CN105772708B - A kind of method that nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite is prepared using biomass castoff - Google Patents
A kind of method that nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite is prepared using biomass castoff Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a kind of method that nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite is prepared using biomass castoff, comprise the following steps：Biomass castoff and KOH are well mixed in deionized water first, obtained non-homogeneous mixture is carbonized under inert gas shielding, obtains biomass carbon；Then biomass carbon and nitrogenous nonmetallic compound, water-soluble divalent metal are well mixed in methyl alcohol, gained non-homogeneous mixture is pyrolyzed under inert gas shielding, that is, obtains target product.The present invention realizes the growth of CNT using two step pyrolytic processes, promotes scattered and synergy mechanism the formation of metal oxide nanoparticles；The structure of CNT coated metal oxide nano particle, strengthen the stability of composite；The in-situ modification of nitrogen, improve carbon-coating surface-active and dispersiveness；The formation of abundant pore structure and high-specific surface area, improve contact, active sites points.
Description
Technical field
The present invention relates to a kind of coated metal oxide particulate composite is prepared using biomass castoff for raw material
Method, belong to biomass castoff comprehensive utilizating research field.
Background technology
CNT causes worldwide extensive concern, in electricity because of its unique mechanics, electronics and chemical characteristic
The various fields such as the fields such as, optics, catalysis, biomedicine, which achieve, to be widely applied.In recent years, with to carbon nanomaterial
The popularization goed deep into and applied studied, simple, low cost, preparing carbon nano-composite material in batches, its is wide variety of as promotion
It is crucial.Biomass waste resource cheap and easy to get prepares carbon nano-composite material and had become in exploration and utilization nature
Scientist, the hot issue of engineer's extensive concern.
On the other hand, its performance can be obviously improved to the modification of CNT, is increasingly becoming carbon material in recent years and grinds
Study carefully one of the focus in field.The modification of CNT is broadly divided into：The outside modification of CNT, the doping of CNT and
The filling of tube cavity.The outside modification of CNT mainly splices other organic or oxygen-containing functions in the outer surface of CNT
Group, to improve its dispersiveness.And the doping of CNT is that other nonmetalloids are adulterated on graphitic carbon hexatomic ring, as nitrogen,
Phosphorus, boron etc..The doping of CNT can substantially change its electronics, mechanically and chemically vibration, property.The filling of CNT is then
It is that metal simple-substance, metallic compound etc. are filled inside its pipe, to effectively facilitate the electron motion characteristic of outer carbon nanotube.Its
In, doping and the performance raising filled to CNT are more notable, and the two combination can be lifted preferably into composite
Performance, such as Dehui Deng (Angewandte Chemie International Edition, 2013,52 (1), 371-
375) shown by experimental study and science textual criticism, the nitrogen doped carbon nanotube of iron filling has than the filling of independent iron or nitrogen-doped carbon
The more excellent redox catalysis performance of nanotube.However, how using a kind of technique is simple, cost is cheap, can manufacture
Method have become current facing challenges to synthesize the compound of nitrogen-doped carbon nanometer pipe coating metal nano granule structure.
On preparing loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite wood by raw material of biomass castoff
The method of material has arc discharge method, laser evaporization method, gas combustion method, chemical vapour deposition technique etc..Wherein, graphite acr method with
Equipment that laser evaporization method uses is complicated, technological parameter is not easy to adjust, energy expenditure is big, production cost is high, is unfavorable for a large amount of useless
Abandon biomass as resources.Gas combustion method, chemical vapour deposition technique then need to introduce high-purity carbon-source gas, reducing gas or indifferent gas
Body, catalyst, pre-prepared technique and synthesis step are cumbersome, and the pattern of prepared carbon nanomaterial, structure, distribution are dependent on urging
The self-characteristic of agent and matrix, suitable limitation be present.Meanwhile the pattern and structure of natural biomass discarded object differ,
Constituent is complicated, and impurity is more, if directly preparing nanometer tube composite materials using it as raw material, can produce a large amount of side reactions, causes
Make the carbon base body purity of prepared composite, pore structure, physical and chemical performance, carbon element content, specific surface area, stability, point
Divergence etc. can not meet the requirement of industrialized production.Therefore, how using a kind of technique is simple, cost is cheap and can batch
Loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite has been made in biomass castoff by the method for production
As current main difficult technical.
