CN101249958B - Method for the continuous synthesis of a large number of high specific surface area and high graphitized carbon nanocages by bubbling method - Google Patents
Method for the continuous synthesis of a large number of high specific surface area and high graphitized carbon nanocages by bubbling method Download PDFInfo
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Abstract
一种利用鼓泡法连续合成大量高比表面积高石墨化碳纳米笼的方法，属于纳米材料技术领域。本发明采用乙醇作为碳源，以液态羰基铁分解出的铁为催化剂，以惰性气体氮气为载气和保护气体，使氮气将混合液体鼓泡产生的水汽连续带入反应炉中进行反应，生成大量碳包铁的碳纳米笼结构。同时会被氮气不断带出反应区，在石英管式炉另一端可以连续收集到大量反应吹出的产物。本发明工艺简单易行，产品产量高，合成出的样品质量高，而且成本低廉，对环境无污染，无明显易燃危险原料，气体价格低廉。
The invention discloses a method for continuously synthesizing a large number of high specific surface area and high graphitized carbon nanocages by using a bubbling method, which belongs to the technical field of nanomaterials. The present invention uses ethanol as the carbon source, iron decomposed from liquid carbonyl iron as the catalyst, and inert gas nitrogen as the carrier gas and protective gas, so that the nitrogen gas can continuously bring the water vapor generated by the bubbling of the mixed liquid into the reaction furnace for reaction, forming A carbon nanocage structure with a large number of carbon-coated iron. At the same time, it will be continuously taken out of the reaction zone by nitrogen, and a large amount of reaction blown products can be continuously collected at the other end of the quartz tube furnace. The invention has the advantages of simple process, high product yield, high quality of synthesized samples, low cost, no pollution to the environment, no obvious flammable and dangerous raw materials, and low gas price.
Description
Technical field
The present invention relates to a kind of method of technical field of nano material, specifically is a kind of Bubbling method method of synthetic a great amount of high specific surface area highly-graphitized carbon nano-cage continuously.
Background technology
For Proton Exchange Membrane Fuel Cells, because the voltage efficiency of battery and the loss of battery output efficiency are bigger,, can reduce the polarization reaction activity if select suitable eelctro-catalyst for use, improve speed of response, improve the PEMFC effciency of energy transfer.Nano cages wall chamber is that multiple gases is adsorbed/perfect medium of desorption fast, is aided with the surface treatment of suitable introducing specific function group, can increase its application in selecting suction/desorption separation technology field greatly.Nano cages is of a size of nanometer scale, belong to zero dimension quantum material, its peculiar conductivity, high-specific surface area, can fill and adsorption particle, and under many complex conditions, have very high stability, make it aspect support of the catalyst, good application prospects be arranged.Pt is dispersed in the dispersity that has not only increased Pt on the nano cages carrier, makes preparation nanometer Pt crystal grain become possibility, and can reduce the carrying capacity of Pt.The interaction of Pt and carbon has simultaneously reduced the coalescent speed of Pt again.In fuel cell, the catalyzer of conventional P t/C structure is because a large amount of Pt particle is isolated in porous sooty micropore inside, away from the necessary proton of catalyst reaction, electronics, gas three-phase passage and inefficiency, its utilization ratio only is 10～20%, so just cause high Pt carrying capacity, cause preparation cost high.And in the eelctro-catalyst of Pt/CNCs structure, all Pt particles all expose in the CNCs outside, make the Pt particle fully contact with the three-phase passage of cell reaction and improve the utilization ratio of catalyzer greatly.Because the electrochemical reaction condition of catalyzer is very complicated, and CNCs makes that than carbon black stable performance Pt is difficult for being peeled off, thereby causes extensive concern.
Find seldom have the investigator to adopt simple method to synthesize a great amount of high specific surface area highly-graphitized carbon nano-cage continuously through literature search to prior art." Platinum supported onfunctionalized ordered mesoporous carbon as electrocatalyst for directmethanol fuel cells " (platinum is deposited on the direct methanol fuel cell eelctro-catalyst of functional ordered mesoporous carbon) that L.Calvillo etc. delivered on the phase 59-64 page or leaf at " Journal of Power Sources " (" power technology ") in 2007 the 169th, a kind of method of utilizing the silicon oxide template to come synthesizing ordered mesoporous carbon is proposed in this article, its deficiency is: the preparation procedure complexity, and can not synthesize a large amount of samples continuously.
