CN1974083A - Prepn process and application of metal-carbon nanometer composite material - Google Patents
Prepn process and application of metal-carbon nanometer composite material Download PDFInfo
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- CN1974083A CN1974083A CN 200610134142 CN200610134142A CN1974083A CN 1974083 A CN1974083 A CN 1974083A CN 200610134142 CN200610134142 CN 200610134142 CN 200610134142 A CN200610134142 A CN 200610134142A CN 1974083 A CN1974083 A CN 1974083A
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Abstract
The present invention relates to preparation process and application of metal-carbon nanometer composite material. The present invention prepares metal-carbon nanometer composite material by using furfural or its derivative as carbon source and metal salt as the furfural polymerizing catalyst, and through a hydrothermal or solvent thermal process and a carbonizing process. Thus prepared metal-carbon nanometer composite material has controllable appearance, hollow structure and great specific surface area as well as homogeneous distribution of metal on the carbon carrier. The preparation process has the advantages of facile material, simple operation, short period, low cost, etc. and is suitable for industrial production. The obtained metal-carbon nanometer composite material is used as the precursor for high activity catalyst, adsorbent, high grade ink, etc.
Description
Technical field
The present invention relates to preparation of nanomaterials and application thereof, particularly relate to a kind of method for preparing metal-carbon nanometer composite material.
Background technology
Metal-carbon nanometer composite material is because specific area is big and the special interaction of metal-carbon, shown the characteristic different with common metal-carbon composite, therefore at the aspects such as presoma of high activated catalyst, adsorbent, special oil ink material, super capacitor material, lithium battery material, hard material and metal carbides, demonstrate very strong application prospect.
The preparation method of metal-carbon nanometer composite material has vapor phase method usually, as imperfect combustion, vapour deposition; Solid phase method is as high-energy ball milling method, organic metal salt high temperature pyrolytic cracking (HTP); Liquid phase method is as sol-gel process, coprecipitation etc.For the preparation of metal-carbon nanometer composite material, vapor phase method yields poorly, and the preparation temperature height; With solid phase method preparation then be difficult to reach metal on charcoal equally distributed purpose [referring to document: CN 1401563A; Advanced Materials, 2005,17,2957-2960.].Studying more is to prepare metal-carbon nanometer composite material with the sol-gel process in the liquid phase method, sol-gel process prepares preparation process general following several steps of needs, i.e. formation, organogel, supercritical drying and the carbonization process of metal/organic charcoal hybrid gel of metal-carbon nanometer composite material.The method preparation technology is loaded down with trivial details, and the cycle is long, needs exchange of solvent; Adopt Supercritical Drying Technology, need high-tension apparatus, thereby the cost height is [referring to document: CN 1843958A; Chemistry ofMaterials, 2003,15 (20), 3745-3747].
Shuhong Yu in 2004 etc. have reported that employing starch and noble metal are that raw material and hydro-thermal charing co-reducing process prepare metal-carbon nanometer composite material [referring to document: Advanced materials, 2004,16 (18): 1636].After this, adopt easy charing carbon source under the hydrothermal condition, as starch, glucose, sucrose and cyclodextrin etc., and silver, the existing report of metal-carbon nanometer composite material [Angewandte Chemie International Edition, 2004 of the synthetic different-shape of source metal such as copper, 43,597; But furfural and derivative thereof yet there are no report as carbon source, and furfural has the reproducibility aldehyde groups, and easily polymerization and charing has very strong reproducibility to metal gold, silver, copper etc. under hydrothermal condition, and metallic cobalt, nickel etc. is had more weak reproducibility.Furfural is inexpensive, is easy to get, and than starch, the phosphorus content height of glucose, sucrose, cyclodextrin etc.
Summary of the invention:
The method that the purpose of this invention is to provide the metal-carbon nanometer composite material that a kind of manufacturing cycle is short, cost is low is a raw material with the furfural or derivatives thereof, adopt hydro-thermal polymerization coreduction-charing method to prepare pattern and controlled platinum, ruthenium, palladium, gold, silver, the copper of structure, cobalt, nano composite material and the application in relating to the hydrogen catalysis reaction thereof such as nickel-charcoal.
Technical scheme of the present invention is to realize by following step: slaine and carbon source are reacted in solvent, obtain described metal-carbon nanometer composite material presoma, obtain metal-carbon nanometer composite material through charing under inert atmosphere conditions.
