CN103803554B - A kind of carbon nanotube/porous silica composite granule and preparation method thereof - Google Patents
A kind of carbon nanotube/porous silica composite granule and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of carbon nanotube/porous silica composite granule and preparation method thereof, its technical scheme is: rice husk is placed in hydrochloric acid, sulfuric acid or oxalic acid solution that concentration is 0.1 ~ 5wt%, at 90 ~ 100 DEG C of Water Under bath 1 ~ 2h, filters; Be 6 ~ 8 with water cleaning rice husk to the pH value of scavenging solution, dry, obtain pre-treatment rice husk.Joined by pre-treatment rice husk in the solution of nickeliferous organic coordination compound, in the organic coordination compound of pre-treatment rice husk and described nickel, the mass ratio of nickel element is 1 ︰ (0.001 ~ 0.02) again, places 20 ~ 24h, dry, obtains reprocessing rice husk.Then reprocessing rice husk is incubated 3 ~ 4h under 1000 ~ 1400 DEG C of conditions in argon gas or nitrogen, obtains carbon nanotube/porous silica composite granule.The present invention is with low cost, technique is simple, environmental friendliness, applicable large-scale industrial production and added value of product are high; Its goods have carbon nanotube original position and are formed, are evenly distributed, without the need to the feature of additional carbon or carbon nanotube.
Description
Technical field
The invention belongs to porous composite granule technical field, be specifically related to a kind of carbon nanotube/porous silica composite granule and preparation method thereof.
Background technology
China is annual produces paddy more than 400,000,000 ton, and can produce more than 8,000 ten thousand tons, rice husk, account for more than 30% of Gross World Product, rank first in the world, mostly utilize as primary fuel, comprehensive utilization ratio is less than 10%; Density because of rice husk is little and volume large, causes pollution to environment, and the rice hull ash formed after burning does not mostly process, and becomes agricultural wastes, exert heavy pressures on to environment in many places.Therefore, for rice husk seeks the very big concern that suitable outlet has caused scientific and technical personnel.
Be rich in silicon-dioxide in rice husk, be mainly distributed in the appearance internal layer of rice husk, granular size is at about 50nm, mainly exist with metamict, massfraction shared in rice husk is 3.0% ~ 22.0%, and in rice husk, remaining overwhelming majority is organism, also has a small amount of inorganic oxide.Research finds, forming amorphous silica by biomineralization in organism is complete under the physiological status of gentleness.These biogenic silicon-dioxide have accurate Genetic Control, and present the exquisite structure of nanometer level, in density, component, calorifics and mechanical property etc., have diversity widely, be that the mankind at present cannot be produced.
Porous material silicon-dioxide has the characteristics such as larger specific surface area, spacious skeleton structure and abundant pore passage structure, is widely applied to the fields such as catalysis, absorption, separation, electrochemistry.In order to obtain optimum performance, porous silica silicon materials need to carry out modifying or combining with other materials usually.Meanwhile, carbon nanotube, owing to having unique mechanics, electricity and absorption property, makes it demonstrate good application potential in fields such as Flied emission, electrochemistry and Chu Qing.Therefore, if can prepare the composite granule of a kind of carbon nanotube and porous silica, the pore structure of carbon nanotube to silicon-dioxide is become more meticulous further, and this composite granule will present the performance more more excellent than bi-material.
At present, preparing carbon nanotube/silicon dioxide composite powder main technique for using silicon-dioxide to be matrix, passing into organic gas, adopting chemical Vapor deposition process, or prepare after directly using silica sol to mix with carbon nanotube.Recently, carbon nano tube suspension is mixed (physical mixed) and has prepared SiO afterwards by Alonso Gamero-Quijano with silica sol presoma
2-SWCNT composite granule, and research finds that it has good chemical property (Alonso Gamero-Quijano, Francisco Huerta, David Salinas-Torres, Emilia Morall ó n, Francisco Montilla. Electrocatalytic Performance of SiO
2-SWCNT Nanocomposites Prepared by Electroassisted Deposition. Electrocatalysis. DOI 10.1007/s12678-013-0144-3), Raja N. Othman utilizes the silica gel of porous as matrix, floating catalytic agent chemical vapor deposition method is adopted to prepare silica-carbon nanotube microballoon (Raja N. Othman, Ian A. Kinloch, Arthur N. Wilkinson. Synthesis and characterisation of silica – carbon nanotube hybrid microparticles and their effect on the electrical properties of poly (vinyl alcohol) composites. CARBON 60 (2013) 461-470).But, use the method for physical mixed be difficult to making even carbon nanotube with silicon oxide compound; Chemical Vapor deposition process is used then to there is two problems: the matrix of porous silica is difficult to preparation, needs non-renewable organic gas to provide carbon source.
