CN106179200A - A kind of preparation method and applications of magnetic porous carbon based on native cellulose - Google Patents
A kind of preparation method and applications of magnetic porous carbon based on native cellulose Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of magnetic porous carbon based on native cellulose, first native cellulose is immersed in strong base solution, activate 0.5 ~ 24 hour, then neutrality it is washed to, filter, be dried, then be placed in the metal salt solution with catalytic action, stir 0.5 ~ 24 hours, through filtering, being dried, obtain cellulose/metal salt mixture presoma；By gained cellulose/metal salt mixture presoma under reducing atmosphere 400 ~ 1000 DEG C calcine 0.5 ~ 12 hour, naturally cool to room temperature, to obtain final product.Cheaper starting materials of the present invention, being easy to get, equipment and operation are simply, easily operate, pollution-free, low cost, it is easy to industrialization, large-scale production；The composite preparing gained has the character of magnetic Nano metal and porous carbon materials concurrently, meets absorbing material well to electromagnetic wave dissipation capabilities and the requirement of impedance matching, has the electro-magnetic wave absorption performance of excellence.
Description
Technical field
The invention belongs to technical field of composite materials, be specifically related to the system of a kind of magnetic porous carbon based on native cellulose
Preparation Method and application thereof.
Background technology
Cellulose is Renewable resource the abundantest on the earth, and native cellulose is cheap and easy to get, originates the abundantest.Its knot
Structure is β-(1 → 4)-dewatered grape glycopolymers.Because the response function of its uniqueness and molecular characterization, such as nontoxic, safety, biology
Degradability, hydrophilic and semi-rigid, cellulose, cellulose composite modification material and derivant product, except being used for weaving and making
Outside the traditional industries such as paper, also it is applied in fields such as food, daily-use chemical industry, medicine, building, biochemistrys.Meanwhile, often
The various discarded textiles in the year whole world but reach 30,000,000 tons, incredible amount.
Traditional waste textile processes approach to be had burning and buries, and on the one hand the burning of fiber can produce substantial amounts of flue dust
And toxic gas, cause atmospheric pollution；On the other hand, along with the minimizing of land resource, substantial amounts of textile solid waste is covered
Bury the waste that can cause land resource.Meanwhile, waste textile is dealt with improperly, also can pollute water resource.Therefore, efficiently
Utilize cellulose fibre and waste textile can save substantial amounts of resource, be of great immediate significance.In January, 2012,
In " textile industry " 12 " planning (2011-2015) " that the Ministry of Industry and Information Technology formulates, " waste and old spinning will be supported first
Fabric recycles " list in wherein.
In electromagnetic wave absorbent material research field, magnetic porous material with carbon element is the lightweight absorbing material of a kind of great potential,
It is constantly subjected to the extensive concern of people.From the point of view of inhaling ripple principle, magnetic porous carbon nano-composite material is a kind of great potential
Lightweight absorbing material, on the one hand, magnetic metal and material with carbon element all have certain electromagnetic wave dissipation capabilities, and the two is combined, can
To give material more electromagnetic wave dissipation mechanism, expand it and effectively inhale ripple frequency range.On the other hand, the loose structure of composite
It is possible not only to reduce the global density of material, is additionally favorable for improving the impedance matching behavior of material, thus contributes to electromagnetic wave and enter
To material internal.Additionally, magnetic porous carbon has the spies such as superhigh specific surface area, high pore volume, high adsorption capacity, magnetic is separable
Point, is a very effective material for water treatment of class.Preparation method about magnetic porous carbon is more, such as vapour deposition process, water
Full-boiled process, template etc., these method reaction raw materials and relatively costly, step is complicated, biological affine poor.
Cellulose macromolecule carbon content is the highest, is good carbon source, can obtain absorption property good after pyrolysis
Porous carbon materials.At present, prepare magnetic porous carbon composite with native cellulose for raw material and there is not yet document and patent report
Road.
Summary of the invention
Based on the deficiencies in the prior art, it is an object of the invention to provide a kind of magnetic porous carbon based on native cellulose
Preparation method and applications.