Summary of the invention
The object of the invention is at the deficiencies in the prior art, the method of the synthetic continuously a great amount of high specific surface area highly-graphitized carbon nano-cage of a kind of Bubbling method is provided, makes synthesizing continuously that it can be simple quantity is big, high-specific surface area, high graphitization, low defective porous carbon nanocages.The porous carbon nanocages output that is generated can reach the per hour above order of magnitude of 5 grams, and specific surface area reaches 350m
2More than/the g.
The present invention is achieved by the following technical solutions; the present invention adopts ethanol as carbon source; the iron that decomposites with liquid iron carbonyl is catalyzer; with the inert nitrogen gas is carrier gas and shielding gas; the steam that the mixing liquid bubbling is produced by nitrogen is brought in the Reaktionsofen continuously and is reacted; generate the nano cages structure of a large amount of carbon iron clads, can constantly be taken out of reaction zone by nitrogen simultaneously, collect the product that big quantitative response blows out continuously at the quartz tube furnace the other end.
Below the present invention is further detailed, comprise the steps:
The first step, be 1 with liquid iron carbonyl and ethanol with volume ratio: 3-2: 1 mixes, in the container of packing into (as microscler glass test tube);
Second step, mixed glass test tube put into 0 ℃ frozen water mixing liquid, be connected to high quartz tube furnace one end with rubber hose, then the high quartz tube furnace is warmed up to 900 ℃-1100 ℃ of temperature of reaction, after homo(io)thermism, feed inert nitrogen gas, by nitrogen the steam of mixing liquid bubbling generation is brought in the Reaktionsofen continuously and reacted, collect product at the quartz tube furnace the other end simultaneously;
Described intensification, its temperature rise rate are 10 ℃/minute.
Described feeding inert nitrogen gas, gas flow are 50l/h-300l/h.
The 3rd step under temperature of reaction, kept tubular type furnace gas flow, and reaction continues to carry out.Collect the black carbon iron clad nano cages sample of average 5g/h after having reacted continuously.
Described reaction continues to carry out, and its time is 2-4 hour.
The invention solves present synthesizing porous nano cages technology more complicated, and major part can not synthesize the problem of a large amount of samples continuously, decompose the nano cages sample that ethanol produces the carbon iron clad by the continuous quick catalysis of iron.The utilization ratio height of reactant at first substantially can complete reaction, and can synthesize continuously, greatly reduces cost; Secondly the sample size size can be controlled by parameters such as adjustments of gas flow and temperature.The present invention is simple for process, and raw material adopts cheap and widely used ethanol, iron carbonyl and ordinary nitrogen, can be easily by the continuous a large amount of nano cages sample that synthesizes the high-specific surface area high graphitization of simple tubular type furnace apparatus.
The present invention adopts ethanol as carbon source, the iron that decomposites with liquid iron carbonyl is catalyzer, is carrier gas and shielding gas with the inert nitrogen gas, and raw material is simple and easy to, and is with low cost, environmentally safe; Adopt protection of inert gas, do not have obvious inflammable dangerous raw material, gas price is cheap; Apparatus and process is simple, the prepared nano cages sample specific surface area height that goes out, and crystalline quality is good, and impurity and defective are few.
Description of drawings
The high-resolution-ration transmission electric-lens photo of the high specific surface area highly-graphitized carbon nano-cage that Fig. 1 the present invention prepares.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Present embodiment adopts ethanol as carbon source; the iron that decomposites with liquid iron carbonyl is catalyzer; with the inert nitrogen gas is carrier gas and shielding gas, and the steam that nitrogen is produced the mixing liquid bubbling is brought in the Reaktionsofen continuously and reacted, and generates the nano cages structure of carbon iron clad.Can constantly be taken out of reaction zone by nitrogen simultaneously, can collect in a large number the (～5g/h) product that blows out of reaction at the quartz tube furnace the other end continuously.
