CN105772708A - Method for using biomass waste for preparing nitrogen-doped carbon nanotube coated metal particle composite material - Google Patents
Method for using biomass waste for preparing nitrogen-doped carbon nanotube coated metal particle composite material Download PDFInfo
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Abstract
The invention discloses a method for using biomass waste for preparing a nitrogen-doped carbon nanotube coated metal particle composite material. The method includes the following steps that firstly, the biomass waste and KOH are evenly mixed in deionized water, an obtained heterogeneous mixture is carbonized under the protection of inert gas, and biomass charcoal is obtained; and then, the biomass charcoal, a nitrogenous nonmetallic compound and water-soluble divalent metal salt are evenly mixed in methyl alcohol, the obtained heterogeneous mixture is subjected to pyrolysis under the protection of the inert gas, and therefore a target product is obtained. By the adoption of the method, a two-step pyrolysis technology is adopted for achieving growth of carbon nanotubes, and dispersion of metal nanoparticles and formation of a cooperative acting mechanism are promoted; the stability of the composite material is reinforced through the structure of carbon nanotube coated metal nanoparticles; the surface activity and dispersity of a carbon layer are improved through in-situ decoration of the nitrogen element; and the contact and active site point number is increased through the formation of a rich pore structure and the high specific surface area.
Description
Technical field
The present invention relates to a kind of method utilizing biomass castoff to prepare coating metal particles composite for raw material, belong to biomass castoff comprehensive utilizating research field.
Background technology
CNT, because of the mechanics of its uniqueness, electronics and chemical characteristic, causes worldwide extensive concern, achieves in various fields such as field such as electricity, optics, catalysis, biomedicines and is widely applied.In recent years, along with carbon nanomaterial is studied deeply and the popularization of application, simple, low cost, batch prepare carbon nano-composite material becomes its wide variety of key of promotion.Explore and develop biomass waste resource cheap and easy to get in nature to prepare carbon nano-composite material and have become as the hot issue of scientist, engineer's extensive concern.
On the other hand, the modification of CNT can be obviously improved its performance, be increasingly becoming one of focus of material with carbon element research field in recent years.The modification of CNT is broadly divided into: CNT outside is modified, the filling of the doping of CNT and tube cavity.CNT outside is modified and mainly splices other organic or oxygen-containing functional groups at the outer surface of CNT, to improve its dispersibility.And the doping of CNT is other nonmetalloids that adulterate on graphitic carbon hexatomic ring, such as nitrogen, phosphorus, boron etc..The doping of CNT can substantially change its electronics, vibration, mechanically and chemically character.The filling of CNT is then at its pipe internal filler metal simple substance, metallic compound etc., to effectively facilitate the electron motion characteristic of outer carbon nanotube.Wherein, the performance of CNT is improved more notable by doping and filling, and the two is combined the performance that can promote composite better, such as DehuiDeng (AngewandteChemieInternationalEdition, 2013,52 (1), 371-375) by experiment research and science textual criticism show, the nitrogen doped carbon nanotube that ferrum is filled has fills than independent ferrum or redox catalysis performance that nitrogen-doped carbon nanometer pipe is more excellent.But, how to adopt the complex that a kind of method that technique is simple, with low cost, can manufacture carrys out synthetic nitrogen doped carbon nanometer pipe coating metal nano granule structure to have become as current facing challenges.
Arc discharge method, laser evaporization method, gas combustion method, chemical vapour deposition technique etc. are had about the method preparing loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite for raw material with biomass castoff.Wherein, the equipment that graphite acr method and laser evaporization method use is complicated, technological parameter not easily regulates, energy expenditure is big, production cost is high, is unfavorable for a large amount of abandoned biomass resource.Gas combustion method, chemical vapour deposition technique then need to introduce high-purity carbon-source gas, reducing gas or noble gas, catalyst, pre-prepared technique is loaded down with trivial details with synthesis step, and the pattern of prepared carbon nanomaterial, structure, distribution depend on the self-characteristic of catalyst and matrix, there is suitable limitation.Simultaneously, pattern and the structure of natural biomass garbage differ, constituent is complicated, impurity is more, if directly preparing nanometer tube composite materials with it for raw material, a large amount of side reaction can be produced, cause the aspects such as the carbon base body purity of prepared composite, pore structure, physical and chemical performance, carbon element content, specific surface area, stability, dispersion can not meet the requirement of industrialized production.Therefore, how to utilize a kind of technique simple, with low cost and biomass castoff is made loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite and had become as current main difficult technical by the method that can manufacture.