To achieve these goals, the technical solution used in the present invention is:
The preparation method of a kind of magnetic porous carbon based on native cellulose, comprises the following steps:
(1) native cellulose is placed in strong base solution, soaks 0.5 ~ 24 hour, be then washed to neutrality, filter, be dried,
To activated cellulose；
(2) being placed in the metal salt solution with catalytic action by step (1) gained activated cellulose, stirring reaction 0.5 ~ 24 is little
Time, through filtering, being dried, obtain cellulose/metal salt mixture presoma；
(3) by step (2) gained cellulose/metal salt mixture presoma under reducing atmosphere 400 ~ 1000 DEG C calcining 0.5 ~
12 hours, naturally cool to room temperature, to obtain final product；
Wherein, the one during described native cellulose is cotton fiber, linen, straw, bagasse and paper.
Preferably, described in step (1), highly basic is the one in sodium hydroxide, potassium hydroxide and Lithium hydrate.
Further, the molar concentration of described strong base solution is 0.5 ~ 10 mol/L.
Preferably, described in step (2), slaine is Nickel dichloride., nickel sulfate, nickel nitrate, cobalt nitrate, ferric nitrate, chlorination
One in ferrum, cobaltous chloride, iron sulfate, cobaltous sulfate, ferric acetyl acetonade, nickel acetate, cobalt acetate and sodium iron ethylenediaminetetraacetate or
Two or more.
Further, the molar concentration of described metal salt solution is 0.1 ~ 1.5 mol/L.In the present invention, native cellulose exists
Addition in strong base solution and activated cellulose addition in metal salt solution are without essential requirements, main by controlling
The concentration of strong base solution and the concentration of metal salt solution control the performance of products obtained therefrom.
Preferably, it is dried employing normal heating described in step (2) to be dried or atmospheric freeze drying.
Preferably, described in step (3), reducing atmosphere is hydrogen-argon-mixed atmosphere or ammonia atmosphere.
Based on native cellulose the magnetic porous carbon that above-mentioned preparation method obtains.
The aperture of described magnetic porous carbon is 10 nm ~ 3 μm, in magnetic porous carbon the particle diameter of magnetic metal particle be 50 ~
200 nm。
Above-mentioned magnetic porous carbon based on native cellulose is as wave absorbing agent application in electro-magnetic wave absorption.
The highly basic, the slaine that use in above-mentioned preparation method are common commercially available prod.
The present invention, under gentle reaction condition, with native cellulose as raw material, prepares the porous of high-specific surface area
Material with carbon element, in preparation process, the reduction of in-situ accomplishes metal ion, and well solve the chi of magnetic nanometer metal particle
Very little control and scattering problem；This preparation method cheaper starting materials, being easy to get, equipment and operation are simply, easily operate, pollution-free, low cost,
It is prone to industrialization, large-scale production.The composite preparing gained has the character of magnetic Nano metal and porous carbon materials concurrently, no
Only can be used as efficient absorption material in water treatment field, meet absorbing material the most well to electromagnetic wave dissipation capabilities and resistance
The requirement of anti-coupling, is only 5 ~ 10 wt% at filer content, i.e. has the electro-magnetic wave absorption performance of excellence, can absorb more than 90%
Electromagnetic wave energy, be the efficient and light weight absorbing material of a kind of great potential.The present invention the most only makes full use of waste and old fibre element
One new application approach of developing material, it is achieved that its recycling；Meanwhile, also it is electromagnetic wave absorbent material and adsorption material
The preparation of material provides new inexpensive raw material, reduces production cost, and therefore, the present invention processes for waste water and electromagnetic environment is dirty
The improvement of dye is significant.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the magnetic porous carbon that embodiment 1 prepares；
Fig. 2 is the transmission electron microscope picture of the magnetic porous carbon that embodiment 1 prepares；
Fig. 3 is the X ray diffracting spectrum of the magnetic porous carbon that embodiment 1 prepares；
Fig. 4 is the Raman spectrogram of the magnetic porous carbon that embodiment 1 prepares；
Fig. 5 is the embodiment 1 prepared magnetic porous carbon electro-magnetic wave absorption performance curve chart as wave absorbing agent；
Fig. 6 is the scanning electron microscope (SEM) photograph of the magnetic porous carbon that embodiment 2 prepares；
Fig. 7 is the scanning electron microscope (SEM) photograph of the magnetic porous carbon that embodiment 3 prepares；
Fig. 8 is the scanning electron microscope (SEM) photograph of the magnetic porous carbon that embodiment 4 prepares；
Fig. 9 is the scanning electron microscope (SEM) photograph of the magnetic porous carbon that embodiment 5 prepares；
Figure 10 is the XRD figure spectrum of the magnetic porous carbon that embodiment 5 prepares；
Figure 11 is the embodiment 5 prepared magnetic porous carbon electro-magnetic wave absorption performance curve chart as wave absorbing agent；
Figure 12 is the scanning electron microscope (SEM) photograph of the magnetic porous carbon that embodiment 6 prepares；
Figure 13 is the scanning electron microscope (SEM) photograph of the magnetic porous carbon that embodiment 7 prepares；
Figure 14 is the scanning electron microscope (SEM) photograph of the magnetic porous carbon that embodiment 8 prepares；
Figure 15 is the scanning electron microscope (SEM) photograph of the magnetic porous carbon that embodiment 9 prepares；
Figure 16 is the scanning electron microscope (SEM) photograph of the magnetic porous carbon that embodiment 10 prepares；
Figure 17 is the embodiment 10 prepared magnetic porous carbon electro-magnetic wave absorption performance curve chart as wave absorbing agent.