The step of concrete reaction is: single slaine or bimetal salt are joined in single solvent or the mixed solvent, treat that slaine dissolves fully after, add carbon source again, 150 ℃ of-220 ℃ of reactions, obtain described metal-carbon nanometer composite material presoma then.The presoma of preparation gained is placed carbide furnace in the presence of inert nitrogen gas, helium or argon gas charing 2-5 hour, obtain metal-carbon nanometer composite material.Wherein carbon source is the furfural or derivatives thereof.The volume ratio of mixed solvent is 0-100%; The concentration of described metal ion solution is 0.01-0.5mol/L, and the mol ratio of described furfural or derivatives thereof and metal ion is 1-100: 1.
Metal ion is platinum, ruthenium, palladium, gold, silver, copper, cobalt or nickel ion etc., can be its soluble-salt, and waiting as nitrate, sulfate, acetate or hydrochloride provides; Solvent is a single solvent water, ethanol, ethylene glycol, propane diols, glycerine or water and ethylene glycol, water and propane diols, the mixed solvent of water and glycerine etc.; Described furfural derivatives is to be selected from hydroxymethylfurfural, methyl furfural, sulfidomethyl furfural, amino furfural or the phenyl furfural that substituted radical is arranged on the furan nucleus.
The present invention is with single solvent water or alcohol or water and pure mixed solvent system, with soluble metallic salt, hydro-thermal carbon source is raw material, prepare metal-carbon nanometer composite material, by regulating solvent composition, the carbonization temperature of presoma waits physical propertys such as the specific area of the content of controlling metal in the composite and composite and pore-size distribution.
The present invention is used for nitrobenzene compounds, unsaturated aldehyde ketonic compound, benzene, toluene, alkene or alkynes catalytic hydrogenation reaction method to cobalt-charcoal, the nickel-Pd/carbon catalyst for preparing: in the catalytic reduction reaction process, reducing agent is H
2, the reaction temperature of catalytic reaction is 60-150 ℃, and reaction pressure is 0.2-4.0MPa, and the reaction time is 0.5-20h; The weight of catalyst is the 1%-40% of substrate weight, and reducing agent is H
2, the reaction temperature of catalytic reaction is 60-150 ℃, and reaction pressure is 0.2-4.0MPa, and the reaction time is 0.5-20h; Nitrobenzene compounds can be a nitrobenzene, contains substituting group in the nitrobenzene: the Cl in the halogen, Br, I, in the alkyl-CH
3,-CH
2CH
3, or amino-NH
2The unsaturated aldehyde ketonic compound can be cinnamic acid, crotonaldehyde, citral or acetophenone.
The inventive method is easy, safety, carbon source are inexpensive, is easy to get; Production cost is low, manufacturing cycle is short, the gained material compatibility is wide.The metal-carbon nanometer composite material that is obtained can be used as the presoma of high activated catalyst, adsorbent, special oil ink material, super capacitor material, lithium battery material, hard material and metal carbides etc.
Description of drawings
Fig. 1 is the cobalt-carbon precursor stereoscan photograph of embodiment 1 gained.
Fig. 2 is the cobalt-charcoal compound stereoscan photograph of embodiment 1 gained.
Fig. 3 is the XRD spectra of the cobalt-charcoal compound of embodiment 1 gained, and abscissa is 2 θ, and ordinate is an intensity, and unit is an arbitrary unit, shows that cobalt is a metallic cobalt in cobalt-charcoal compound of implementing 1 gained.
Fig. 4 is the cobalt-charcoal compound transmission electron microscope photo of embodiment 1 gained.
Fig. 5 is the stereoscan photograph of the nickel-charcoal compound of embodiment 6 gained.
Fig. 6 is the XRD spectra of the nickel-charcoal compound of embodiment 6 gained, and abscissa is 2 θ, and ordinate is an intensity, and unit is an arbitrary unit, shows that the nickel in nickel-charcoal compound of implementing 6 gained is metallic nickel.
The specific embodiment
Embodiment 1
Take by weighing 0.3g Co (AC)
2Join in the 30mL deionized water, stirring and dissolving pipettes 0.5mL furfural solution again and adds, and stirs, and places the withstand voltage reactor of stainless steel of 40mL, and behind 180 ℃ of reaction 15h, the gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.With scanning electron microscopic observation gained sample micron ball, micron ball size is at the 2-5 micron.The gained powder is placed tubular heater, and the heating rate with 2 ℃/min under the high pure nitrogen atmosphere is heated to 700 ℃, keeps 3 hours, obtains cobalt-carbon nanometer composite material, is accredited as metallic cobalt through x-ray powder.This sample specific area is 339m
2/ g.ICP result shows that the quality percentage composition of metallic cobalt is 6.1%.