Summary of the invention
The present invention is intended to overcome prior art defect, and object is to provide that a kind of with low cost, technique is simple, the method preparing carbon nanotube/porous silica composite granule of environmental friendliness and applicable large-scale industrial production.The carbon nanotube prepared by the method/porous silica composite granule has carbon nanotube original position and is formed, is evenly distributed, without the need to the feature of additional carbon or carbon nanotube.
For achieving the above object, the concrete steps of the technical solution used in the present invention are:
The pre-treatment of step one, rice husk
Rice husk is placed in the solution of hydrochloric acid, sulfuric acid or the oxalic acid that concentration is 0.1 ~ 5wt%, at 90 ~ 100 DEG C of Water Under bath 1 ~ 2h, filters; Be 6 ~ 8 with water cleaning rice husk to the pH value of scavenging solution again, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain pre-treatment rice husk.
The reprocessing of step 2, rice husk
Pre-treatment rice husk is joined in the solution of nickeliferous organic coordination compound, in the organic coordination compound of pre-treatment rice husk and described nickel, the mass ratio of nickel element is 1 ︰ (0.001 ~ 0.02), 20 ~ 24h is placed under room temperature and condition of normal pressure, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain reprocessing rice husk.
The pyroprocessing of step 3, rice husk
Reprocessing rice husk is incubated under argon gas and 1000 ~ 1400 DEG C of conditions 3 ~ 4h or is incubated 3 ~ 4h under nitrogen and 1000 ~ 1400 DEG C of conditions, obtain carbon nanotube/porous silica composite granule.
The organic coordination compound of described nickel is the one in the organic coordination compound of the organic coordination compound of phthalate bridging nickel, the organic coordination compound of nickel dimethylglyoximate, the organic coordination compound of 4'-p-methoxyphenyl terpyridyl nickel, the organic coordination compound of four major esters tetraene nickel, pyridine-2-formaldehyde oxime nickel.
Owing to adopting technique scheme, the present invention compared with prior art, has following positively effect:
1, the raw material that the present invention adopts is agricultural wastes, cheap, renewable; By carrying out pre-treatment to rice husk, adopting the organic coordination compound solution of nickel to heat-treat under the condition of different temperatures of nitrogen or argon gas atmosphere to the reprocessing of rice husk with to reprocessing rice husk, directly prepare carbon nanotube/porous silica composite granule, preparation technology is simple.
2, the present invention prepares carbon nanotube/porous oxidation silicon powder, without the need to preparing porous oxidation silicon substrate, without the need to external carbon nanotube or add carbon source, simplifies preparation technology, conservation.
3, the present invention take rice husk as raw material, while utilizing rice husk cracking carbon to form three-dimensional hole, original position forms carbon nanotube, directly prepare carbon nanotube/porous silica composite granule, CNT (carbon nano-tube) well grows on the hole of porous silica and surface, forms uniform composite granule.
4, the present invention adopts the organic coordination compound of nickel, makes it to form alloy with high reactivity silicon-dioxide in rice husk under the high temperature conditions, under its katalysis, use plant organic matter to prepare carbon nanotube as carbon source.
Therefore, the present invention is with low cost, technique is simple, environmental friendliness, applicable large-scale industrial production and added value of product are high; Prepared carbon nanotube/porous silica composite granule has carbon nanotube original position and is formed, is evenly distributed, without the need to the feature of additional carbon or carbon nanotube.
Accompanying drawing explanation
Fig. 1 is the SEM shape appearance figure of a kind of carbon nanotube/porous silica composite granule prepared by the present invention;
Fig. 2 is the HRTEM photo of carbon nanotube in the carbon nanotube shown in Fig. 1/porous silica composite granule.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described, not limiting the scope of the invention.
embodiment 1
A kind of carbon nanotube/porous silica composite granule and preparation method thereof, the concrete steps of the method are:
The pre-treatment of step one, rice husk
Rice husk is placed in the hydrochloric acid soln that concentration is 0.1 ~ 0.5wt%, at 90 ~ 100 DEG C of Water Under bath 1 ~ 2h, filters; Be 6 ~ 8 with water cleaning rice husk to the pH value of scavenging solution again, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain pre-treatment rice husk;
The reprocessing of step 2, rice husk
Pre-treatment rice husk is joined in the solution containing the organic coordination compound of phthalate bridging nickel, in the organic coordination compound of pre-treatment rice husk and phthalate bridging nickel, the mass ratio of nickel element is 1 ︰ (0.001 ~ 0.005), 20 ~ 24h is placed under room temperature and condition of normal pressure, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain reprocessing rice husk;
The pyroprocessing of step 3, rice husk
Reprocessing rice husk is incubated 3 ~ 4h under argon gas and 1000 ~ 1100 DEG C of conditions, obtains carbon nanotube/porous silica composite granule.