Detailed description of the invention
Below by way of preferred embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited to
This.
Embodiment 1
The preparation method of a kind of magnetic porous carbon based on native cellulose, comprises the following steps:
(1) 10 grams of cotton fibers being placed in 500 mL concentration is in 1 mol/L sodium hydroxide solution, soaks 4 hours so that it is cellulose
There is hydrolytic activation, then with distilled water, the cotton water after activation is washed till pH=7, filter, be dried, obtain activated cellulose；
(2) step (1) gained activated cellulose 5 grams is immersed in the nickel nitrate solution that 250 mL concentration are 0.5 mol/L, magnetic
Power stirs 24 hours, and through filtering, normal heating is dried, and obtains cellulose/metal salt mixture presoma；
(3) step (2) gained cellulose/metal salt mixture presoma is put in the Noah's ark cleaned up, Noah's ark is put in
The RC position of tube furnace quartz ampoule, is continually fed into ammonia, and regulation tube furnace makes it be warming up to 800 DEG C with 10 DEG C/min, protects
Temperature 4 hours, takes out after then naturally cooling to room temperature, to obtain final product.
Above-mentioned based on native cellulose the magnetic porous carbon prepared is carried out microscopic appearance sign, result such as Fig. 1
And shown in Fig. 2.Fig. 1 is SEM figure (scanning electron microscope (SEM) photograph) of magnetic porous carbon, and Fig. 2 is that the TEM of magnetic porous carbon schemes (transmission electron microscope
Figure), there it can be seen that obtained material is porous material, and it is evenly distributed with nano-metal particle, magnetic porous carbon
Aperture is about 1 μm, and the particle diameter of magnetic metal particle is about 100 nm.The magnetic porous carbon of gained is carried out X-ray diffraction
(XRD) analyze, as it is shown on figure 3, XRD figure is composed 2θ=45.1 °, 52.4 °, all have the appearance of diffraction maximum at 76.5 °, and three are spread out
Penetrate peak and correspond respectively to (111), (200) and (220) three crystal faces of face-centered cubic nickel, there is no the appearance at other miscellaneous peak.To institute
The magnetic porous carbon obtained enters Raman (Raman) spectrum analysis, and as shown in Figure 4, what in Raman spectrogram, D peak represented is C atom
Lattice defect, G peak represent C atom at SP2Stretching vibration in hydridization face, therefore, may certify that institute from Raman spectrogram
Obtain the existence of carbon in magnetic porous carbon.
The magnetic porous carbon of above-mentioned gained is mixed with paraffin, makes standard rings and carry out electromagnetic performance test, standard sample
In ring, the content of magnetic porous carbon is 10 wt%.According to transmission line theory, utilize the electromagnetic performance that test obtains to different-thickness
The absorbing property of model is fitted.Result is as it is shown in figure 5, when model thickness is at 2 ~ 5 mm, at the widest band limits, its
Reflectance peak is below-10dB(and namely absorbs the electromagnetic wave energy of more than 90%), this illustrates that this magnetic porous carbon has
Preferably electro-magnetic wave absorption performance.