For above technological difficulties, pyrolysismethod because with it is simple to operate, yield is high, metal and nonmetal doping content
Controllable, high-purity, carbonization rate are high, are easy to large-scale production and the technological merit such as repeat and be widely used.Pyrolysismethod is
Using biological material as carbon source, it is respectively source metal and nitrogen source containing metal, nitrogenous nonmetallic compound, is formed through pre-prepared technique
After precursor or non-homogeneous mixture, it is pyrolyzed in specific inertia or reducing gas high temperature, it is nano combined produces biomass class
Material.Chunlei Wang(The Journal of Physical Chemistry C,2008,112(45),17596-
17602) using cotton, filter paper and timber as raw material, it is impregnated in FeCl3Methanol solution in, dry after be placed in pyrroles's atmosphere, gas
Phase-polymerization forms precursor, through microwave-heating and nitric acid treatment, obtains porous carbon nano-composite material；It the method achieve porous
The formation of nanostructured, but synthesis technique cycle length, it is costly, and nitric acid treatment is destroyed carbon-coating original structure,
Had some limitations in practical application.Patent No. CN104787747A discloses one kind with biomass or carbon containing organic waste
The method that thing raw material prepare multi-walled carbon nanotube, by microwave reinforced fast pyrogenation discarded object, obtain target product；The preparation
Technique is simple, pyrolysis is efficiently quick, but metallic filling and nonmetal doping is not implemented, and is confined to relatively low production
Rate, to selectivity of raw material etc..Wu-Jun Liu etc. (Environment Science＆Technology, 2014,48
(23), 13951-13959) with sawdust and FeCl3For raw material, after forming preloaded precursor, it is pyrolyzed, obtains a kind of under a nitrogen
Porous carbon nano tube compound material；This method is simple to operate, and cost is cheap, but it is less than normal to be confined to product specific surface area, carbon base body
Purity is low, and nonmetal doping etc. is not implemented.
To sum up, the existing method for preparing loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite, it is made
The shape characteristic of standby CNT, pore structure, specific surface area, metal filled amount, carbon base body purity, physical and chemical performance etc.
The requirement of practical application is not reached, and precursor utilization rate is relatively low, is not suitable for the industrialized production of waste resource.Therefore, one
Kind cost is cheap, technique is simple, adapts to the loose structure nitrogen-doped carbon nanometer pipe coating metal particles composite of batch production
Method need to be excavated.
The content of the invention
The present invention is intended to provide one kind prepares nitrogen-doped carbon nanometer pipe coated metal oxide using biomass castoff
The method of granules composite material, to be solved is preparation, the CNT cladding of functional living being matter carbon nano tube compound material
Metal receives the technical barriers such as the formation of oxide rice grain structure, nitrogen in-situ modification, and overcomes in traditional preparation methods and make
Standby cost height, complex steps, yield and the more low technical disadvantages of purity.
In order to solve the above-mentioned technical problem, the technical scheme that the present invention takes is as follows：
As shown in figure 1, the present invention prepares nitrogen-doped carbon nanometer pipe coated metal oxide particle using biomass castoff
The method of composite, its feature are to carry out as follows：
(1) biomass castoff is carbonized
Biomass castoff and KOH are added in the beaker containing deionized water, being stirred at 25 DEG C, (stirring 4~12 is small
When), dry, grinding, obtain non-homogeneous mixture A；The non-homogeneous mixture A is placed in the tubular electric resistance for being connected with inert gas
The uniform temperature zone of stove is carbonized, pickling, washing, the drying successively at normal temperatures of gained reaction product, obtains biomass carbon；
(2) pyrolysis prepares nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite
Biomass carbon and nitrogenous nonmetallic compound, water-soluble divalent metal prepared by step (1), which adds, contains methanol
Beaker in, stir (4~8h of magnetic agitation at 25 DEG C of temperature), then dries, grinds, obtains non-homogeneous mixture B；Will
The uniform temperature zone that the non-homogeneous mixture B is placed in the tube type resistance furnace for being connected with inert gas is pyrolyzed, and products therefrom cleaning, is done
The target product nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite with loose structure is obtained after dry.
