CN102390827B - Method for catalyzing and synthesizing spiral carbon nano material by using water-soluble alkali metal carbonate - Google Patents
Method for catalyzing and synthesizing spiral carbon nano material by using water-soluble alkali metal carbonate Download PDFInfo
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- CN102390827B CN102390827B CN 201110203895 CN201110203895A CN102390827B CN 102390827 B CN102390827 B CN 102390827B CN 201110203895 CN201110203895 CN 201110203895 CN 201110203895 A CN201110203895 A CN 201110203895A CN 102390827 B CN102390827 B CN 102390827B
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Abstract
The invention discloses a method for catalyzing and synthesizing a spiral carbon nano material by using water-soluble alkali metal carbonate. The method comprises the following steps of: synthesizing a catalyst precursor; putting the catalyst precursor into a tubular reactor in which temperature can be precisely controlled, feeding helium and thermally treating the catalyst precursor to obtain catalyst alkali metal carbonate nano particles, wherein the thermal treatment temperature is between 400 and 600 DEG C and the thermal treatment time is 3 to 10 hours; after thermal treatment, stopping feeding the helium, then feeding acetylene gas immediately, and catalyzing and splitting the acetylene on the surfaces of the catalyst alkali metal carbonate nano particles, wherein the reaction temperature is between 400 and 600 DEG C and the reaction time is 3 to 8 hours; and thus obtaining the black spiral carbon nano material. In the method, the adopted catalyst is the water-soluble alkali metal carbonate, so the water-soluble alkali metal carbonate can be washed away conveniently and the pure spiral carbon nano material can be obtained; furthermore, the method is environment-friendly and pollution-free; and preparation process and equipment are simple, the reaction temperature is low, the cost is low and large-scale production can be realized.
Description
Technical field
The present invention relates to a kind of new nano material synthetic method, adopting water miscible alkaline carbonate is that catalyzer synthesizes the spiral carbon nanomaterial, because therefore the catalyzer water soluble can be removed from the spiral carbon nanomaterial easily, obtains pure carbon nanomaterial.
Background technology
In recent years, one-dimensional carbon nano material (such as carbon nanotube, nanofiber, nanometer spiral etc.) has been subject to people and has paid close attention to widely.These carbon nanomaterials have many potential application, as being used for hydrogen storage material, absorption of electromagnetic wave, electrode materials, feds, fuel cell etc.The preparation method of bibliographical information mainly relies on impurity such as mixing sulphur in the catalyzer at present, and introducing sulfurous gas (such as thiophene), or the Nanometer Copper monocrystalline that obtains by the modification of chiral reagent tartrate is as catalyzer, complicated condition and restive, the product pattern that obtains is not single, purity is lower, temperature of reaction is high, energy consumption is large, but also faces many problem of environmental pollutions.
Having recently a lot of reports to adopt transition metal nanoparticles is catalyzer, can synthesize the nano materials such as spiral carbon nanofiber or spiral carbon nanotubes by the catalytic pyrolysis acetylene gas under lower temperature.But transition metal nanoparticles can be wrapped in and be difficult in the carbon nanomaterial remove.In order to remove these catalyzer, often adopt the methods such as concentrated acid thermal treatment, not only expend a large amount of manpower and materials and plenty of time, and can damage the structure of carbon nanomaterial, affect the performance of carbon nanomaterial, seriously restricted the application of carbon nanomaterial.It is that catalyzer synthesizes the spiral carbon nanomaterial that innovation of the present invention adopts water miscible alkaline carbonate, because therefore the catalyzer water soluble can be removed catalyzer from the spiral carbon nanomaterial easily, obtains pure carbon nanomaterial.Both saved the cost of purifying, can structure and the performance of carbon nanomaterial do not exerted an influence again.
Summary of the invention
The present invention seeks to: proposing a kind of new employing water soluble alkali metal carbonate is the method for the synthetic spiral carbon nanomaterial of catalyzer.
Technical scheme of the present invention is: water soluble alkali metal carbonate catalyzes and synthesizes the method for spiral carbon nanomaterial, synthetic catalyst presoma at first: take sodium hydroxide or/and potassium hydroxide as raw material, citric acid or ethylene glycol are complexing agent, dehydrated alcohol or Virahol are that solvent forms even non-aqueous sol, form gel through dehydration by evaporation, organism is removed in preroasting in the air, obtains catalyzer alkaline carbonate presoma; Wherein the basic metal raw material can be simple sodium hydroxide, simple potassium hydroxide, or both mixtures (sodium and potassium can arbitrary proportion mix); The mol ratio of alkalimetal ion summation and complexing agent is 1:0.5 ~ 1:2; The dehydration by evaporation temperature is 60 ~ 80
oC; Xerogel calcined temperature in air is 400 ~ 600
oC, roasting time 4 ~ 10 hours;
Catalyst precursor is positioned over and can accurately controls in the tubular reactor of temperature, pass into helium heat treatment catalyst presoma and obtain catalyzer alkaline carbonate nano particle.Thermal treatment temp is 400 ~ 600
OC, heat treatment time 3 ~ 10 hours; Thermal treatment is closed helium after finishing, and switches immediately to enter acetylene gas, at catalyzer alkaline carbonate nano grain surface catalytic pyrolysis acetylene; Temperature of reaction 400 ~ 600
OC, in 3 ~ 8 hours reaction times, can in reactor, obtain black spiral carbon nanomaterial.