Taking in the organic wastewater of magnetic porous carbon addition experimental simulation of above-mentioned gained, the addition of magnetic porous carbon is
2.0g/L, organic wastewater is rhodamine B solution, records with ultraviolet spectrophotometer, and at 550 nm, rhodamine B solution initiates
Absorbance be 0.98, after adding magnetic porous carbon, start stirring, start simultaneously at timing, react and sample after 2 min, through filtering
Recording the absorbance of filtrate at 550 nm is 0.49, samples, record filtrate at 550 nm through filtering after reacting 30 min
Absorbance is 0.32.This illustrates that magnetic porous carbon can organic pollution in active adsorption organic wastewater.
Embodiment 2
The preparation method of a kind of magnetic porous carbon based on native cellulose, comprises the following steps:
(1) 10 grams of Caulis et Folium Lini being placed in 500 mL concentration is in 2 mol/L lithium hydroxide solutions, soaks 12 hours so that it is cellulose
There is hydrolytic activation, then with distilled water, the Caulis et Folium Lini after activation is washed to pH=7, filter, be dried, obtain activated cellulose；
(2) step (1) gained activated cellulose 5 grams is immersed in the cobalt acetate solution that 250 mL concentration are 0.5 mol/L, super
Continuing mechanical agitation 4 hours after sound 30min, through filtering, normal heating is dried, and obtains cellulose/metal salt mixture presoma；
(3) step (2) gained cellulose/metal salt mixture presoma is put in the Noah's ark cleaned up, Noah's ark is put in
The RC position of tube furnace quartz ampoule, is continually fed into ammonia, and regulation tube furnace makes it be warming up to 800 DEG C with 10 DEG C/min, protects
Temperature 4 hours, takes out after then naturally cooling to room temperature, to obtain final product.
As shown in Figure 6, magnetic is many for the scanning electron microscope (SEM) photograph of above-mentioned based on native cellulose the magnetic porous carbon prepared
The aperture of hole carbon is 0.5 ~ 1 μm, and the particle diameter of magnetic metal particle is about 100 nm.By magnetic porous carbon and the ring of above-mentioned gained
Epoxy resins mixes, and makes the standard sample of photo that thickness is 2mm and carries out electro-magnetic wave absorption test, and in print, the content of magnetic porous carbon is
10 wt%, the electromagnetic wave energy of absorbable more than 90%.
Embodiment 3
The preparation method of a kind of magnetic porous carbon based on native cellulose, comprises the following steps:
(1) 10 grams of Boehmerias being placed in 250 mL concentration is in 1 mol/L potassium hydroxide solution, soaks 4 hours, to remove Boehmeria table
The impurity in face, and make its cellulose generation hydrolytic activation, then with distilled water, the Boehmeria after activation is washed to pH=7, filter,
It is dried, obtains activated cellulose；
(2) step (1) gained activated cellulose 5 grams is immersed in the iron nitrate solution that 250 mL concentration are 0.5 mol/L, machine
Tool stirs 8 hours, and through filtering, normal heating is dried, and obtains cellulose/metal salt mixture presoma；
(3) step (2) gained cellulose/metal salt mixture presoma is put in the Noah's ark cleaned up, Noah's ark is put in
The RC position of tube furnace quartz ampoule, is continually fed into ammonia, and regulation tube furnace makes it be warming up to 800 DEG C with 10 DEG C/min, protects
Temperature 4 hours, takes out after then naturally cooling to room temperature, to obtain final product.
The scanning electron microscope (SEM) photograph of above-mentioned based on native cellulose the magnetic porous carbon prepared is as it is shown in fig. 7, magnetic is many
The aperture of hole carbon is about 1 μm, and the particle diameter of magnetic metal particle is about 200 nm.By magnetic porous carbon and the epoxy of above-mentioned gained
Mixed with resin, makes the standard sample of photo that thickness is 2mm and carries out electro-magnetic wave absorption test, and in print, the content of magnetic porous carbon is 10
Wt%, the electromagnetic wave energy of absorbable more than 90%.