For above technological difficulties, pyrolysismethod because of have simple to operate, productivity is high, metal and nonmetal doping content is controlled, high-purity, carbonization rate high, be prone to the technological merit such as large-scale production and repetitive operation and be widely used.Pyrolysismethod is with biological material for carbon source, containing metal, nitrogenous nonmetallic compound respectively source metal and nitrogenous source, form precursor or non-homogeneous mixture through pre-prepared technique after, high temperature pyrolysis in specific inertia or reducing gas, produce biomass class nano composite material.ChunleiWang (TheJournalofPhysicalChemistryC, 2008,112 (45), 17596-17602), with Cotton Gossypii, filter paper and timber for raw material, impregnated in FeCl3Methanol solution in, be placed in pyrroles's atmosphere after drying, gas-phase polymerization formed precursor, through microwave-heating and nitric acid treatment, obtain porous carbon nano composite material；The method achieve the formation of porous nanometer structure, but the synthesis technique cycle is long, cost intensive, and nitric acid treatment makes carbon-coating original structure be destroyed, and has some limitations in actual applications.Patent No. CN104787747A discloses a kind of method preparing multi-walled carbon nano-tubes with biomass or carbon containing organic waste raw material, by microwave reinforced fast pyrogenation garbage, it is thus achieved that target product；This preparation technology is simple, pyrolysis is efficiently quick, but unrealized metallic is filled and nonmetal doping, and be confined to relatively low productivity, to raw-material selectivity etc..Wu-JunLiu etc. (EnvironmentScience&Technology, 2014,48 (23), 13951-13959) with sawdust and FeCl3For raw material, after forming preloaded precursor, pyrolysis under a nitrogen, it is thus achieved that a kind of porous carbon nanometer tube composite materials；The method is simple to operate, with low cost, but it is less than normal to be confined to product specific surface area, and carbon base body purity is low, unrealized nonmetal doping etc..
To sum up, the existing method preparing loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite, the aspects such as the prepared shape characteristic of CNT, pore structure, specific surface area, metal filled amount, carbon base body purity, physical and chemical performance do not reach the requirement of practical application, and precursor utilization rate is relatively low, it is not suitable for the industrialized production of waste resource.Therefore, one is with low cost, technique simple, and the method adapting to the loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite of batch production needs to be excavated.
Summary of the invention
It is desirable to provide a kind of method utilizing biomass castoff to prepare nitrogen-doped carbon nanometer pipe coating metal particles composite, to be solved is the technical barriers such as the preparation of functional living being matter carbon nano tube compound material, the formation of CNT coating metal nano granule structure, nitrogen element in-situ modification, and the technical disadvantages such as overcome preparation cost height, complex steps, productivity and purity in traditional preparation methods relatively low.
In order to solve above-mentioned technical problem, the technical scheme that the present invention takes is as follows:
As it is shown in figure 1, the present invention utilizes the method that biomass castoff prepares nitrogen-doped carbon nanometer pipe coating metal particles composite, it is characterized in that and carries out as follows:
(1) carbonization biomass castoff
Being added in the beaker containing deionized water with KOH by biomass castoff, stir at 25 DEG C (stirring 4～12 hours), dry, grinding, it is thus achieved that non-homogeneous mixture A；The uniform temperature zone that described non-homogeneous mixture A is placed in the tube type resistance furnace being connected with noble gas carries out carbonization, the pickling successively at normal temperatures of gained product, washing, dry, it is thus achieved that biomass carbon；
(2) nitrogen-doped carbon nanometer pipe coating metal particles composite is prepared in pyrolysis
The biomass carbon prepare step (1) and nitrogenous nonmetallic compound, water-soluble divalent metal add in the beaker containing methanol, stir (at temperature 25 DEG C magnetic agitation 4～8h), then dry, grind, it is thus achieved that non-homogeneous mixture B；The uniform temperature zone that described non-homogeneous mixture B is placed in the tube type resistance furnace being connected with noble gas is carried out pyrolysis, and products therefrom cleans, obtains the target product nitrogen-doped carbon nanometer pipe coating metal particles composite with loose structure after drying.
