CN1386722A - Process for preparing nano metal particles/carbon composite material - Google Patents
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Abstract
本发明一种纳米金属粒子/炭复合材料的制备方法涉及用烃类化合物与过渡金属化合物经过炭化反应制备纳米金属粒子/炭复合材料的新方法。将烃类化合物与过渡金属化合物按重量比1∶1－1∶0.01混合在惰性气氛中、自升压下、400－550℃温度范围内进行炭化反应6小时得到热解产物,经热溶抽提后得到纳米金属粒子/炭复合材料。所用烃类化合物为链烷烃、烯烃、炔烃或芳烃;过渡金属化合物为茂基过渡有机金属化合物、羰基过渡有机金属化合物、乙酰丙酮基过渡有机金属化合物、过渡金属乙酸盐或过渡金属硝酸盐。该方法能使纳米级金属粒子均匀地分散在炭基体中,具有工艺简单、纯度高、金属类型可选择范围广等特点,易实现大规模制备。The invention relates to a method for preparing a nanometer metal particle/carbon composite material, which relates to a new method for preparing a nanometer metal particle/carbon composite material through a carbonization reaction of a hydrocarbon compound and a transition metal compound. Mix hydrocarbon compounds and transition metal compounds in a weight ratio of 1:1-1:0.01 in an inert atmosphere, under self-increasing pressure, and carry out carbonization reaction within the temperature range of 400-550°C for 6 hours to obtain pyrolysis products, which are then heated and extracted. After extraction, the nano metal particle/carbon composite material is obtained. The hydrocarbon compound used is alkane, alkene, alkyne or aromatic hydrocarbon; the transition metal compound is a cyanoyl transition organometallic compound, a carbonyl transition organometallic compound, an acetylacetonyl transition organometallic compound, a transition metal acetate or a transition metal nitrate. The method can uniformly disperse nanoscale metal particles in the carbon matrix, and has the characteristics of simple process, high purity, wide range of metal types, etc., and is easy to realize large-scale preparation.
Description
Technical field
The present invention relates to a kind of novel method for preparing nano metal particles/carbon composite, is to prepare through carbonization reaction with hydrocarbon compound and transistion metal compound.
Technical background
Nano metal particles/raw material of wood-charcoal material is a kind of novel nano level functional composite material, wherein the metallics size below 100nm, particle diameter fitly is dispersed in the carbon matrix, can be steady in a long-term in air, good heat resistance has solved the difficult problem that nano metal particles can not stable existence in air.This type material is considered to a kind of novel exotic materials of extensive application prospect once the very big interest that chemical boundary, material educational circles and business circles occur promptly causing.Different according to metallics type and carbon matrix, this material is expected as electrotechnical, electronic material (transmitter, conductive resin, electrode, electromagnetic sealing, lithium ion battery negative material etc.), magneticsubstance (magnetic, electric wave shielding material, magnetic recording material etc.), redox catalyst (hydrogenating reduction etc.), fine ceramics material and anti-biotic material etc.If this material activation also can be made the sp act raw material of wood-charcoal material with flourishing central hole structure, as chemical substance sorbent material (discoloring agent, reodorant etc.), artificial organs manufacturing and blood filtration etc., Application Areas is very wide.
Traditional nano metal particles/charcoal preparation methods is arc discharge method and chemical Vapor deposition process (CVD), arc discharge method comprises direct current arc discharge and plasma discharge etc., experimental implementation temperature higher (〉=2000 ℃), product purity is relatively poor (when nanoparticle forms, also follow the generation of soccerballene and carbon nanotube), output is also very low.Chemical Vapor deposition process is the gas phase carbon source method of (about 1000 ℃) and metal catalyst prepared in reaction nano metal/raw material of wood-charcoal material at high temperature, the control reaction conditions is except that mainly obtaining charcoal clad nano metallic particles, also often be mixed with vapor-grown carbon fibers or/and carbon nanotube, the product component complexity, be difficult to separate, and be difficult to realize scale operation.