Embodiment 4
The preparation method of a kind of magnetic porous carbon based on native cellulose, comprises the following steps:
(1) 10 grams of corn straw being placed in 500 mL concentration is in 5 mol/L sodium hydroxide solutions, soaks 12 hours, to remove
The impurity on corn straw surface, and make its cellulose generation hydrolytic activation, then with distilled water by the corn straw water after activation
It is washed till pH=7, filters, be dried, obtain activated cellulose；
(2) step (1) gained activated cellulose 5 grams is immersed in the ferric chloride solution that 250 mL concentration are 0.5 mol/L, adopts
Stirring 4 hours with cutter, through filtering, normal heating is dried, and obtains cellulose/metal salt mixture presoma；
(3) step (2) gained cellulose/metal salt mixture presoma is put in the Noah's ark cleaned up, Noah's ark is put in
The RC position of tube furnace quartz ampoule, is continually fed into ammonia, and regulation tube furnace makes it be warming up to 800 DEG C with 10 DEG C/min, protects
Temperature 6 hours, takes out after then naturally cooling to room temperature, to obtain final product.
As shown in Figure 8, magnetic is many for the scanning electron microscope (SEM) photograph of above-mentioned based on native cellulose the magnetic porous carbon prepared
The aperture of hole carbon is 0.1 ~ 0.5 μm, and the particle diameter of magnetic metal particle is about 200 nm.By the magnetic porous carbon of above-mentioned gained
Mixing with epoxy resin, make the standard sample of photo that thickness is 2mm and carry out electro-magnetic wave absorption test, in print, magnetic porous carbon contains
Amount is 10 wt%, the electromagnetic wave energy of absorbable more than 90%.
Embodiment 5
The preparation method of a kind of magnetic porous carbon based on native cellulose, comprises the following steps:
(1) 10 grams of straws being placed in 500 mL concentration is in 7 mol/L sodium hydroxide solutions, soaks 6 hours, to remove straw table
The impurity in face, and make its cellulose generation hydrolytic activation, then with distilled water, the straw after activation is washed to pH=7, filter,
It is dried, obtains activated cellulose；
(2) step (1) gained activated cellulose 5 grams is immersed in the nickel nitrate solution that 300 mL concentration are 1.5 mol/L, super
Sound 2 hours, through filtering, normal heating is dried, and obtains cellulose/metal salt mixture presoma；
(3) step (2) gained cellulose/metal salt mixture presoma is put in the Noah's ark cleaned up, Noah's ark is put in
The RC position of tube furnace quartz ampoule, is continually fed into the mixed gas of hydrogen, argon, and regulation tube furnace makes it with 10 DEG C/min
It is warming up to 1000 DEG C, is incubated 2 hours, take out after then naturally cooling to room temperature, to obtain final product.
The scanning electron microscope (SEM) photograph of above-mentioned based on native cellulose the magnetic porous carbon prepared is as it is shown in figure 9, magnetic is many
The aperture of hole carbon is about 1 μm, and the particle diameter of magnetic-particle is about 200 nm.The magnetic porous carbon of gained is carried out X-ray diffraction
(XRD) analyzing, as shown in Figure 10, XRD figure is composed 2θ=45.1 °, 52.4 °, all have the appearance of diffraction maximum, and three at 76.5 °
Diffraction maximum corresponds respectively to (111), (200) and (220) three crystal faces of face-centered cubic nickel, does not has the appearance at other miscellaneous peak；2
There is the appearance of graphitization diffraction maximum at θ=26.5 °, illustrate that magnetic metal nickel has certain promotion and makees the graphitization of material with carbon element
With.
The magnetic porous carbon of above-mentioned gained is mixed with paraffin, makes standard rings and carry out electromagnetic performance test, standard sample
In ring, the content of magnetic porous carbon is 5 wt%.According to transmission line theory, utilize the electromagnetic performance that test obtains to different-thickness sample
The absorbing property of plate is fitted.Result as shown in figure 11, when model thickness is at 2 ~ 5 mm, at the widest band limits, its
Reflectance peak is below-10dB(and namely absorbs the electromagnetic wave energy of more than 90%), this illustrates that this magnetic porous carbon has
Preferably electro-magnetic wave absorption performance.