The present invention utilizes the method that biomass castoff prepares nitrogen-doped carbon nanometer pipe coating metal particles composite, and its feature lies also in:
In step (1), biomass castoff is 1:0.5～1:2 with the mass ratio of KOH；The amount ratio of KOH and deionized water is 1.78～3.56mol/L；In step (2), the amount ratio of biomass carbon and nitrogenous nonmetallic compound, water-soluble divalent metal is 0.1～0.4g:0.015～0.035mol:0.14～0.72mmol；The amount ratio of biomass carbon and methanol is 0.1～0.4g/100mL.
Biomass castoff described in step (1) is corn straw garbage, distiller grains garbage, Cunninghamia lanceolata (Lamb.) Hook. bits garbage or rice hull waste；Diluted acid used by pickling is at least one in hydrochloric acid, sulphuric acid, nitric acid and aqueous acetic acid, and concentration is 0.5～1.5mol/L.Nitrogenous nonmetallic compound described in step (2) is at least one in tripolycyanamide, dicyandiamide, carbamide, cyanamide and hexamethylenetetramine；Described water-soluble divalent metal is at least one in the solubility divalent salts of transition-metal Fe, Co and Ni.Noble gas used in step (1) and step (2) is high pure nitrogen.
Carbonization described in step (1) is to be warming up to 600～750 DEG C with the heating rate of 5～10 DEG C/min, then constant temperature carbonization 1～3 hour.The process of the pyrolysis described in step (2) is: be first warming up to 500～600 DEG C with the heating rate of 5～10 DEG C/min, constant temperature 1～3 hour；It is warming up to 700～900 DEG C again, constant temperature 1～2 hour with the heating rate of 5～10 DEG C/min.
Compared with existing technology and report, beneficial effects of the present invention is embodied in:
(1) present invention adopts two step pyrolytic processes to achieve the growth of CNT, has promoted the dispersion of metal nanoparticle and the formation of synergism mechanism；CNT coating metal nano granule structure, strengthens the stability of composite；The in-situ modification of nitrogen element, improves carbon-coating surface activity and dispersibility；The formation of abundant pore structure and high-specific surface area, improves contact, active sites is counted.Wherein, the pyrolytic reaction that graphite-phase carbide converted in-situ is CNT that the thermal polycondensation of biomass carbon material organic aromatic compounds is at high temperature reacted by metal nanoparticle and metal surface fusing precipitates out has double catalytic action, and carburizing temperature can be reduced, it is CNT growth in situ and the essential condition of synergistic mechanism formation；Secondly, metal ion is had a reduction at pyrolytic process by nitrogen-containing material, and graphite carbon-coating can carry out the in-situ modification of nitrogen, finally realizes the modification of metallic particles filling carbon nano-pipe, improves the redox catalysis activity of composite further.
(2) raw material in the present invention is natural biomass garbage cheap and easy to get, and wide material sources, potential using value are high.Not additionally introducing catalyst and carbon-source gas in whole preparation process, technique is simple, with low cost.KOH in the present invention serves the activation of biomass castoff, biomass castoff can be converted into by regulating and controlling the experiment condition such as carbonization reaction time and temperature there is high-specific surface area, abundant pore structure and the rich surface function Carbon Materials containing oxygen-containing functional group, and it serves carbonaceous sources, triple pivotal roles containing oxygen source and material support in subsequent synthetic processes.Secondly, in the preparation of the present invention, by regulating and controlling the technological parameter such as nitrogenous source and the consumption of source metal, pyrolysis reaction temperature and time, the fast pyrogenation of biomass castoff can be realized, and then make the gaseous product that pyrolysis produces can in the temperature adapted to interfacial reaction occurred in the shorter time, along with the continuity in response time, finally prepare target product.The present invention has opened up the new technology being prepared high added value carbon mano-tube composite by natural product, significantly reduces the cost of carbon nano-composite material, it will help promote the potential application of CNT.