The spiral carbon nanomaterial that obtains with method of the present invention, can remove the alkaline carbonate catalyzer by simple water washing process, obtain highly purified spiral carbon nanomaterial, can be applicable to many fields such as hydrogen storage material, absorption of electromagnetic wave, electrode materials, feds, fuel cell.Compare with the method for preparing the spiral carbon nanomaterial of document and patent report, maximum difference of the present invention is to utilize water soluble alkali metal carbonate to be catalyzer, fundamentally solved in the past take transition metal as catalyzer, and catalyzer is difficult to the problem removed from carbon nanomaterial.Do not use any sulfurous gas (such as thiophene) and chiral reagent in the building-up process, temperature of reaction is low, and productive rate is high, and economic environmental protection is conducive to scale production.
Product with the present invention preparation carries out structure and performance characterization by following means: the D/Max-RA type rotating anode X-ray diffractometer (XRD) that the phase of product adopts Japanese Rigaku company to make is analyzed (CuK α); Sirion field emission scanning electron microscope (FE-SEM) and JEOL-2010 type high resolution transmission electron microscopy (HRTEM) that the pattern of product adopts JSM-5610LV type scanning electronic microscope (SEM), FEI Co. to produce characterize.
The invention has the beneficial effects as follows: the present invention is in tubular reactor, and take basic metal (Na and K) carbonate as catalyzer, the catalytic pyrolysis acetylene gas synthesizes the spiral carbon nanomaterial.Owing in whole building-up process, do not need to add any sulfurous gas (such as thiophene) and chiral reagent, saved material cost, and environmental friendliness, pollution-free.This preparation technology's equipment is simple, temperature of reaction is low, cost is low, process is controlled easily, is easy to mass-producing; The most important thing is, the catalyzer that the present invention adopts is water soluble carbonate, can remove easily and obtain pure spiral carbon material, greatly saved the purifying cost of carbon nanomaterial, kept simultaneously the structure of spiral carbon nanomaterial and the impact that performance is not subjected to purge process, significant for the application of spiral carbon nanomaterial.
It is catalyzer that the present invention adopts the water soluble alkali metal carbonate nano particle, and the catalytic pyrolysis acetylene gas synthesizes the spiral carbon nanomaterial.By simple water washing process, obtain highly purified spiral carbon nanomaterial thereby can from synthetic product, remove easily catalyzer.Owing in whole building-up process, do not need to add any sulfurous gas (such as thiophene) and chiral reagent, saved material cost and purifying cost, and environmental friendliness, pollution-free.This preparation technology's equipment is simple, temperature of reaction is low, cost is low, process is controlled easily, is easy to large-scale production.
Description of drawings
Fig. 1 is field emission scanning electron microscope (FE-SEM) photo of the spiral carbon nanomaterial that obtains of embodiment 1.Studies show that the product that obtains is the carbon nanometer spiral, selectivity is up to 83%; Diameter 120 nm of carbon nanometer spiral, length reaches several millimeters.Figure a, b are different magnification ratio diagrams.
Fig. 2 is field emission scanning electron microscope (FE-SEM) photo of the spiral carbon nanomaterial that obtains of embodiment 2.Can find out diameter 100 nm of spiral carbon nanomaterial.Figure a, b are different magnification ratio diagrams.
Fig. 3 is field emission scanning electron microscope (FE-SEM) photo of the spiral carbon nanomaterial that obtains of embodiment 3.The selectivity of spiral carbon nanomaterial is up to 88%, and sample length is slightly shorter than sample synthetic among the embodiment 1.Figure a, b are different magnification ratio diagrams.
Fig. 4 is field emission scanning electron microscope (FE-SEM) photo of the spiral carbon nanomaterial that obtains of embodiment 4.The selectivity of spiral carbon nanomaterial further improves, up to 94%.The pattern of sample is more even, diameter 200 nm, length about 4
μM.Figure a, b are different magnification ratio diagrams.