Embodiment 6
The preparation method of a kind of magnetic porous carbon based on native cellulose, comprises the following steps:
(1) 10 grams of Caulis et Folium Oryzaes being placed in 500 mL concentration is in 3 mol/L sodium hydroxide solutions, soaks 6 hours, to remove Caulis et Folium Oryzae table
The impurity in face, and make its cellulose generation hydrolytic activation, then with distilled water, the Caulis et Folium Oryzae after activation is washed to pH=7, filter,
It is dried, obtains activated cellulose；
(2) step (1) gained activated cellulose 5 grams is immersed in the EDTA-Fe that 200 mL concentration are 0.1 mol/L
In sodium solution, cutter stirs 8 hours, and through filtering, normal heating is dried, and obtains cellulose/metal salt mixture presoma；
(3) step (2) gained cellulose/metal salt mixture presoma is put in the Noah's ark cleaned up, Noah's ark is put in
The RC position of tube furnace quartz ampoule, is continually fed into the mixed gas of hydrogen, argon, and regulation tube furnace makes it with 10 DEG C/min
It is warming up to 400 DEG C, is incubated 4 hours, take out after then naturally cooling to room temperature, to obtain final product.
As shown in figure 12, magnetic is many for the scanning electron microscope (SEM) photograph of above-mentioned based on native cellulose the magnetic porous carbon prepared
The aperture of hole carbon is 50 ~ 200 nm, and the particle diameter of magnetic metal particle is 50 ~ 100 nm.By the magnetic porous carbon of above-mentioned gained with
Epoxy resin mixes, and makes the standard sample of photo that thickness is 3mm and carries out electro-magnetic wave absorption test, the content of magnetic porous carbon in print
It is 10 wt%, the electromagnetic wave energy of absorbable more than 90%.
Embodiment 7
The preparation method of a kind of magnetic porous carbon based on native cellulose, comprises the following steps:
(1) 10 grams of bagasse being placed in 500 mL concentration is in 5 mol/L sodium hydroxide solutions, soaks 12 hours, sweet to remove
The impurity on bagasse surface, and make its cellulose generation hydrolytic activation, then with distilled water, the bagasse after activation is washed to pH=
7, filter, be dried, obtain activated cellulose；
(2) step (1) gained activated cellulose 5 grams is immersed in the mixed solution of 300 mL nickel nitrates and Nickel dichloride., machinery
Stirring 8 hours, through filtering, normal heating is dried, and obtains cellulose/metal salt mixture presoma；Wherein, nickel nitrate and chlorination
In the mixed solution of nickel, the molar concentration of nickel nitrate and Nickel dichloride. is 0.15 mol/L；
(3) step (2) gained cellulose/metal salt mixture presoma is put in the Noah's ark cleaned up, Noah's ark is put in
The RC position of tube furnace quartz ampoule, is continually fed into the mixed gas of hydrogen, argon, and regulation tube furnace makes it with 10 DEG C/min
It is warming up to 600 DEG C, is incubated 4 hours, take out after then naturally cooling to room temperature, to obtain final product.
As shown in figure 13, magnetic is many for the scanning electron microscope (SEM) photograph of above-mentioned based on native cellulose the magnetic porous carbon prepared
The aperture of hole carbon is 50 nm ~ 1 μm, and the particle diameter of magnetic metal particle is about 100 nm.By the magnetic porous carbon of above-mentioned gained with
Epoxy resin mixes, and makes the standard sample of photo that thickness is 3mm and carries out electro-magnetic wave absorption test, the content of magnetic porous carbon in print
It is 8 wt%, the electromagnetic wave energy of absorbable more than 90%.
Embodiment 8
The preparation method of a kind of magnetic porous carbon based on native cellulose, comprises the following steps:
(1) 10 grams of paper being placed in 500 mL concentration is in 2 mol/L sodium hydroxide solutions, soaks 10 hours, to remove paper
The impurity on surface, and make its cellulose generation hydrolytic activation, then with distilled water, the paper after activation is washed to pH=7, mistake
Filter, be dried, obtain activated cellulose；
(2) step (1) gained activated cellulose 5 grams is immersed in the Ni-acetate solution that 300 mL concentration are 0.5 mol/L, machine
Tool stirs 8 hours, through filtration, atmospheric freeze drying, obtains cellulose/metal salt mixture presoma；
(3) step (2) gained cellulose/metal salt mixture presoma is put in the Noah's ark cleaned up, Noah's ark is put in
The RC position of tube furnace quartz ampoule, is continually fed into the mixed gas of hydrogen, argon, and regulation tube furnace makes it with 10 DEG C/min
It is warming up to 1000 DEG C, is incubated 1 hour, take out after then naturally cooling to room temperature, to obtain final product.