(3) in the biomass class nano-functional material of present invention synthesis, CNT clad structure not only avoid environment and its interior metal nano-particle produce the impact of oxidation and acid and base effect, and it has machine-processed, the high specific surface area of excellent synergism and abundant pore structure, can be used for adsorbing material, electricity material (electrode, conduction, energy storage material), nano-device, catalysis material etc.；And the in-situ modification of nitrogen element makes the carbon back of nano composite material show more excellent properties, there is potential using value in fields such as electricity, optics, mechanics, biomedicines.By in loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite prepared by the present invention, CNT particle diameter is controlled in 15～80nm, high purity 85～95%, high degree of dispersion between granule, CNT excellent performance, and productivity is higher, it is adaptable to industrialized production.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Fig. 2 is the XRD photo of the loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite of the embodiment of the present invention 1 preparation, and as can be seen from the figure product has higher purity, and N element doping does not affect product crystal form.
Fig. 3 is the SEM photograph of the loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite of the embodiment of the present invention 1 preparation, it can be seen that this composite has porous/clad structure.
Fig. 4 is the TEM photo of the loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite of the embodiment of the present invention 1 preparation.
Detailed description of the invention
Present invention is described in detail by below example and accompanying drawing, but does not limit the scope of the invention.
Embodiment 1:
(1) carbonization distiller grains garbage: weigh 10.0g (0.1782mol) KOH and 10.0g distiller grains garbage, is mixed in the beaker containing 80mL deionized water by the two, continuously stirred 8h at 25 DEG C, dry, grinding, it is thus achieved that non-homogeneous mixture A；This non-homogeneous mixture A is placed in quartz boat; and quartz boat is moved to the flat-temperature zone of the tube type resistance furnace being connected with nitrogen protection gas; it is warming up to 750 DEG C with the heating rate of 10 DEG C/min; then constant temperature carbonization 2 hours; product concentration is dilute hydrochloric acid solution and the distilled water cleaning of 0.5mol/L, obtains distiller grains charcoal after drying.
(2) nitrogen-doped carbon nanometer pipe coating metal particles composite is prepared in pyrolysis
Weigh 0.2g distiller grains charcoal, 80.0mg (0.2878mmol) FeSO respectively4·7H2O and 4.0g (0.0317mol) tripolycyanamide；Being mixed in heterogeneous for three in the beaker containing 100mL methanol, magnetic agitation 5h makes three's mix homogeneously, then dries, grinds, it is thus achieved that non-homogeneous mixture B；This non-homogeneous mixture B is placed in quartz boat; and quartz boat is moved to the flat-temperature zone of the tube type resistance furnace being connected with nitrogen protection gas, it is warming up to 600 DEG C with the heating rate of 10 DEG C/min, constant temperature 3 hours; it is warming up to 900 DEG C again, constant temperature 1 hour with the heating rate of 10 DEG C/min.Question response terminates, and products therefrom cleans, dries, and namely obtains target product loose structure nitrogen-doped carbon nanometer pipe cladding Fe3O4Composite.
After tested, the specific surface area of composite obtained by the present embodiment is 680.703m2/ g, quality is 0.14g.
Fig. 2 is the XRD photo of target product prepared by the present embodiment, and as can be seen from the figure product has higher purity, and N element doping does not affect product crystal form.
Fig. 3 is the SEM photograph of target product prepared by the present embodiment, and Fig. 4 is the TEM photo of target product prepared by the present embodiment, and in as can be seen from the figure prepared product, biomass carbon nanotube is wrapped in metallic.