Embodiment 2
Take by weighing 0.3g Co (AC)
2Join in 15mL deionized water and the 15mL ethylene glycol mixed solution, stirring and dissolving pipettes 0.5mL furfural solution again and adds, stir, place the withstand voltage reactor of stainless steel of 40mL, behind 180 ℃ of reaction 15h, gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.With scanning electron microscopic observation gained sample is the micron ball that sheet is formed about 50nm, and micron ball size is at the 3-7 micron, and specific area is 26m
2/ g.The gained powder is placed tubular heater, heating rate with 2 ℃/min under the high pure nitrogen atmosphere is heated to 700 ℃, kept 3 hours, obtain cobalt-carbon nanometer composite material, be accredited as metallic cobalt through x-ray powder, the pattern of presoma, just size decreases have been kept by ESEM and transmission electron microscope observing to its pattern.The size of metallic cobalt particle is about 3.5nm, and metallic cobalt is evenly distributed on charcoal.This sample specific area is 385m
2/ g, pore-size distribution are 3.8nm.ICP result shows that the quality percentage composition of metallic cobalt is 9.2%.
Embodiment 3
Take by weighing 0.3g Co (AC)
2Join in the 30mL ethylene glycol mixed solution, stirring and dissolving pipettes 0.5mL furfural solution again and adds, and stirs, and places the withstand voltage reactor of stainless steel of 40mL, and behind 180 ℃ of reaction 15h, the gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.With scanning electron microscopic observation gained sample is bead about 500nm, and the dispersiveness of bead is not fine.The gained powder is placed tubular heater, and the heating rate with 2 ℃/min under the high pure nitrogen atmosphere is heated to 700 ℃, keeps 3 hours, obtains cobalt-carbon nanometer composite material, is accredited as the mixture of metallic cobalt and cobalt oxide through x-ray powder, is mainly metallic cobalt.This sample specific area is 309m
2/ g, pore-size distribution are 0.5nm.ICP result shows that the quality percentage composition of metallic cobalt is 11.74%.
Embodiment 4
Take by weighing 0.3g Ni (AC)
2Join in the 30mL deionized water, stirring and dissolving pipettes 0.5mL furfural solution again and adds, and stirs, and places the withstand voltage reactor of stainless steel of 40mL, and behind 180 ℃ of reaction 15h, the gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.For to be made up of the blocky-shaped particle that develops into the micron order ball, granular size and contains some flaky substances in the sample about 2 microns, increased its specific area with scanning electron microscopic observation gained sample.The gained powder is placed tubular heater, and the heating rate with 2 ℃/min under the high pure nitrogen atmosphere is heated to 700 ℃, keeps 3 hours, obtains nickel-carbon nanometer composite material, is accredited as metallic nickel through x-ray powder.This sample specific area is 365m
2/ g, pore-size distribution are 3.7nm.ICP result shows that the quality percentage composition of metallic nickel is 29.7%.
Embodiment 5
Take by weighing 0.3g Ni (AC)
2Join in 20mL deionized water and the 10mL ethylene glycol mixed solution, stirring and dissolving pipettes 0.5mL furfural solution again and adds, stir, place the withstand voltage reactor of stainless steel of 40mL, behind 180 ℃ of reaction 15h, gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.With scanning electron microscopic observation gained sample is that thickness is that 50nm left and right sides diameter is the sheet composition about 2 microns, and small quantities of particles is arranged.The gained powder is placed tubular heater, and the heating rate with 2 ℃/min under the high pure nitrogen atmosphere is heated to 700 ℃, keeps 3 hours, obtains nickel-carbon nanometer composite material, is accredited as metallic nickel through x-ray powder.This product specific area is 404m
2/ g, pore-size distribution are 3.7nm.ICP result shows that the quality percentage composition of metallic nickel is 17.8%.