embodiment 2
A kind of carbon nanotube/porous silica composite granule and preparation method thereof, the concrete steps of the method are:
The pre-treatment of step one, rice husk
Rice husk is placed in the sulphuric acid soln that concentration is 0.1 ~ 0.5wt%, at 90 ~ 100 DEG C of Water Unders bath, 1 ~ 2h, filters, then be 6 ~ 8 by water cleaning rice husk to the pH value of scavenging solution, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain pre-treatment rice husk;
The reprocessing of step 2, rice husk
Pre-treatment rice husk is joined in the solution containing the organic coordination compound of nickel dimethylglyoximate, in the organic coordination compound of pre-treatment rice husk and nickel dimethylglyoximate, the mass ratio of nickel element is 1 ︰ (0.005 ~ 0.01), 20 ~ 24h is placed under room temperature and condition of normal pressure, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain reprocessing rice husk;
The pyroprocessing of step 3, rice husk
Reprocessing rice husk is incubated 3 ~ 4h under nitrogen and 1100 ~ 1200 DEG C of conditions, obtains carbon nanotube/porous silica composite granule.
embodiment 3
A kind of carbon nanotube/porous silica composite granule and preparation method thereof, the concrete steps of the method are:
The pre-treatment of step one, rice husk
Rice husk is placed in the oxalic acid solution that concentration is 0.5 ~ 1wt%, at 90 ~ 100 DEG C of Water Unders bath, 1 ~ 2h, filters, then be 6 ~ 8 by water cleaning rice husk to the pH value of scavenging solution, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain pre-treatment rice husk;
The reprocessing of step 2, rice husk
Pre-treatment rice husk is joined in the solution containing the organic coordination compound of 4'-p-methoxyphenyl terpyridyl nickel, in the organic coordination compound of pre-treatment rice husk and 4'-p-methoxyphenyl terpyridyl nickel, the mass ratio of nickel element is 1 ︰ (0.01 ~ 0.015), 20 ~ 24h is placed under room temperature and condition of normal pressure, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain reprocessing rice husk;
The pyroprocessing of step 3, rice husk
Reprocessing rice husk is incubated 3 ~ 4h under nitrogen and 1200 ~ 1300 DEG C of conditions, obtains carbon nanotube/porous silica composite granule.
embodiment 4
A kind of carbon nanotube/porous silica composite granule and preparation method thereof, the concrete steps of the method are:
The pre-treatment of step one, rice husk
Rice husk is placed in the hydrochloric acid soln that concentration is 1 ~ 3wt%, at 90 ~ 100 DEG C of Water Unders bath, 1 ~ 2h, filters, then be 6 ~ 8 by water cleaning rice husk to the pH value of scavenging solution, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain pre-treatment rice husk;
The reprocessing of step 2, rice husk
Pre-treatment rice husk is joined in the solution containing the organic coordination compound of four major esters tetraene nickel, in the organic coordination compound of pre-treatment rice husk and four major esters tetraene nickel, the mass ratio of nickel element is 1 ︰ (0.015 ~ 0.02), 20 ~ 24h is placed under room temperature and condition of normal pressure, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain reprocessing rice husk;
The pyroprocessing of step 3, rice husk
Reprocessing rice husk is incubated 3 ~ 4h under nitrogen and 1300 ~ 1400 DEG C of conditions, obtains carbon nanotube/porous silica composite granule.
embodiment 5
A kind of carbon nanotube/porous silica composite granule and preparation method thereof, the concrete steps of the method are:
The pre-treatment of step one, rice husk
Rice husk is placed in the sulphuric acid soln that concentration is 0.8 ~ 1.5wt%, at 90 ~ 100 DEG C of Water Unders bath, 1 ~ 2h, filters, then be 6 ~ 8 by water cleaning rice husk to the pH value of scavenging solution, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain pre-treatment rice husk;
The reprocessing of step 2, rice husk
Pre-treatment rice husk is joined in the solution containing the organic coordination compound of pyridine-2-formaldehyde oxime nickel, in the organic coordination compound of pre-treatment rice husk and pyridine-2-formaldehyde oxime nickel, the mass ratio of nickel element is 1 ︰ (0.001 ~ 0.005), 20 ~ 24h is placed under room temperature and condition of normal pressure, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain reprocessing rice husk;
The pyroprocessing of step 3, rice husk
Reprocessing rice husk is incubated 3 ~ 4h under nitrogen and 1000 ~ 1100 DEG C of conditions, obtains carbon nanotube/porous silica composite granule.