The present invention prepares nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite using biomass castoff
Method, its feature are lain also in：
Biomass castoff and KOH mass ratio are 1 in step (1):0.5~1:2；KOH and deionized water amount ratio
For 1.78~3.56mol/L；Biomass carbon and nitrogenous nonmetallic compound, the dosage of water-soluble divalent metal in step (2)
Than for 0.1~0.4g：0.015~0.035mol：0.14~0.72mmol；The amount ratio of biomass carbon and methanol be 0.1~
0.4g/100mL。
Biomass castoff described in step (1) is maize straw discarded object, vinasse discarded object, Chinese fir consider discarded object to be worth doing or
Rice hull waste；Diluted acid used in pickling is at least one of hydrochloric acid, sulfuric acid, nitric acid and aqueous acetic acid, concentration is 0.5~
1.5mol/L。
Nitrogenous nonmetallic compound described in step (2) is melamine, dicyandiamide, urea, cyanamide and six methylenes
At least one of urotropine；Described water-soluble divalent metal is in the soluble divalent salts of transition-metal Fe, Co and Ni
At least one.Inert gas used is high pure nitrogen in step (1) and step (2).
Charing is to be warming up to 600~750 DEG C with 5~10 DEG C/min heating rate described in step (1), then constant temperature charcoal
Change 1~3 hour.The process of pyrolysis described in step (2) is：500 are warming up to 5~10 DEG C/min heating rate first~
600 DEG C, constant temperature 1~3 hour；700~900 DEG C are warming up to 5~10 DEG C/min heating rate again, constant temperature 1~2 hour.
Compared with existing technology and report, beneficial effects of the present invention are embodied in：
(1) present invention realizes the growth of CNT using two step pyrolytic processes, promotes metal oxide nano
Scattered and synergy mechanism the formation of grain；CNT coats metal nano oxide particle structure, strengthens composite wood
The stability of material；The in-situ modification of nitrogen, improve carbon-coating surface-active and dispersiveness；Abundant pore structure and high-ratio surface
Long-pending formation, improve contact, active sites points.Wherein, metal oxide nanoparticles are at high temperature to biomass carbon material
The graphite-phase carbide converted in-situ that the thermal polycondensation reaction and metal surface fusing of organic aromatic compounds separate out is CNT
Pyrolytic reaction there is double catalytic action, and carburizing temperature can be reduced, be CNT growth in situ and synergistic mechanism shape
Into necessary condition；Secondly, nitrogen-containing material has reduction to metal ion in pyrolytic process, and graphite carbon-coating can be carried out
The in-situ modification of nitrogen, the modification of metallic particles filling carbon nano-pipe is finally realized, further improve the redox of composite
Catalytic activity.
(2) raw material in the present invention is natural biomass discarded object cheap and easy to get, wide material sources, potential using value
It is high.Catalyst and carbon-source gas are not additionally introduced in whole preparation process, technique is simple, cost is cheap.KOH in the present invention
The activation of biomass castoff is served, can be by biomass by regulating and controlling the experiment conditions such as carbonization reaction time and temperature
Discarded object is converted into the function Carbon Materials that oxygen-containing functional group is rich in high-specific surface area, abundant pore structure and surface, and its
Carbonaceous sources, triple key effects containing oxygen source and material support are served in subsequent synthetic processes.Secondly, in the system of the present invention
In standby, the technological parameter such as dosage, pyrolysis reaction temperature and time by regulating and controlling nitrogen source and source metal, achievable biomass is discarded
The fast pyrogenation of thing, so allow gaseous product caused by pyrolysis the temperature of adaptation and in the shorter time occur interface it is anti-
Should, with the continuity in reaction time, finally prepare target product.The present invention has opened up to be received by natural products preparation high added value carbon
The new technology of mitron compound, significantly reduce the cost of carbon nano-composite material, it will help promote the potential of CNT
Using.
(3) in the biomass class nano-functional material that the present invention synthesizes, CNT clad structure not only avoid environment
Oxidation and the influence of acid and base effect are produced to its interior metal oxide nano particles, and it has excellent synergy machine
System, high specific surface area and abundant pore structure, available for sorbing material, electricity material (electrode, conduction, energy storage material),
Nano-device, catalysis material etc.；And the in-situ modification of nitrogen makes the carbon-based of nano composite material show more superiority
Can, there is potential application value in fields such as electricity, optics, mechanics, biomedicines.The loose structure prepared by the present invention
In nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite, CNT particle diameter is controllable in 15~80nm, purity
Up to 85~95%, high degree of dispersion between particle, CNT excellent performance, and yield is higher, suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Fig. 2 is loose structure nitrogen-doped carbon nanometer pipe coated metal oxide Particles dispersed prepared by the embodiment of the present invention 1
The XRD photos of material, as can be seen from the figure product there is higher purity, N element doping does not influence product crystalline form.