Embodiment 6
Take by weighing 0.3gNi (AC)
2Join in 15mL deionized water and the 15mL ethylene glycol mixed solution, stirring and dissolving pipettes 0.5mL furfural solution again and adds, stir, place the withstand voltage reactor of stainless steel of 40mL, behind 180 ℃ of reaction 15h, gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.With scanning electron microscopic observation gained sample be thickness about 50nm, the sheet of size about 4 microns, these sheets have the trend of column sphere, specific area is 67m
2/ g.The gained powder is placed tubular heater, heating rate with 2 ℃/min under the high pure nitrogen atmosphere is heated to 700 ℃, kept 3 hours, obtain nickel-carbon nanometer composite material, be accredited as metallic nickel through x-ray powder, to its morphology analysis, observe the pattern that its pattern has kept presoma with ESEM and transmission electron microscope, just size decreases.The size of metallic nickel particle is about 20nm, and metallic nickel and carbon are evenly distributed.This product specific area is 566m
2/ g, pore-size distribution are 3.88nm.ICP result shows that the quality percentage composition of metallic nickel is 13.3%.
Embodiment 7
Take by weighing 0.3gNi (AC)
2Join in 10mL deionized water and the 20mL ethylene glycol mixed solution, stirring and dissolving pipettes 0.5mL furfural solution again and adds, stir, place the withstand voltage reactor of stainless steel of 40mL, behind 180 ℃ of reaction 15h, gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.With scanning electron microscopic observation gained sample by 50nm about sheet colored shape micron ball and the blocky-shaped particle formed form.The gained powder is placed tubular heater, and the heating rate with 2 ℃/min under the high pure nitrogen atmosphere is heated to 700 ℃, keeps 3 hours, obtains nickel-carbon nanometer composite material, is accredited as metallic nickel through x-ray powder.This product specific area is 429m
2/ g, pore-size distribution are 3.7nm.ICP result shows that the quality percentage composition of metallic nickel is 18.3%.
Embodiment 8
Take by weighing 0.3gNi (AC)
2Join in the 30mL ethylene glycol mixed solution, stirring and dissolving pipettes 0.5mL furfural solution again and adds, and stirs, and places the withstand voltage reactor of stainless steel of 40mL, and behind 180 ℃ of reaction 15h, the gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.With scanning electron microscopic observation gained sample is that dispersiveness is not that good bead is formed about 50nm.The gained powder is placed tubular heater, and the heating rate with 2 ℃/min under the high pure nitrogen atmosphere is heated to 700 ℃, keeps 3 hours, obtains nickel-carbon nanometer composite material, is accredited as metallic nickel through x-ray powder.This product specific area is 268m
2/ g, pore-size distribution are 3.7nm.ICP result shows that the quality percentage composition of metallic nickel is 38.9%.
Embodiment 9
Take by weighing 0.3g AgNO
3Join in 15mL deionized water and the 15mL ethylene glycol mixed solution, stirring and dissolving pipettes 0.5mL furfural solution again and adds, stir, place the withstand voltage reactor of stainless steel of 40mL, behind 180 ℃ of reaction 15h, gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.With scanning electron microscopic observation gained sample is the bead that 50nm forms.Transmission electron microscope results is shown as and contains carbon polymer and silver for core-shell structure.
Take by weighing 0.3g AgNO
3Join in the 30mL deionized water, stirring and dissolving pipettes 2mL furfural solution again and adds, and stirs, and places the withstand voltage reactor of stainless steel of 40mL, and behind 180 ℃ of reaction 24h, the gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.With scanning electron microscopic observation gained sample is fiber about 2 microns.The transmission electron microscope results display fibers is to be filled by argent.
Embodiment 11
Take by weighing 0.3g AgNO
3Join in the mixed solution of 15mL deionized water and 15mL ethylene glycol, stirring and dissolving pipettes 2mL furfural solution again and adds, stir, place the withstand voltage reactor of stainless steel of 40mL, behind 180 ℃ of reaction 24h, gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.With transmission electron microscope observing gained sample for containing carbon polymer contracted payment ball shaped nano particle.
Embodiment 12
Take by weighing 0.1g PdCl
2Join in the 30mL deionized water, stirring and dissolving pipettes 2mL furfural solution again and adds, and stirs, and places the withstand voltage reactor of stainless steel of 40mL, and behind 180 ℃ of reaction 24h, the gained precipitation after filtration, after the washing, drying, obtain brown ceramic powder.Be dispersed in the carbon containing polymer nanocomposite ball with Metal Palladium in the transmission electron microscope observing gained sample.