Embodiment 1
Building-up process is that the high quartz tube furnace at both ends open carries out.With liquid iron carbonyl and ethanol with 1: 3 ratio (volume) mix, in the microscler glass test tube of packing into; Mixed glass test tube is put into 0 ℃ frozen water mixing liquid, be connected to high quartz tube furnace one end with rubber hose.With 10 ℃/minute of temperature rise rates the high quartz tube furnace is warmed up to 900 ℃ of temperature of reaction then, after homo(io)thermism, feed inert nitrogen gas, gas flow is 50l/h, the steam that nitrogen is produced the mixing liquid bubbling is brought in the Reaktionsofen continuously and is reacted, simultaneously receiving flask is housed, constantly collects the product that reaction blows out at the quartz tube furnace the other end; Under temperature of reaction, keep tubular type furnace gas flow, reaction continued to carry out 2 hours.React the back and in receiving flask, collected the nano cages sample of the black carbon iron clad of average 5g/h continuously.The porous carbon nanocages that is generated has carbonization structure preferably, and its specific surface area can reach 614m
2/ g.
Embodiment 2
Building-up process is that the high quartz tube furnace at both ends open carries out.With liquid iron carbonyl and ethanol with 1: 1 ratio (volume) mix, in the microscler glass test tube of packing into; Mixed glass test tube is put into 0 ℃ frozen water mixing liquid, be connected to high quartz tube furnace one end with rubber hose.With 10 ℃/minute of temperature rise rates the high quartz tube furnace is warmed up to 1000 ℃ of temperature of reaction then, after homo(io)thermism, feed inert nitrogen gas, gas flow is 200l/h, the steam that nitrogen is produced the mixing liquid bubbling is brought in the Reaktionsofen continuously and is reacted, simultaneously receiving flask is housed, constantly collects the product that reaction blows out at the quartz tube furnace the other end; Under temperature of reaction, keep tubular type furnace gas flow, reaction continued to carry out 3 hours.React the back and in receiving flask, collected the nano cages sample of the black carbon iron clad of average 5g/h continuously.As can be seen from Figure 1, the porous carbon nanocages that is generated has extraordinary carbonization structure, and its specific surface area can reach 500.9m
2/ g.
Embodiment 3
Building-up process is that the high quartz tube furnace at both ends open carries out.With liquid iron carbonyl and ethanol with 1: 2 ratio (volume) mix, in the microscler glass test tube of packing into; Mixed glass test tube is put into 0 ℃ frozen water mixing liquid, be connected to high quartz tube furnace one end with rubber hose.With 10 ℃/minute of temperature rise rates the high quartz tube furnace is warmed up to 1100 ℃ of temperature of reaction then, after homo(io)thermism, feed inert nitrogen gas, gas flow is 200l/h, the steam that nitrogen is produced the mixing liquid bubbling is brought in the Reaktionsofen continuously and is reacted, simultaneously receiving flask is housed, constantly collects the product that reaction blows out at the quartz tube furnace the other end; Under temperature of reaction, keep tubular type furnace gas flow, reaction continued to carry out 4 hours.React the back and in receiving flask, collected the nano cages sample of the black carbon iron clad of average 5g/h continuously.The porous carbon nanocages that is generated has carbonization structure preferably, and its specific surface area can reach 419.8m
2/ g.
Embodiment 4
Building-up process is that the high quartz tube furnace at both ends open carries out.With liquid iron carbonyl and ethanol with 2: 1 ratio (volume) mix, in the microscler glass test tube of packing into; Mixed glass test tube is put into 0 ℃ frozen water mixing liquid, be connected to high quartz tube furnace one end with rubber hose.With 10 ℃/minute of temperature rise rates the high quartz tube furnace is warmed up to 1000 ℃ of temperature of reaction then, after homo(io)thermism, feed inert nitrogen gas, gas flow is 120l/h, the steam that nitrogen is produced the mixing liquid bubbling is brought in the Reaktionsofen continuously and is reacted, simultaneously receiving flask is housed, constantly collects the product that reaction blows out at the quartz tube furnace the other end; Under temperature of reaction, keep tubular type furnace gas flow, reaction continued to carry out 2 hours.React the back and in receiving flask, collected the nano cages sample of the black carbon iron clad of average 5g/h continuously.The porous carbon nanocages that is generated has carbonization structure preferably, and its specific surface area can reach 350m
2More than/the g.