Fig. 3 is loose structure nitrogen-doped carbon nanometer pipe coated metal oxide Particles dispersed prepared by the embodiment of the present invention 1
The SEM photograph of material, it can be seen that the composite has porous/clad structure.
Fig. 4 is loose structure nitrogen-doped carbon nanometer pipe coated metal oxide Particles dispersed prepared by the embodiment of the present invention 1
The TEM photos of material.
Embodiment
Present invention is described in detail by following embodiment and accompanying drawing, but is not limited the scope of the invention.
Embodiment 1：
(1) vinasse discarded object is carbonized：10.0g (0.1782mol) KOH and 10.0g vinasse discarded objects are weighed, the two is mixed
In the beaker of the deionized water containing 80mL, 8h is persistently stirred at 25 DEG C, dries, grinding, obtains non-homogeneous mixture A；Should
Non-homogeneous mixture A is placed in quartz boat, and quartz boat is moved to the flat-temperature zone for the tube type resistance furnace for being connected with nitrogen protection gas, with
10 DEG C/min heating rate is warming up to 750 DEG C, and then constant temperature carbonizes 2 hours, the watery hydrochloric acid that product is 0.5mol/L with concentration
Solution and distilled water cleaning, obtain vinasse charcoal after drying.
(2) pyrolysis prepares nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite
0.2g vinasse charcoal, 80.0mg (0.2878mmol) FeSO are weighed respectively4·7H2O and 4.0g (0.0317mol) trimerization
Cyanamide；Be mixed in three is heterogeneous in the beaker of the methanol containing 100mL, magnetic agitation 5h is well mixed three, then drying,
Grinding, obtain non-homogeneous mixture B；Non-homogeneous mixture B is placed in quartz boat, and quartz boat is moved to and is connected with nitrogen guarantor
Protect the flat-temperature zone of the tube type resistance furnace of gas, 600 DEG C be warming up to 10 DEG C/min heating rate, constant temperature 3 hours, then with 10 DEG C/
Min heating rate is warming up to 900 DEG C, constant temperature 1 hour.Question response terminates, and products therefrom cleaning, drying, that is, obtains target production
Thing loose structure nitrogen-doped carbon nanometer pipe coats Fe3O4Composite.
After tested, the specific surface area of composite obtained by the present embodiment is 680.703m2/ g, quality 0.14g.
Fig. 2 is the XRD photos of target product manufactured in the present embodiment, and as can be seen from the figure product has higher pure
Degree, N element doping do not influence product crystalline form.
Fig. 3 is the SEM photograph of target product manufactured in the present embodiment, and Fig. 4 is the TEM of target product manufactured in the present embodiment
Photo, as can be seen from the figure biomass carbon nanotube is wrapped in metal oxide particle in prepared product.
Embodiment 2：
(1) maize straw discarded object is carbonized：10.0g (0.1782mol) KOH and 10.0g maize straw discarded objects are weighed, will
The two is mixed in the beaker of the deionized water containing 80mL, and 8h is persistently stirred at 25 DEG C, is dried, grinding, is obtained heterogeneous mixing
Thing A；Non-homogeneous mixture A is placed in quartz boat, and quartz boat is moved to the tube type resistance furnace for being connected with nitrogen protection gas
Flat-temperature zone, 750 DEG C are warming up to 10 DEG C/min heating rate, then constant temperature carbonizes 2 hours, and product is 0.5mol/L with concentration
Dilute hydrochloric acid solution and distilled water cleaning, after drying obtain maize straw charcoal.
(2) pyrolysis prepares nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite
0.2g maize straws charcoal, 80.0mg (0.2878mmol) FeSO are weighed respectively4·7H2O and 4.0g (0.0317mol)
Melamine；It is mixed in three is heterogeneous in the beaker of the methanol containing 100mL, magnetic agitation 5h is well mixed three, then
Drying, grinding, obtain non-homogeneous mixture B；Non-homogeneous mixture B is placed in quartz boat, and quartz boat is moved to and is connected with
The flat-temperature zone of the tube type resistance furnace of nitrogen protection gas, 600 DEG C are warming up to 10 DEG C/min heating rate, constant temperature 3 hours, then with
10 DEG C/min heating rate is warming up to 900 DEG C, constant temperature 1 hour.Question response terminates, and products therefrom cleaning, drying, that is, obtains mesh
Mark 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 are~0.15g.