embodiment 6
A kind of carbon nanotube/porous silica composite granule and preparation method thereof, the concrete steps of the method are:
The pre-treatment of step one, rice husk
Rice husk is placed in the oxalic acid solution that concentration is 3 ~ 5wt%, at 90 ~ 100 DEG C of Water Unders bath, 1 ~ 2h, filters, then be 6 ~ 8 by water cleaning rice husk to the pH value of scavenging solution, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain pre-treatment rice husk;
The reprocessing of step 2, rice husk
Pre-treatment rice husk is joined in the solution containing the organic coordination compound of phthalate bridging nickel, in the organic coordination compound of pre-treatment rice husk and phthalate bridging nickel, the mass ratio of nickel element is 1 ︰ (0.005 ~ 0.01), 20 ~ 24h is placed under room temperature and condition of normal pressure, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain reprocessing rice husk;
The pyroprocessing of step 3, rice husk
Reprocessing rice husk is incubated 3 ~ 4h under nitrogen and 1100 ~ 1200 DEG C of conditions, obtains carbon nanotube/porous silica composite granule.
embodiment 7
A kind of carbon nanotube/porous silica composite granule and preparation method thereof, the concrete steps of the method are:
The pre-treatment of step one, rice husk
Rice husk is placed in the hydrochloric acid soln that concentration is 3 ~ 5wt%, at 90 ~ 100 DEG C of Water Unders bath, 1 ~ 2h, filters, then be 6 ~ 8 by water cleaning rice husk to the pH value of scavenging solution, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain pre-treatment rice husk;
The reprocessing of step 2, rice husk
Pre-treatment rice husk is joined in the solution containing the organic coordination compound of nickel dimethylglyoximate, in the organic coordination compound of pre-treatment rice husk and nickel dimethylglyoximate, the mass ratio of nickel element is 1 ︰ (0.01 ~ 0.015), 20 ~ 24h is placed under room temperature and condition of normal pressure, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain reprocessing rice husk;
The pyroprocessing of step 3, rice husk
Reprocessing rice husk is incubated 3 ~ 4h under nitrogen and 1200 ~ 1300 DEG C of conditions, obtains carbon nanotube/porous silica composite granule.
embodiment 8
A kind of carbon nanotube/porous silica composite granule and preparation method thereof, the concrete steps of the method are:
The pre-treatment of step one, rice husk
Rice husk is placed in the sulphuric acid soln that concentration is 0.5 ~ 1wt%, at 90 ~ 100 DEG C of Water Unders bath, 1 ~ 2h, filters, then be 6 ~ 8 by water cleaning rice husk to the pH value of scavenging solution, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain pre-treatment rice husk;
The reprocessing of step 2, rice husk
Pre-treatment rice husk is joined in the solution containing the organic coordination compound of phthalate bridging nickel, in the organic coordination compound of pre-treatment rice husk and phthalate bridging nickel, the mass ratio of nickel element is 1 ︰ (0.015 ~ 0.02), 20 ~ 24h is placed under room temperature and condition of normal pressure, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain reprocessing rice husk;
The pyroprocessing of step 3, rice husk
Reprocessing rice husk is incubated 3 ~ 4h under nitrogen and 1300 ~ 1400 DEG C of conditions, obtains carbon nanotube/porous silica composite granule.
embodiment 9
A kind of carbon nanotube/porous silica composite granule and preparation method thereof, the concrete steps of the method are:
The pre-treatment of step one, rice husk
Rice husk is placed in the oxalic acid solution that concentration is 1 ~ 3wt%, at 90 ~ 100 DEG C of Water Unders bath, 1 ~ 2h, filters, then be 6 ~ 8 by water cleaning rice husk to the pH value of scavenging solution, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain pre-treatment rice husk;
The reprocessing of step 2, rice husk
Pre-treatment rice husk is joined in the solution containing the organic coordination compound of nickel dimethylglyoximate, in the organic coordination compound of pre-treatment rice husk and nickel dimethylglyoximate, the mass ratio of nickel element is 1 ︰ (0.01 ~ 0.015), 20 ~ 24h is placed under room temperature and condition of normal pressure, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain reprocessing rice husk;
The pyroprocessing of step 3, rice husk
Reprocessing rice husk is incubated 3 ~ 4h under nitrogen and 1200 ~ 1300 DEG C of conditions, obtains carbon nanotube/porous silica composite granule.