Embodiment 2:
(1) carbonization corn straw garbage: weigh 10.0g (0.1782mol) KOH and 10.0g corn straw garbage, the two is mixed in the beaker containing 80mL deionized water, continuously stirred 8h at 25 DEG C, dry, grinding, it is thus achieved that non-homogeneous mixture A；This non-homogeneous mixture A is placed in quartz boat; and quartz boat is moved to the flat-temperature zone of the tube type resistance furnace being connected with nitrogen protection gas; it is warming up to 750 DEG C with the heating rate of 10 DEG C/min; then constant temperature carbonization 2 hours; product concentration is dilute hydrochloric acid solution and the distilled water cleaning of 0.5mol/L, obtains corn straw charcoal after drying.
(2) nitrogen-doped carbon nanometer pipe coating metal particles composite is prepared in pyrolysis
Weigh 0.2g corn straw charcoal, 80.0mg (0.2878mmol) FeSO respectively4·7H2O and 4.0g (0.0317mol) tripolycyanamide；Being mixed in heterogeneous for three in the beaker containing 100mL methanol, magnetic agitation 5h makes three's mix homogeneously, then dries, grinds, it is thus achieved that non-homogeneous mixture B；This non-homogeneous mixture B is placed in quartz boat; and quartz boat is moved to the flat-temperature zone of the tube type resistance furnace being connected with nitrogen protection gas, it is warming up to 600 DEG C with the heating rate of 10 DEG C/min, constant temperature 3 hours; it is warming up to 900 DEG C again, constant temperature 1 hour with the heating rate of 10 DEG C/min.Question response terminates, and products therefrom cleans, dries, and namely obtains target product loose structure nitrogen-doped carbon nanometer pipe cladding Fe3O4Composite.
After tested, the specific surface area of composite obtained by the present embodiment is 588.633m2/ g, quality is～0.15g.
Embodiment 3:
(1) charring rice husk garbage: weigh 10.0g (0.1782mol) KOH and 10.0g rice hull waste, is mixed in the beaker containing 80mL deionized water by the two, continuously stirred 8h at 25 DEG C, dry, grinding, it is thus achieved that non-homogeneous mixture A；This non-homogeneous mixture A is placed in quartz boat; and quartz boat is moved to the flat-temperature zone of the tube type resistance furnace being connected with nitrogen protection gas; it is warming up to 750 DEG C with the heating rate of 10 DEG C/min; then constant temperature carbonization 2 hours; product concentration is dilute hydrochloric acid solution and the distilled water cleaning of 0.5mol/L, obtains rice hull carbon after drying.
(2) nitrogen-doped carbon nanometer pipe coating metal particles composite is prepared in pyrolysis
Weigh 0.2g rice hull carbon, 80.0mg (0.2878mmol) FeSO respectively4·7H2O and 4.0g (0.0317mol) tripolycyanamide；Being mixed in heterogeneous for three in the beaker containing 100mL methanol, magnetic agitation 5h makes three's mix homogeneously, then dries, grinds, it is thus achieved that non-homogeneous mixture B；This non-homogeneous mixture B is placed in quartz boat; and quartz boat is moved to the flat-temperature zone of the tube type resistance furnace being connected with nitrogen protection gas, it is warming up to 600 DEG C with the heating rate of 10 DEG C/min, constant temperature 3 hours; it is warming up to 900 DEG C again, constant temperature 1 hour with the heating rate of 10 DEG C/min.Question response terminates, and products therefrom cleans, dries, and namely obtains target product loose structure nitrogen-doped carbon nanometer pipe cladding Fe3O4Composite.
After tested, the specific surface area of composite obtained by the present embodiment is 541.764m2/ g, quality is～0.12g.
Embodiment 4:
(1) carbonization Cunninghamia lanceolata (Lamb.) Hook. bits garbage: weigh 10.0g (0.1782mol) KOH and 10.0g Cunninghamia lanceolata (Lamb.) Hook. bits garbage, the two is mixed in the beaker containing 80mL deionized water, continuously stirred 8h at 25 DEG C, dry, grinding, it is thus achieved that non-homogeneous mixture A；This non-homogeneous mixture A is placed in quartz boat; and quartz boat is moved to the flat-temperature zone of the tube type resistance furnace being connected with nitrogen protection gas; it is warming up to 750 DEG C with the heating rate of 10 DEG C/min; then constant temperature carbonization 2 hours; product concentration is dilute hydrochloric acid solution and the distilled water cleaning of 0.5mol/L, obtains Cunninghamia lanceolata (Lamb.) Hook. bits charcoal after drying.