Embodiment 13
3.2mmol o-chloronitrobenzene and 50mL ethanol are added in the autoclave of 100mL, add cobalt-carbon nanometer composite material that 0.1g embodiment 2 prepares, charge into the hydrogen of 3MPa, 140 ℃ of reaction 3h, the conversion ratio of o-chloronitrobenzene is 99%, and the selectivity of product o-chloraniline is 98%.
The reaction result of the different chloronitrobenzenes of cobalt-carbon nanometer composite material catalytic reduction is listed table 1 in.
Embodiment 14
1mL cinnamic acid and 50mL ethanol are added in the autoclave of 100mL, add the cobalt-carbon nanometer composite material of 0.1g embodiment 2 preparations, charge into the hydrogen of 2MPa, 120 ℃ of reaction 1h, the conversion ratio of cinnamic acid is 27%, the selectivity of product cinnamyl alcohol is 30%.
Embodiment 15
2mL furfural and 50mL ethanol are added in the autoclave of 100mL, add the cobalt-carbon nanometer composite material of 0.1g embodiment 2 preparations, charge into the hydrogen of 2MPa, 110 ℃ of reaction 1h, the conversion ratio of furfural is 15%, the selectivity of product furfuryl alcohol is 100%.
Embodiment 16
5mmol o-chloronitrobenzene and 50mL ethanol are added in the autoclave of 100mL, add nickel-carbon nanometer composite material that 0.1g embodiment 6 prepares, charge into the hydrogen of 2MPa, 140 ℃ of reaction 1.5h, the conversion ratio of o-chloronitrobenzene is 100%, and the selectivity of product o-chloraniline is 99%.
The reaction result of nickel-carbon nanometer composite material catalytic reduction distinct fragrance nitro compound is listed in table 2 (0.1g nickel-carbon nanometer composite material, 5mmol substrate).
Table one embodiment 2 preparation gained cobalt-carbon nanometer composite material catalytic hydrogenation chloronitrobenzene reaction results
Table two embodiment 6 preparation gained nickel-carbon nanometer composite material catalytic hydrogenation nitrobenzene compounds reaction results
Claims (6)
1, a kind of preparation method of metal-carbon nanometer composite material, it is characterized in that this method be earlier be added to single or bimetal salt single or mixed solvent in, the volume ratio of mixed solvent is 0-100%, after treating that slaine dissolves fully, the concentration of metal ion solution is 0.01-0.5mol/L, add carbon source again and be furfural or it contains the derivative of aldehyde radical, make furfural or its contain the derivative of aldehyde radical and the mol ratio of metal ion is 1-100: 1,150 ℃-220 ℃ reactions 10-48 hour, obtain the presoma of metal-carbon nanometer composite material; Then, presoma is placed retort, inert gas as: in the presence of nitrogen, helium or the argon gas charing 2-5 hour, obtain metal-carbon nanometer composite material.
2,, it is characterized in that the slaine described in this method is to be selected from nitrate, sulfate, acetate or the hydrochloride etc. that metal ion is platinum, ruthenium, palladium, gold, silver, copper, cobalt or nickel according to the preparation method of the described metal-carbon nanometer composite material of claim 1.
3,, it is characterized in that the single solvent described in this method is selected from water, ethanol, ethylene glycol, propane diols or glycerine according to the preparation method of the described metal-carbon nanometer composite material of claim 1; Mixed solvent is selected from water and ethylene glycol, water and propane diols or water and glycerine.
4,, it is characterized in that furfural derivatives described in this method is to be selected from hydroxymethylfurfural, methyl furfural, sulfidomethyl furfural, amino furfural or the phenyl furfural that substituted radical is arranged on the furan nucleus according to the preparation method of the described metal-carbon nanometer composite material of claim 1.
5, a kind of purposes of the metal-carbon nanometer composite material that makes according to claim 1 is characterized in that being used for nitrobenzene compounds, unsaturated aldehyde ketonic compound, benzene, toluene, alkene or alkynes catalytic hydrogenation reaction, and reducing agent is H
2, the reaction temperature of catalytic reaction is 60-150 ℃, and reaction pressure is 0.2-4.0MPa, and the reaction time is 0.5-20h; The weight of catalyst is the 1%-40% of substrate weight.
6, nitrobenzene compounds according to claim 5 can be a nitrobenzene, contains substituting group in the nitrobenzene: the Cl in the halogen, Br, I, in the alkyl-CH
3,-CH
2CH
3, or amino-NH
2The unsaturated aldehyde ketonic compound can be cinnamic acid, crotonaldehyde, citral or acetophenone etc.
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