to claim 5, it is characterized in that the reduction activation before being applied to Fischer-Tropsch synthesis is carried out in tube furnace, reducing condition is as follows: H
2/ Ar flow velocity is 20 ~ 60 ml/min, and reduction temperature is 300 ~ 600
oc, the recovery time is 180 ~ 2880 min.
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| WO2014174394A2 (en) * | 2013-04-25 | 2014-10-30 | Mandal Dr Swadhin K | Method of synthesis and composite thereof |
| EP3302791A1 (en) * | 2015-05-26 | 2018-04-11 | Council of Scientific & Industrial Research | Magnetically separable iron-based heterogeneous catalysts for dehydrogenation of alcohols and amines |
| CN105964263B (en) * | 2016-05-14 | 2019-01-29 | 复旦大学 | Graphene-supported efficient iron-base F- T synthesis producing light olefins catalyst and preparation method thereof |
| CN108155020B (en) * | 2016-12-02 | 2019-10-25 | 中国石油化工股份有限公司 | Graphene composite material and its preparation method and application |
| CN107754793B (en) * | 2017-11-23 | 2020-04-17 | 中科合成油技术有限公司 | Porous carbon loaded Fischer-Tropsch synthesis catalyst and preparation method and application thereof |
| CN108976130B (en) * | 2018-09-20 | 2019-07-16 | 张磊 | A method of preparing treatment ovarian cancer intermediate |
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| CN102671661A (en) * | 2012-03-20 | 2012-09-19 | 清华大学 | Multi-walled carbon nanotube-loaded nano ferroferric oxide catalyst and preparation method and application thereof |
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| CN101376114A (en) * | 2008-10-09 | 2009-03-04 | 大连理工大学 | Method for preparing metal or metallic oxide/carbon composite material |
| CN102125844A (en) * | 2010-01-15 | 2011-07-20 | 复旦大学 | Method for preparing iron-carbon microsphere material and use thereof |
| CN102671661A (en) * | 2012-03-20 | 2012-09-19 | 清华大学 | Multi-walled carbon nanotube-loaded nano ferroferric oxide catalyst and preparation method and application thereof |
Non-Patent Citations (1)
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|---|
| "The production of self-assembled Fe2O3–graphene hybrid materials by a hydrothermal process for improved Li-cycling";Leilei Tian et al;《Electrochimica Acta》;20120116;第65卷;第2.1节 * |
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