(2) nitrogen-doped carbon nanometer pipe coating metal particles composite is prepared in pyrolysis
Weigh 0.2g Cunninghamia lanceolata (Lamb.) Hook. bits charcoal, 80.0mg (0.2878mmol) FeSO respectively4·7H2O and 4.0g (0.0317mol) tripolycyanamide；Being mixed in heterogeneous for three in the beaker containing 100mL methanol, magnetic agitation 5h makes three's mix homogeneously, then dries, grinds, it is thus achieved that non-homogeneous mixture B；This non-homogeneous mixture B is placed in quartz boat; and quartz boat is moved to the flat-temperature zone of the tube type resistance furnace being connected with nitrogen protection gas, it is warming up to 600 DEG C with the heating rate of 10 DEG C/min, constant temperature 3 hours; it is warming up to 900 DEG C again, constant temperature 1 hour with the heating rate of 10 DEG C/min.Question response terminates, and products therefrom cleans, dries, and namely obtains target product loose structure nitrogen-doped carbon nanometer pipe cladding Fe3O4Composite.
After tested, the specific surface area of composite obtained by the present embodiment is 662.213m2/ g, quality is 0.16g.
Embodiment 5:
The present embodiment is identical with the preparation method of embodiment 1, differs only in: the carbonization time in step (1) is 1h；Nitrogenous source selected by step (2) is carbamide, and selected water-soluble divalent metal is Co (NO3)2, prepare loose structure nitrogen-doped carbon nanometer pipe cladding cobalt/cobalt oxide composite.
After tested, the specific surface area of composite obtained by the present embodiment is 658.465m2/ g, quality is 0.11g.
Embodiment 6:
The present embodiment is identical with the preparation method of embodiment 1, differs only in: the carbonization time in step (1) is 3h；Nitrogenous source selected by step (2) is hexamethylenetetramine；The temperature control program of pyrolytic process is for being first warming up to 550 DEG C, constant temperature 2h, then is warming up to 800 DEG C, constant temperature 1h, prepares loose structure nitrogen-doped carbon nanometer pipe cladding silicon/iron oxide composite material.
After tested, the specific surface area of composite obtained by the present embodiment is 633.966m2/ g, quality is 0.16g.
Embodiment 7:
The present embodiment is identical with the preparation method of embodiment 2, differ only in: in step (2), the temperature control program of pyrolytic process is for being first warming up to 500 DEG C, constant temperature 1h, it is warming up to 700 DEG C, constant temperature 2h again, prepares loose structure nitrogen-doped carbon nanometer pipe cladding silicon/iron oxide composite material.
After tested, the specific surface area of composite obtained by the present embodiment is 577.477m2/ g, quality is 0.15g.
Embodiment 8:
The present embodiment is identical with the preparation method of embodiment 3, differs only in: in step (2), the mole of tripolycyanamide is 0.025mol, FeSO4·7H2The mole of O is 0.4mmol.
After tested, the specific surface area of composite obtained by the present embodiment is 593.329m2/ g, quality is 0.15g.
Embodiment 9:
The present embodiment is identical with the preparation method of embodiment 3, differs only in: the water-soluble divalent metal selected by step (2) is Co (NO3)2, prepare loose structure nitrogen-doped carbon nanometer pipe cladding cobalt/cobalt oxide composite.
After tested, the specific surface area of composite obtained by the present embodiment is 651.854m2/ g, quality is 0.12g.
Embodiment 10:
The present embodiment is identical with the preparation method of embodiment 4, differs only in: the water-soluble divalent metal selected by step (2) is NiCl2, prepare loose structure nitrogen-doped carbon nanometer pipe cladding nickel oxide composite.
After tested, the specific surface area of composite obtained by the present embodiment is 644.879m2/ g, quality is 0.14g.