Embodiment 3：
(1) charring rice husk discarded object：10.0g (0.1782mol) KOH and 10.0g rice hull wastes are weighed, the two is mixed
In the beaker of the deionized water containing 80mL, 8h is persistently stirred at 25 DEG C, dries, grinding, obtains non-homogeneous mixture A；Should
Non-homogeneous mixture A is placed in quartz boat, and quartz boat is moved to the flat-temperature zone for the tube type resistance furnace for being connected with nitrogen protection gas, with
10 DEG C/min heating rate is warming up to 750 DEG C, and then constant temperature carbonizes 2 hours, the watery hydrochloric acid that product is 0.5mol/L with concentration
Solution and distilled water cleaning, rice hull carbon is obtained after drying.
(2) pyrolysis prepares nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite
0.2g rice hull carbons, 80.0mg (0.2878mmol) FeSO are weighed respectively4·7H2O and 4.0g (0.0317mol) trimerization
Cyanamide；Be mixed in three is heterogeneous in the beaker of the methanol containing 100mL, magnetic agitation 5h is well mixed three, then drying,
Grinding, obtain non-homogeneous mixture B；Non-homogeneous mixture B is placed in quartz boat, and quartz boat is moved to and is connected with nitrogen guarantor
Protect the flat-temperature zone of the tube type resistance furnace of gas, 600 DEG C be warming up to 10 DEG C/min heating rate, constant temperature 3 hours, then with 10 DEG C/
Min heating rate is warming up to 900 DEG C, constant temperature 1 hour.Question response terminates, and products therefrom cleaning, drying, that is, obtains target production
Thing loose structure nitrogen-doped carbon nanometer pipe coats Fe3O4Composite.
After tested, the specific surface area of composite obtained by the present embodiment is 541.764m2/ g, quality are~0.12g.
Embodiment 4：
(1) Chinese fir bits discarded object is carbonized：10.0g (0.1782mol) KOH and 10.0g Chinese firs bits discarded object are weighed, incite somebody to action the two
It is mixed in the beaker of the deionized water containing 80mL, 8h is persistently stirred at 25 DEG C, dries, grinding, obtain non-homogeneous mixture A；
Non-homogeneous mixture A is placed in quartz boat, and quartz boat is moved to the constant temperature for the tube type resistance furnace for being connected with nitrogen protection gas
Area, 750 DEG C are warming up to 10 DEG C/min heating rate, then constant temperature carbonizes 2 hours, and product is the dilute of 0.5mol/L with concentration
Hydrochloric acid solution and distilled water cleaning, Chinese fir bits charcoal is obtained after drying.
(2) pyrolysis prepares nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite
0.2g Chinese firs bits charcoal, 80.0mg (0.2878mmol) FeSO are weighed respectively4·7H2O and 4.0g (0.0317mol) three
Poly cyanamid；It is mixed in three is heterogeneous in the beaker of the methanol containing 100mL, magnetic agitation 5h is well mixed three, then dries
Dry, grinding, obtains non-homogeneous mixture B；Non-homogeneous mixture B is placed in quartz boat, and quartz boat is moved to and is connected with nitrogen
The flat-temperature zone of the tube type resistance furnace of gas shielded gas, 600 DEG C are warming up to 10 DEG C/min heating rate, constant temperature 3 hours, then with 10
DEG C/min heating rate is warming up to 900 DEG C, constant temperature 1 hour.Question response terminates, and products therefrom cleaning, drying, that is, obtains target
Product loose structure nitrogen-doped carbon nanometer pipe coats Fe3O4Composite.
After tested, the specific surface area of composite obtained by the present embodiment is 662.213m2/ g, quality 0.16g.
Embodiment 5：
The present embodiment is identical with the preparation method of embodiment 1, differs only in：Carbonization time in step (1) is 1h；Step
Suddenly the nitrogen source selected by (2) is urea, and selected water-soluble divalent metal is Co (NO3)2, loose structure N doping is made
CNT coats cobalt/cobalt oxide composite.
After tested, the specific surface area of composite obtained by the present embodiment is 658.465m2/ g, quality 0.11g.
Embodiment 6：
The present embodiment is identical with the preparation method of embodiment 1, differs only in：Carbonization time in step (1) is 3h；Step
Suddenly the nitrogen source selected by (2) is hexa；The temperature control program of pyrolytic process is first to be warming up to 550 DEG C, constant temperature 2h,
800 DEG C, constant temperature 1h are warming up to again, and loose structure nitrogen-doped carbon nanometer pipe cladding silicon/iron oxide composite material is made.
After tested, the specific surface area of composite obtained by the present embodiment is 633.966m2/ g, quality 0.16g.