Fig. 5 is field emission scanning electron microscope (FE-SEM) photo of the spiral carbon nanomaterial that obtains of embodiment 5.Experimental result shows that the productive rate of the simple spiral carbon nanomaterial that synthesizes take the yellow soda ash nano particle as catalyzer is lower, but selectivity is up to 96%.Diameter 50 nm of spiral carbon nanomaterial, length reaches several millimeters.Figure a, b are different magnification ratio diagrams.
Fig. 6 is field emission scanning electron microscope (FE-SEM) photo of the spiral carbon nanomaterial that obtains of embodiment 6.Experimental result shows that potassium content increase in the catalyzer is conducive to the generation of spiral carbon nanomaterial, and the productive rate of synthetic spiral carbon nanomaterial is higher.Diameter 140 nm of spiral carbon nanomaterial, length is tens microns to several millimeters.Figure a, b are different magnification ratio diagrams.
Fig. 7 is field emission scanning electron microscope (FE-SEM) photo of the spiral carbon nanomaterial that obtains of embodiment 7.Experimental result shows that the productive rate of the simple spiral carbon nanomaterial that synthesizes take salt of wormwood as catalyzer is the highest.Diameter 250 nm of spiral carbon nanomaterial, length is tens microns and arrives the hundreds of micron.Figure a, b are different magnification ratio diagrams.
Embodiment
Below be embodiments of the invention (agents useful for same is chemical pure among the embodiment).
Embodiment 1:
Step 1Take by weighing 0.05 mol NaOH(solid), 0.05 mol KOH(solid) and 0.05 mol citric acid be dissolved in the 200 mL dehydrated alcohols, 60
°Continue under the C temperature to stir 6 hours, form homogeneous transparent colloidal sol; 80
oThe C dehydration by evaporation is until white powder; Powder is placed under the retort furnace Air atmosphere 600
oC preroasting 4 hours obtains catalyst precursor.
Step 2Take by weighing 0.10 gram catalyst precursor, be tiled in wide 3 cm, in the ceramic Noah's ark of long 6 cm.Noah's ark is placed into internal diameter 6cm, in the quartz reactor of long 80cm, then with the quartz reactor horizontal positioned in tube furnace, make Noah's ark just in time place the middle part (place, temperature thermocouple place) of tube furnace.
Step 3Pass into helium in the reactor, with 5
°C/ minute speed is warming up to 450 ° of C, is incubated 1 hour, closes helium, switches immediately acetylene gas, and 450 ° of C reacted 6 hours.In Noah's ark, obtain a large amount of black spiral carbon nanomaterials.The pattern of product is seen accompanying drawing 1.
Dehydrated alcohol in the step 1 is replaced with Virahol, obtain similar results.
With 0.05 mol NaOH(solid in the step 1) and 0.05 mol KOH(solid) quality double, change and make 0.1 mol NaOH(solid) and 0.1 mol KOH(solid) obtain similar results.The dehydration by evaporation temperature is 60
oC also can, but time lengthening, efficient is lower; Xerogel calcined temperature in air is 400 ~ 500
oC, roasting time can be grown by 10 hours.
Embodiment 2:
Step 3Pass into helium in the reactor, with 5
°C/ minute speed is warming up to 400 ° of C, is incubated 1 hour, closes hydrogen, switches immediately acetylene gas, and 400 ° of C reacted 6 hours.In Noah's ark, obtain a large amount of black spiral carbon nanomaterials.The pattern of product is seen accompanying drawing 2.
Dehydrated alcohol in the step 1 is replaced with Virahol, obtain similar results.
With 0.05 mol NaOH(solid in the step 1) and 0.05 mol KOH(solid) change and make 0.02 mol NaOH(solid caustic soda) and 0.02mol KOH(solid) similar results obtained.
Also can adopt mass concentration is that NaOH or KOH solution more than 95% is raw material.
Embodiment 3:
Step 3Pass into helium in the reactor, with 5
°C/ minute speed is warming up to 500 ° of C, is incubated 1 hour, closes hydrogen, switches immediately acetylene gas, and 500 ° of C reacted 6 hours.In Noah's ark, obtain a large amount of black spiral carbon nanomaterials.The pattern of product is seen accompanying drawing 3.
Embodiment 4:
Step 3Pass into helium in the reactor, with 5
°C/ minute speed is warming up to 600 ° of C, is incubated 1 hour, closes hydrogen, switches immediately acetylene gas, and 600 ° of C reacted 6 hours.In Noah's ark, obtain a large amount of black spiral carbon nanomaterials.The pattern of product is seen accompanying drawing 4.