This embodiment, by carrying out pre-treatment to rice husk, adopting the organic coordination compound solution of nickel to heat-treat under differing temps under nitrogen or argon gas atmosphere to the reprocessing of rice husk with to reprocessing rice husk, obtains carbon nanotube/porous silica composite granule.Compared with prior art, this embodiment tool has the following advantages:
1, this embodiment is by carrying out pre-treatment, adopting the organic coordination compound solution of nickel to heat-treat under differing temps under nitrogen or argon gas atmosphere to the reprocessing of rice husk with to reprocessing rice husk to rice husk, directly prepare carbon nanotube/porous silica composite granule, low in raw material price, renewable, preparation technology is simple.
2, this embodiment prepares carbon nanotube/porous silica composite granule, without the need to preparing porous oxidation silicon substrate, without the need to external carbon nanotube or add carbon source, simplifies preparation technology, conservation.
3, this embodiment take rice husk as main raw material, while utilizing rice husk cracking carbon to form three-dimensional hole, original position forms carbon nanotube, even carbon nanotube be distributed in porous silica hole, the carbon nanotube/porous silica composite granule of directly preparation is as shown in Figure 1 or be similar to shown in Fig. 1.A kind of carbon nanotube/porous silica the composite granule of Fig. 1 prepared by embodiment in this embodiment 1, the diameter of obtained carbon nanotube is about 200nm.Can find out: CNT (carbon nano-tube) well grows on the hole of porous silica and surface, forms uniform composite granule.
4, use the organic coordination compound of nickel, make it to form alloy with high reactivity silicon-dioxide in rice husk under the high temperature conditions, under its katalysis, use plant organic matter to prepare carbon nanotube as carbon source.
Therefore, this embodiment is with low cost, technique simple, environmental friendliness, applicable large-scale industrial production and added value of product are high; Prepared carbon nanotube/porous silica composite granule has carbon nanotube original position and is formed, is evenly distributed, without the need to the feature of additional carbon or carbon nanotube.
Claims (1)
1. a preparation method for carbon nanotube/porous silica composite granule, is characterized in that the concrete steps of described preparation method are:
The pre-treatment of step one, rice husk
Rice husk is placed in the solution of hydrochloric acid, sulfuric acid or the oxalic acid that concentration is 0.1 ~ 5wt%, at 90 ~ 100 DEG C of Water Under bath 1 ~ 2h, filters; Be 6 ~ 8 with water cleaning rice husk to the pH value of scavenging solution again, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain pre-treatment rice husk;
The reprocessing of step 2, rice husk
Pre-treatment rice husk is joined in the solution of nickeliferous organic coordination compound, in the organic coordination compound of pre-treatment rice husk and described nickel, the mass ratio of nickel element is 1 ︰ (0.001 ~ 0.02), 20 ~ 24h is placed under room temperature and condition of normal pressure, then under 80 ~ 100 DEG C of conditions, be incubated 24 ~ 30h, obtain reprocessing rice husk;
The pyroprocessing of step 3, rice husk
Reprocessing rice husk is incubated under argon gas and 1000 ~ 1400 DEG C of conditions 3 ~ 4h or is incubated 3 ~ 4h under nitrogen and 1000 ~ 1400 DEG C of conditions, obtain carbon nanotube/porous silica composite granule;
The organic coordination compound of described nickel is the one in the organic coordination compound of the organic coordination compound of phthalate bridging nickel, the organic coordination compound of nickel dimethylglyoximate, the organic coordination compound of 4'-p-methoxyphenyl terpyridyl nickel, the organic coordination compound of four major esters tetraene nickel, pyridine-2-formaldehyde oxime nickel.
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| CN104192829B (en) * | 2014-09-04 | 2016-05-25 | 武汉科技大学 | A kind of multidimensional-multi-stage porous SiO2/ C composite granule and preparation method thereof |
| CN105529447B (en) * | 2016-01-21 | 2018-06-15 | 昆明理工大学 | A kind of carbon nanotube-carbon-porous silicon composite material preparation method and application |
| CN106862589A (en) * | 2017-02-15 | 2017-06-20 | 珠海市吉林大学无机合成与制备化学重点实验室 | Metallic nickel nitrogen-doped porous carbon material, preparation method and applications |
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| CN101837948A (en) * | 2010-05-05 | 2010-09-22 | 吉林大学 | Novel method of rice hull liquification and integrated utilization |
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