At " the superfine metal particle for preparing stable existence in the air that is dispersed in the charcoal by the polymer composite body pyrolysis " (S.Miyanaga et al, J.Macromol.Sci.-Chem., 1990, A27 (9-11), 1347) reported the method for preparing nano metal particles/raw material of wood-charcoal material by the charing under certain pressure and temperature of pure organometallic compound, organometallic polymer complex compound and organometallic polymer polymkeric substance in the paper.The raw material that uses is mainly: the interpolymer of vinyl cyanide (AN), vinylbenzene (St), methyl methacrylate (MMA), 4-ethylpyridine monomers such as (VP) and transistion metal compound such as iron, cobalt, nickel, copper, titanium, silver, gold, osmium, Liao, Palladium etc., and at rare gas element (N
2Or Ar) protection down with heat-up rate very slowly (0.3 ℃/min.) charing stopped 1-2 days to 650-1400 ℃.Yogo is at " synthetic nickel/carbon composite of nickelocene under the pressure-Vinylstyrene pyrolysis and character thereof " (J.Mater.Sci., 1986,21,941) and " from synthetic α iron particle/carbon composite of Vinylstyrene-vinyl ferrocene and character thereof " (J.Mater.Sci., 1989,24,2071) introduced in the paper from nickelocene (or the method for ferrocene) synthesis nano nickel (or iron)/carbon composite: at first vinyl nickelocene (or ferrocene) is dissolved in the Vinylstyrene, copolymerization is 2 hours under 300 ℃-100MPa, obtain the polystyrene copolymer of nickel metal (metallic iron), then under 125Mpa in 700-850 ℃ of pyrolysis 2 hours, promptly obtain the purpose product.Obviously this method exists complex process (needs synthetic metal multipolymer, and through dissolving, evaporation, slow processes such as charing), carbonization yield is lower (in the polymkeric substance outside de-carbon, hydrogen and the metallic element, the heteroatomss such as O, N, S that also contain some amount), metal content is difficult to control in charing pressure height (reaching 100MPa), the material, material cost is high, is difficult to defectives such as mass preparation.
Summary of the invention
The purpose of this invention is to provide a kind of nano metal particles and be dispersed in the new preparation method who forms metal/carbon composite in the carbon matrix, its preparation method only need pass through mixing, charing, extraction process just can obtain nano metal particles/carbon composite, have characteristics such as technology is simple, the material preparation cost is low, purity is high, the metal types selectable range is wide, easily realize mass preparation.
The preparation method of a kind of nano metal particles/carbon composite of the present invention, with hydrocarbon compound and transistion metal compound uniform mixing, in inert atmosphere, boost down certainly, carry out carbonization reaction in the 400-550 ℃ temperature range and obtained pyrolysis product in 6 hours, after pyrolysis product carried out the thermosol extracting, the solid product that obtains is nano metal particles/carbon composite, and the weight ratio of raw materials used middle hydrocarbon compound and transistion metal compound is 1: 1-1: 0.01.Hydrocarbon compound is: paraffinic hydrocarbons, alkene, alkynes or aromatic hydrocarbons; Transistion metal compound is: cyclopentadienyl transition organometallic compound, carbonyl transition organometallic compound, acetylacetone based transition organometallic compound, transition metal acetate or transition metal nitrate.
Paraffinic hydrocarbons is: carbonatoms is at the alkane more than 6 or 6.
Alkene is: cyclopentenes, cyclopentadiene, tetrahydrobenzene, cyclohexadiene, hexadiene, divinyl or vinylbenzene.
Alkynes is: 2-butyne, divinylacetylene, 1,4-hexadiyne, 1,5--hexadiyne or 2,4--hexadiyne.
Aromatic hydrocarbons is: coal tar, petroleum residual oil, pitch, methylbenzene, naphthalene, anthracene or phenanthrene.
The cyclopentadienyl transistion metal compound is: ferrocene, dicyclopentadienylcobalt or nickelocene.
The carbonyl transistion metal compound is: iron carbonyl, cobalt-carbonyl or nickle carbonoxide.
Acetylacetone based transistion metal compound is: chromium acetylacetonate, methyl ethyl diketone platinum or palladium acetylacetonate.
The transition metal acetate is: venus crystals, cobaltous acetate, nickelous acetate or ironic acetate.
Transition metal nitrate is: iron nitrate, Xiao Suangu or nickelous nitrate.
The raw material that the present invention uses is reactive stronger under middle temperature (400-550 ℃) condition, and the cheap hydro carbons organic compound that obtains easily, paraffinic hydrocarbons is typically arranged as pentane, hexane, heptane, homologues such as paraffin, alkene is as cyclopentenes, cyclopentadiene, tetrahydrobenzene, cyclohexadiene, hexadiene, homologue such as divinyl or vinylbenzene, alkynes is as 2-butyne, divinylacetylene, 1, the 4-hexadiyne, 1,5--hexadiyne or 2, homologues such as 4--hexadiyne, aromatic hydrocarbons is as coal tar, petroleum residual oil, pitch, the model aromatic hydroxy compound is as alkylbenzene, naphthalene, anthracene, homologues such as phenanthrene, they are sources of charcoal in the matrix material.The selection principle of transition metal in raw material series compound is a little less than the effect between metal and ligand, and synthetic easily obtaining, and its typical transistion metal compound has: ferrocene, dicyclopentadienylcobalt, nickelocene and homologue thereof; Iron carbonyl, cobalt-carbonyl, nickle carbonoxide and homologue thereof; Chromium acetylacetonate, methyl ethyl diketone platinum, palladium acetylacetonate, ferric acetyl acetonade, acetylacetone cobalt, acetylacetonate nickel and homologue thereof; Nitrate, acetate etc. are as iron nitrate, Xiao Suangu, nickelous nitrate and homologue thereof; Venus crystals, cobaltous acetate, nickelous acetate, ironic acetate and homologue thereof.They are sources of metal in the matrix material.