Embodiment 5:
Step 1Take by weighing 0.10 mol NaOH and 0.05 mol citric acid is dissolved in the 200 mL dehydrated alcohols, 60
°Continue under the C temperature to stir 6 hours, form homogeneous transparent colloidal sol; 80
oThe C dehydration by evaporation is until white powder; Powder is placed under the retort furnace Air atmosphere 600
oC preroasting 4 hours obtains catalyst precursor.
Embodiment 6:
Step 1Take by weighing 0.025 mol NaOH, 0.075 mol KOH and 0.05 mol citric acid are dissolved in the 200 mL dehydrated alcohols, 60
°Continue under the C temperature to stir 6 hours, form homogeneous transparent colloidal sol; 80
oThe C dehydration by evaporation is until white powder; Powder is placed under the retort furnace Air atmosphere 600
oC preroasting 4 hours obtains catalyst precursor.
Embodiment 7:
Step 1Take by weighing 0.10 mol KOH and 0.05 mol citric acid is dissolved in the 200 mL dehydrated alcohols, 60
°Continue under the C temperature to stir 6 hours, form homogeneous transparent colloidal sol; 80
oThe C dehydration by evaporation is until white powder; Powder is placed under the retort furnace Air atmosphere 600
oC preroasting 4 hours obtains catalyst precursor.
Claims (1)
1. water soluble alkali metal carbonate catalyzes and synthesizes the method for spiral carbon nanomaterial, it is characterized in that at first synthetic catalyst presoma: take sodium hydroxide or/and potassium hydroxide as raw material, citric acid or ethylene glycol are complexing agent, dehydrated alcohol or Virahol are that solvent forms even non-aqueous sol, form gel through dehydration by evaporation, organism is removed in preroasting in the air, obtains catalyzer alkaline carbonate presoma; Sodium hydroxide and potassium hydroxide mixed with arbitrary proportion when wherein sodium hydroxide was raw material with potassium hydroxide; The mol ratio of alkalimetal ion summation and complexing agent is 1:0.5～1:2; The dehydration by evaporation temperature is 60～80 ℃; Xerogel calcined temperature in air is 400～600 ℃, roasting time 4～10 hours;
Catalyst precursor is positioned over and can accurately controls in the tubular reactor of temperature, pass into helium heat treatment catalyst presoma and obtain catalyzer alkaline carbonate nano particle; Thermal treatment temp is 400～600 ℃, heat treatment time 3～10 hours; Thermal treatment is closed helium after finishing, and switches immediately to enter acetylene gas, at catalyzer alkaline carbonate nano grain surface catalytic pyrolysis acetylene; 400～600 ℃ of temperature of reaction, 3～8 hours reaction times.
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| CN103013441B (en) * | 2013-01-10 | 2014-03-19 | 贵州大学 | Method for growing low helical carbon nanotube composite microwave absorbing material by in-situ catalysis |
| CN109286018B (en) * | 2018-12-06 | 2021-12-31 | 中国科学院兰州化学物理研究所 | Preparation method of ultrathin two-dimensional carbon sheet |
| CN113896183A (en) * | 2021-10-22 | 2022-01-07 | 北京化工大学 | Method for growing carbon nano material by solar drive |
Citations (2)
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| CN1438072A (en) * | 2003-03-03 | 2003-08-27 | 清华大学 | Catayst for preparing carbon-nano tube |
| CN101531362A (en) * | 2009-04-17 | 2009-09-16 | 北京化工大学 | Method for one-step growth of carbon nanotube by taking carbon composite as catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438072A (en) * | 2003-03-03 | 2003-08-27 | 清华大学 | Catayst for preparing carbon-nano tube |
| CN101531362A (en) * | 2009-04-17 | 2009-09-16 | 北京化工大学 | Method for one-step growth of carbon nanotube by taking carbon composite as catalyst |
Non-Patent Citations (4)
| Title |
|---|
| Synthesis of Carbon Nanofibers and Foam by Catalytic Chemical Vapor Deposition Using a Water‐Soluble Alkali Salt Catalyst;Yongheng Zhang,et.al.;《Advanced Materials》;20071231;第19卷;第961-964页 * |
| Synthesis of helical carbon nanotubes, worm-like carbon nanotubes and nanocoils at 450 C and their magnetic properties;Xiaosi Qi,et.al.;《Carbon》;20090915;第48卷;第365-376页 * |
| Xiaosi Qi,et.al..Synthesis of helical carbon nanotubes, worm-like carbon nanotubes and nanocoils at 450 C and their magnetic properties.《Carbon》.2009,第48卷第365-376页. |
| Yongheng Zhang,et.al..Synthesis of Carbon Nanofibers and Foam by Catalytic Chemical Vapor Deposition Using a Water‐Soluble Alkali Salt Catalyst.《Advanced Materials》.2007,第19卷第961-964页. |
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