Embodiment 7：
The present embodiment is identical with the preparation method of embodiment 2, differs only in：The temperature control of pyrolytic process in step (2)
Processing procedure sequence is first to be warming up to 500 DEG C, constant temperature 1h, then is warming up to 700 DEG C, constant temperature 2h, and loose structure nitrogen-doped carbon nanometer pipe is made
Coat silicon/iron oxide composite material.
After tested, the specific surface area of composite obtained by the present embodiment is 577.477m2/ g, quality 0.15g.
Embodiment 8：
The present embodiment is identical with the preparation method of embodiment 3, differs only in：The mole of melamine in step (2)
For 0.025mol, FeSO4·7H2O mole is 0.4mmol.
After tested, the specific surface area of composite obtained by the present embodiment is 593.329m2/ g, quality 0.15g.
Embodiment 9：
The present embodiment is identical with the preparation method of embodiment 3, differs only in：Watersoluble divalent selected by step (2)
Metal salt is Co (NO3)2, loose structure nitrogen-doped carbon nanometer pipe cladding cobalt/cobalt oxide composite is made.
After tested, the specific surface area of composite obtained by the present embodiment is 651.854m2/ g, quality 0.12g.
Embodiment 10：
The present embodiment is identical with the preparation method of embodiment 4, differs only in：Watersoluble divalent selected by step (2)
Metal salt is NiCl2, loose structure nitrogen-doped carbon nanometer pipe cladding nickel oxide composite is made.
After tested, the specific surface area of composite obtained by the present embodiment is 644.879m2/ g, quality 0.14g.
Claims (5)
1. a kind of method that nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite is prepared using biomass castoff,
Characterized in that, carry out as follows：
(1) biomass castoff is carbonized
Biomass castoff and KOH are added in the beaker containing deionized water, stirred at 25 DEG C, dries, grinding, obtains non-
Homogeneous mixture A；The non-homogeneous mixture A uniform temperature zones for being placed in the tube type resistance furnace for being connected with inert gas are carbonized,
Pickling, washing and the drying successively at normal temperatures of gained reaction product, obtain biomass carbon；
(2) pyrolysis prepares nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite
Biomass carbon and nitrogenous nonmetallic compound and water-soluble divalent metal prepared by step (1) is added containing methanol
In beaker, stir, then dry, grind, obtain non-homogeneous mixture B；The non-homogeneous mixture B is placed in be connected with it is lazy
Property gas the uniform temperature zone of tube type resistance furnace be pyrolyzed, products therefrom cleaning and obtain the target with loose structure after drying
Product nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite；
Described nitrogenous nonmetallic compound be melamine, dicyandiamide, urea, cyanamide and hexa at least
It is a kind of；
Described water-soluble divalent metal is at least one of soluble divalent salts of transition-metal Fe, Co and Ni；
The process of pyrolysis described in step (2) is：500~600 DEG C are warming up to 5~10 DEG C/min heating rate first,
Constant temperature 1~3 hour；700~900 DEG C are warming up to 5~10 DEG C/min heating rate again, constant temperature 1~2 hour.
2. the method as described in claim 1, it is characterised in that：Biomass castoff described in step (1) is maize straw
Discarded object, vinasse discarded object, Chinese fir bits discarded object or rice hull waste.
3. the method as described in claim 1, it is characterised in that：Biomass castoff and KOH mass ratio are 1 in step (1):
0.5~1:2；KOH and the amount ratio of deionized water are 1.78~3.56mol/L；
In step (2) biomass carbon and the amount ratio of nitrogenous nonmetallic compound and water-soluble divalent metal be 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 as described in claim 1, it is characterised in that：Charing is with 5~10 DEG C/min heating described in step (1)
Speed is warming up to 600~750 DEG C, and then constant temperature carbonizes 1~3 hour.
5. the method as described in claim 1, it is characterised in that：Diluted acid used in pickling is hydrochloric acid, sulfuric acid, nitric acid in step (1)
At least one of with aqueous acetic acid, concentration is 0.5~1.5mol/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610137714.6A CN105772708B (en) | 2016-03-10 | 2016-03-10 | A kind of method that nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite is prepared using biomass castoff |
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| CN201610137714.6A CN105772708B (en) | 2016-03-10 | 2016-03-10 | A kind of method that nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite is prepared using biomass castoff |
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| CN105772708A CN105772708A (en) | 2016-07-20 |
| CN105772708B true CN105772708B (en) | 2018-02-02 |
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