The preparation of nano metal particles/carbon composite provided by the invention be according to metal at high temperature to the katalysis of organic hydrocarbon materials carbonization reaction and charcoal reductive action principle to metal, metallic compound and charcoal source are chosen and the principle of mating is that the two mutual solubility is better.At first with the transistion metal compound of above-mentioned carbon raw material hydrocarbon compounds and source metal uniform mixing by a certain percentage, then in autoclave, air several rear enclosed kettle in the inert gas replacement still, be warming up to preset temperature from boosting, stop certain hour then, the cooling release, residue is through acetone, the extraction of pyridine equal solvent in the still, remove unreacted reactant and light constituent, dried solvent insolubles is target product---nano metal particles/carbon composite.The ratio of carbon source and source metal is decided according to need, is generally 1: 1-1: 0.01, and ratio is too low, and the content of metal is low excessively in the matrix material of preparation, and metal will not have the effect of functionalization; Ratio is too high, and charcoal and metal can not be fine compound, and the metallic particles of formation is bigger.Temperature of reaction generally is controlled between 400-550 ℃, and temperature is low excessively, and the thermolysis of carbon raw material not exclusively or is not decomposed, and end product will contain the gas composition of more amount; Temperature is too high, and reaction is violent, and the pressure height is difficult to control, also can be too high to the requirement of pressure exerting device, and cause manufacturing cost high.Reaction times generally was controlled at about 6 hours, and the time is too short, and the pyrolysis of carbon raw material is incomplete; Overlong time, consuming time, improved preparation cost.Method provided by the invention only need be passed through mixing, charing, extraction process just can obtain nano metal particles/carbon composite, and system generally is lower than 10.0Mpa from rising final pressure under mesophilic condition, has advantages such as technology is simple, the metal types selectable range is wide.Nano metal particles/carbon composite nano-sized metal particles can be evenly dispersed in the carbon matrix, and is closely coated by the charcoal layer, and the content sum of nano-sized metal particles and charcoal can reach more than 99%, the purity height.
Embodiment
Embodiment 1
With catalytic cracking turpentole residual oil (constituent content is wt%:C 88.86, and H 9.42, and C/H 0.97, N≤0.3, O 0.42, S 0.82) and analytical pure ferrocene ratio uniform mixing, place autoclave by weight 1: 0.2.Reacting by heating under continuous mechanical stirring and nitrogen protection, temperature rise rate is kept 3 ℃/min, stops 6 hours down at 420 ℃, obtains pyrolysis product, and yield is 56wt%, and system only reaches 5.0Mpa from the power of boosting.With the pyridine is that solvent carries out thermosol extracting repeatedly (80 ℃ of temperature) to reaction product, fades to achromaticity and clarification until filtrate.Filter residue after the oven dry is granulated metal/raw material of wood-charcoal material, and results of elemental analyses shows that the weight percentage of metallic iron is about 9.3%, and the content of carbon is 90.0%.This product is carried out the analysis of X-ray diffraction (XRD) and transmission electron microscope (TEM), and the result shows and is mainly iron simple substance by the metallics that obtains (α-Fe), particle diameter is dispersed in the carbon matrix between 30-80nm, and is closely coated by the charcoal layer.
Embodiment 2
Working method is with embodiment 1, and the weight ratio of petroleum residual oil and ferrocene is 1: 0.01, and all the other conditions are constant, through charing and solvent extraction obtain mainly by α-Fe constitute, size distribution is at nano-iron particle/carbon composite of 10-50nm.
Embodiment 3
Working method is with embodiment 1, and the weight ratio of petroleum residual oil and ferrocene is 1: 1, and all the other conditions are constant, through charing and solvent extraction obtain mainly by α-Fe constitute, size distribution is at nano-iron particle/carbon composite of 20-100nm.Embodiment 4
With analytical pure durol and ferrocene ratio uniform mixing by weight 1: 0.30, put into the autoclave temperature reaction, after stopping 6 hours, 540 ℃ of temperature eventually obtain black powder, again after acetone normal temperature dissolves and washes away, obtain the purpose material, its yield is about 20%, the final pressure 7.0Mpa of system.XRD and tem analysis show that product is that it is dispersed in the charcoal that is undefined structure about α-Fe, particle diameter 5nm.With this material is that catalyzer carries out CO+H
2The reaction of synthesizing ethylene, the result shows that the average conversion of CO can reach 45.7%, the synthesis yield of ethene is 52.4%, illustrates that this material is a kind of redox catalyst preferably.