Claims (8)
1. one kind utilizes the method that biomass castoff prepares nitrogen-doped carbon nanometer pipe coating metal particles composite, it is characterised in that carry out as follows:
(1) carbonization biomass castoff
Biomass castoff is added in the beaker containing deionized water with KOH, stirs at 25 DEG C, dry, grinding, it is thus achieved that non-homogeneous mixture A；The uniform temperature zone that described non-homogeneous mixture A is placed in the tube type resistance furnace being connected with noble gas carries out carbonization, the pickling successively at normal temperatures of gained product, washing, dry, it is thus achieved that biomass carbon；
(2) nitrogen-doped carbon nanometer pipe coating metal particles composite is prepared in pyrolysis
The biomass carbon prepare step (1) and nitrogenous nonmetallic compound, water-soluble divalent metal add in the beaker containing methanol, stir, and then dry, grind, it is thus achieved that non-homogeneous mixture B；The uniform temperature zone that described non-homogeneous mixture B is placed in the tube type resistance furnace being connected with noble gas is carried out pyrolysis, and products therefrom cleans, obtains the target product nitrogen-doped carbon nanometer pipe coating metal particles composite with loose structure after drying.
2. the method for claim 1, it is characterised in that: the biomass castoff described in step (1) is corn straw garbage, distiller grains garbage, Cunninghamia lanceolata (Lamb.) Hook. bits garbage or rice hull waste.
3. the method for claim 1, it is characterised in that: in step (1), biomass castoff is 1:0.5～1:2 with the mass ratio of KOH；The amount ratio of KOH and deionized water is 1.78～3.56mol/L；
In step (2), the amount ratio of biomass carbon and nitrogenous nonmetallic compound, water-soluble divalent metal is 0.1～0.4g:0.015～0.035mol:0.14～0.72mmol；The amount ratio of biomass carbon and methanol is 0.1～0.4g/100mL.
4. the method for claim 1, it is characterised in that: carbonization described in step (1) is to be warming up to 600～750 DEG C with the heating rate of 5～10 DEG C/min, then constant temperature carbonization 1～3 hour.
5. the method for claim 1, it is characterised in that: in step (1), diluted acid used by pickling is at least one in hydrochloric acid, sulphuric acid, nitric acid and aqueous acetic acid, and concentration is 0.5～1.5mol/L.
6. the method for claim 1, it is characterised in that: the nitrogenous nonmetallic compound described in step (2) is at least one in tripolycyanamide, dicyandiamide, carbamide, cyanamide and hexamethylenetetramine.
7. the method for claim 1, it is characterised in that: the water-soluble divalent metal described in step (2) is at least one in the solubility divalent salts of transition-metal Fe, Co and Ni.
8. the method for claim 1, it is characterised in that: the process of the pyrolysis described in step (2) is: be first warming up to 500～600 DEG C with the heating rate of 5～10 DEG C/min, constant temperature 1～3 hour；It is warming up to 700～900 DEG C again, constant temperature 1～2 hour with the heating rate of 5～10 DEG C/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397490A (en) * | 2001-12-28 | 2003-02-19 | 南京师范大学 | Carbon atom wire and process for preparing carbon nanotube and carbon atom wire by pyrolyzing solid-state carbon source |
| WO2004035883A2 (en) * | 2002-10-17 | 2004-04-29 | Nexen Nano Tech Co., Ltd | Fibrous nano-carbon and preparation method thereof |
| JP2007203223A (en) * | 2006-02-02 | 2007-08-16 | National Institute For Materials Science | Visible light-responsive titanium oxide-activated carbon composite photocatalyst and manufacturing method |
| CN101367515A (en) * | 2007-08-17 | 2009-02-18 | 北京化工大学 | Method for preparing metal filling carbon nano-pipe |