Claims (3)
1. the Bubbling method method of synthetic a great amount of high specific surface area highly-graphitized carbon nano-cage continuously; it is characterized in that; adopt ethanol as carbon source; the iron that decomposites with liquid iron carbonyl is catalyzer; with the inert nitrogen gas is carrier gas and shielding gas; the steam that the mixing liquid bubbling is produced by nitrogen is brought in the quartz tube furnace continuously and is reacted; generate the nano cages structure of a large amount of carbon iron clads; simultaneously constantly taken out of reaction zone by nitrogen; collect product continuously at the quartz tube furnace the other end, specifically comprise the steps:
The first step, with liquid iron carbonyl and ethanol with volume ratio 1: 3-2: 1 mixes, in the container of packing into;
Second step, said vesse put into 0 ℃ frozen water mixing liquid, be connected to quartz tube furnace one end with rubber hose, then quartz tube furnace is warmed up to 900 ℃-1100 ℃ of temperature of reaction, after homo(io)thermism, feed inert nitrogen gas, by nitrogen the steam of mixing liquid bubbling generation is brought in the quartz tube furnace continuously and reacted, collect product at the quartz tube furnace the other end simultaneously;
Described feeding inert nitrogen gas, gas flow are 50l/h-300l/h;
Described intensification, its temperature rise rate are 10 ℃/min;
The 3rd step under temperature of reaction, kept gas flow in the quartz tube furnace, and reaction continues to carry out, and collects the nano cages sample of the black carbon iron clad of average 5g/h after having reacted continuously;
Described reaction continues to carry out, and the time length is 2-4 hour.
2. Bubbling method according to claim 1 is the method for synthetic a great amount of high specific surface area highly-graphitized carbon nano-cage continuously, it is characterized in that in the first step, described container is microscler glass test tube.
3. Bubbling method according to claim 1 is the method for synthetic a great amount of high specific surface area highly-graphitized carbon nano-cage continuously, it is characterized in that, in second step, described collection product is at the quartz tube furnace the other end receiving flask to be housed, and constantly collects the product that reaction blows out.
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| CN106006617B (en) * | 2016-05-25 | 2018-04-13 | 广东石油化工学院 | A kind of preparation method and applications of graphene hollow nano cages |
| CN107159902A (en) * | 2017-06-27 | 2017-09-15 | 大连理工大学 | Iron pentacarbonyl is the method that source of iron Gaseous Detonation synthesizes Capability of Carbon-coated Iron Nano-particle |
| CN108745395A (en) * | 2018-04-16 | 2018-11-06 | 浙江农林大学暨阳学院 | A kind of preparation method and catalytic applications of nitrating nanometer carbon tube material |
| CN112661134B (en) * | 2020-12-31 | 2022-10-28 | 西北工业大学 | A kind of method for preparing pyrolysis carbon with acetaldehyde precursor |
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| CN1583552A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Method for mass preparing hollow nanometer carbon cages |
| CN1751989A (en) * | 2004-09-20 | 2006-03-29 | 三星Sdi株式会社 | Method for preparing carbon nanocages |
| CN1785801A (en) * | 2005-11-10 | 2006-06-14 | 上海交通大学 | Method of large quantity preparing hollow carbon nano-cage |
| EP1840082A1 (en) * | 2004-12-24 | 2007-10-03 | Japan Science and Technology Agency | Nanographite structure/metal nanoparticle composite |
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| CN1583552A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Method for mass preparing hollow nanometer carbon cages |
| CN1751989A (en) * | 2004-09-20 | 2006-03-29 | 三星Sdi株式会社 | Method for preparing carbon nanocages |
| EP1840082A1 (en) * | 2004-12-24 | 2007-10-03 | Japan Science and Technology Agency | Nanographite structure/metal nanoparticle composite |
| CN1785801A (en) * | 2005-11-10 | 2006-06-14 | 上海交通大学 | Method of large quantity preparing hollow carbon nano-cage |
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