Embodiment 5
Working method is with embodiment 4, and metallic compound changes iron tetracarbonyl into, and it is constant to keep other condition, obtains nanometer iron/carbon composite.
Embodiment 6
Working method is with embodiment 4, and metallic compound changes chromium acetylacetonate into, and it is constant to keep other condition, obtains nanometer chromium/carbon composite.
Embodiment 7
Working method is with embodiment 4, and it is constant to keep other condition, and metallic compound uses iron nitrate, and the result finally obtains the Fe/C matrix material based on ferric oxide.
Embodiment 8
With analytical pure naphthalene and cobaltous acetate by weight 1: 0.30 uniform mixing, put into the autoclave temperature reaction, after stopping 6 hours, 540 ℃ of whole temperature obtain black powder, again after acetone normal temperature dissolves and washes away, obtain the purpose material, its yield is about 25%, and XRD and tem analysis show that product is mainly Co and CoO, median size about 50nm, is dispersed in the charcoal that is undefined structure.
Embodiment 9
Working method is with embodiment 8, and carbon source changes normal hexane into, and all the other conditions are constant, the result obtains black powder, yield is 23%, and XRD and tem analysis show that the product metal is mainly Co and CoO, particle diameter about 10-50nm, and the charcoal form is mainly particulate state and nanotube-shaped.
Embodiment 10
Working method is with embodiment 8, and it is constant to keep other condition, changes carbon source into paraffin, also obtains nanometer cobalt particle/carbonarius powder by reaction.
Embodiment 11
Working method is with embodiment 8, and it is constant to keep other condition, changes carbon source into 2, and the 4-hexadiene also obtains nanometer cobalt particle/carbonarius powder after the reaction.
Embodiment 12
Working method is with embodiment 8, and it is constant to keep other condition, changes carbon source into 2, and the 4-hexadiyne also obtains nanometer cobalt particle/carbonarius powder by reaction.
Claims (10)
1, a kind of preparation method of nano metal particles/carbon composite, with hydrocarbon compound and transistion metal compound uniform mixing, in inert atmosphere, boost down certainly, carry out carbonization reaction in the 400-550 ℃ temperature range and obtained pyrolysis product in 6 hours, after pyrolysis product carried out the thermosol extracting, the solid product that obtains is nano metal particles/carbon composite, and the weight ratio of raw materials used middle hydrocarbon compound and transistion metal compound is 1: 1-1: 0.01;
(1) hydrocarbon compound is: paraffinic hydrocarbons, alkene, alkynes or aromatic hydrocarbons;
(2) transistion metal compound is: cyclopentadienyl transition organometallic compound, carbonyl transition organo-metallic
Compound, acetylacetone based transition organometallic compound, transition metal acetate or transition
Metal nitrate.
2, method according to claim 1 is characterized in that: paraffinic hydrocarbons is that carbonatoms is at the alkane more than 6 or 6.
3, method according to claim 1 is characterized in that: alkene is cyclopentenes, cyclopentadiene, tetrahydrobenzene, cyclohexadiene, hexadiene, divinyl or vinylbenzene.
4, method according to claim 1 is characterized in that: alkynes is 2-butyne, divinylacetylene, 1,4-hexadiyne, 1,5--hexadiyne or 2,4--hexadiyne.
5, method according to claim 1 is characterized in that: aromatic hydrocarbons is: coal tar, petroleum residual oil, pitch, methylbenzene, naphthalene, anthracene or phenanthrene.
6, method according to claim 1 is characterized in that: the cyclopentadienyl transistion metal compound is ferrocene, dicyclopentadienylcobalt or nickelocene.
7, method according to claim 1 is characterized in that: the carbonyl transistion metal compound is iron carbonyl, cobalt-carbonyl or nickle carbonoxide.
8, method according to claim 1 is characterized in that: acetylacetone based transistion metal compound is chromium acetylacetonate, methyl ethyl diketone platinum or palladium acetylacetonate.
9, method according to claim 1 is characterized in that: the transition metal acetate is venus crystals, cobaltous acetate, nickelous acetate or ironic acetate.
10, method according to claim 1 is characterized in that: transition metal nitrate is iron nitrate, Xiao Suangu or nickelous nitrate.
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| CN101099932B (en) * | 2007-05-23 | 2010-04-21 | 江苏天一超细金属粉末有限公司 | High-efficient iron-series catalyst and its preparation method |
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| CN102110508B (en) * | 2010-12-31 | 2012-08-15 | 深圳大学 | Preparation method of iron-based magnetic material/carbon composite powder |
| WO2013000160A1 (en) * | 2011-06-30 | 2013-01-03 | 北京化工大学 | Tricobalt tetroxide-carbon composite material, preparation method thereof, lithium ion battery and cathode thereof |
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