| CN102002652A (en) * | 2010-12-08 | 2011-04-06 | 上海交通大学 | Carbon nano tube reinforced metal matrix composite material and in-situ preparation method thereof |
| CN102821846A (en) * | 2009-12-18 | 2012-12-12 | 拜耳知识产权有限责任公司 | Nitrogen doped carbon nanotubes with metal nanoparticles |
| CN103072968A (en) * | 2013-01-25 | 2013-05-01 | 北京化工大学 | Carbon nano composite and preparation method thereof |
| CN103935978A (en) * | 2014-03-28 | 2014-07-23 | 新乡学院 | Nano carbon material prepared by pyrolysis of wheat straw and preparation method thereof |
| CN104787747A (en) * | 2015-04-10 | 2015-07-22 | 宁波诺丁汉大学 | Method for preparing multiwalled carbon nanotube through microwave enhanced fast pyrolysis of biomass and/or carbonaceous organic waste |
| CN105271229A (en) * | 2015-10-10 | 2016-01-27 | 华南理工大学 | Method for in-situ preparation of iron carbide filled doped carbon nanotube |
-
2016
- 2016-03-10 CN CN201610137714.6A patent/CN105772708B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397490A (en) * | 2001-12-28 | 2003-02-19 | 南京师范大学 | Carbon atom wire and process for preparing carbon nanotube and carbon atom wire by pyrolyzing solid-state carbon source |
| WO2004035883A2 (en) * | 2002-10-17 | 2004-04-29 | Nexen Nano Tech Co., Ltd | Fibrous nano-carbon and preparation method thereof |
| JP2007203223A (en) * | 2006-02-02 | 2007-08-16 | National Institute For Materials Science | Visible light-responsive titanium oxide-activated carbon composite photocatalyst and manufacturing method |
| CN101367515A (en) * | 2007-08-17 | 2009-02-18 | 北京化工大学 | Method for preparing metal filling carbon nano-pipe |
| CN102821846A (en) * | 2009-12-18 | 2012-12-12 | 拜耳知识产权有限责任公司 | Nitrogen doped carbon nanotubes with metal nanoparticles |
| CN102002652A (en) * | 2010-12-08 | 2011-04-06 | 上海交通大学 | Carbon nano tube reinforced metal matrix composite material and in-situ preparation method thereof |
| CN103072968A (en) * | 2013-01-25 | 2013-05-01 | 北京化工大学 | Carbon nano composite and preparation method thereof |
| CN103935978A (en) * | 2014-03-28 | 2014-07-23 | 新乡学院 | Nano carbon material prepared by pyrolysis of wheat straw and preparation method thereof |
| CN104787747A (en) * | 2015-04-10 | 2015-07-22 | 宁波诺丁汉大学 | Method for preparing multiwalled carbon nanotube through microwave enhanced fast pyrolysis of biomass and/or carbonaceous organic waste |
| CN105271229A (en) * | 2015-10-10 | 2016-01-27 | 华南理工大学 | Method for in-situ preparation of iron carbide filled doped carbon nanotube |
Non-Patent Citations (2)
| Title |
|---|
| MIAN LI,ET AL: "Iron and nitrogen co-doped carbon nanotube@hollow carbon fibers derived from plant biomass as efficient catalysts for the oxygen reduction reaction", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 张成铖: "生物质碳材料的制备及电化学性能", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112028054B (en) * | 2020-09-11 | 2022-07-19 | 辽宁科技大学 | Method for preparing ultra-long multi-walled carbon nano-tube by two-step microwave treatment of biomass |
| CN112331392A (en) * | 2020-11-18 | 2021-02-05 | 湖南华菱线缆股份有限公司 | Impact-resistant oxidation-resistant waterproof cable |
| CN113430565A (en) * | 2021-06-16 | 2021-09-24 | 江西师范大学 | Method for preparing carbon-based transition metal nano composite catalyst from tremella |
| CN113363450A (en) * | 2021-07-01 | 2021-09-07 | 齐鲁工业大学 | Preparation method of carbon nano tube coated high-nickel ternary cathode composite material |
| CN114804073A (en) * | 2022-03-29 | 2022-07-29 | 中国科学院广州能源研究所 | Biomass carbon nanotube and preparation method and application thereof |
| CN114804073B (en) * | 2022-03-29 | 2024-05-17 | 中国科学院广州能源研究所 | Biomass carbon nanotube and preparation method and application thereof |
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