As shown in figure 14, magnetic is many for the scanning electron microscope (SEM) photograph of above-mentioned based on native cellulose the magnetic porous carbon prepared
The aperture of hole carbon is about 2 μm, and the particle diameter of magnetic metal particle is 100 ~ 200 nm.By magnetic porous carbon and the epoxy of above-mentioned gained
Mixed with resin, makes the standard sample of photo that thickness is 2 mm, carries out electro-magnetic wave absorption test, and in standard sample of photo, magnetic porous carbon contains
Amount is 5 wt%, the electromagnetic wave energy of absorbable more than 90%.
Embodiment 9
The preparation method of a kind of magnetic porous carbon based on native cellulose, comprises the following steps:
(1) 10 grams of cotton fiber being placed in 500 mL concentration is in 3 mol/L sodium hydroxide solutions, soaks 10 hours, to remove cotton
The impurity of fiber surface, and make its cellulose generation hydrolytic activation, then with distilled water, the paper after activation is washed to pH=7,
Filter, be dried, obtain activated cellulose；
(2) step (1) gained activated cellulose 5 grams is immersed in the nickel nitrate solution that 300 mL concentration are 0.2 mol/L, machine
Tool stirs 12 hours, and through filtering, normal heating is dried, and obtains cellulose/metal salt mixture presoma；
(3) step (2) gained cellulose/metal salt mixture presoma is put in the Noah's ark cleaned up, Noah's ark is put in
The RC position of tube furnace quartz ampoule, is continually fed into ammonia, and regulation tube furnace makes it be warming up to 800 DEG C with 10 DEG C/min, protects
Temperature 4 hours, takes out after then naturally cooling to room temperature, to obtain final product.
As shown in figure 15, magnetic is many for the scanning electron microscope (SEM) photograph of above-mentioned based on native cellulose the magnetic porous carbon prepared
The aperture of hole carbon is about 0.3 μm, and the particle diameter of magnetic metal particle is about 100 nm.By magnetic porous carbon and the ring of above-mentioned gained
Epoxy resins mixes, and makes the standard sample of photo that thickness is 3 mm and carries out electro-magnetic wave absorption test, the content of magnetic porous carbon in print
It is 10 wt%, the electromagnetic wave energy of absorbable more than 90%.
Embodiment 10
The preparation method of a kind of magnetic porous carbon based on native cellulose, comprises the following steps:
(1) 8 grams of cotton fiber being placed in 500 mL concentration is in 3 mol/L sodium hydroxide solutions, soaks 10 hours, cotton fine to remove
The impurity in dimension table face, and make its cellulose generation hydrolytic activation, then with distilled water, the cotton water after activation is washed till pH=7, mistake
Filter, be dried, obtain activated cellulose；
(2) step (1) gained activated cellulose 5 grams is immersed in the nickel nitrate solution that 300 mL concentration are 1.0 mol/L, machine
Tool stirs 12 hours, and through filtering, normal heating is dried, and obtains cellulose/metal salt mixture presoma；
(3) step (2) gained cellulose/metal salt mixture presoma is put in the Noah's ark cleaned up, Noah's ark is put in
The RC position of tube furnace quartz ampoule, is continually fed into ammonia, and regulation tube furnace makes it be warming up to 800 DEG C with 10 DEG C/min, protects
Temperature 4 hours, takes out after then naturally cooling to room temperature, to obtain final product.
As shown in figure 16, magnetic is many for the scanning electron microscope (SEM) photograph of above-mentioned based on native cellulose the magnetic porous carbon prepared
The aperture of hole carbon is about 0.5 μm, and the particle diameter of magnetic metal particle is 50 ~ 200 nm.By magnetic porous carbon and the stone of above-mentioned gained
Wax mixes, and makes standard rings and carries out electromagnetic performance test, and in standard rings, the content of magnetic porous carbon is 5 wt%.According to biography
Defeated lineation opinion, the absorbing property of different-thickness model is fitted by the electromagnetic performance utilizing test to obtain.Result such as Figure 17 institute
Showing, when model thickness is at 2 ~ 5 mm, at the widest band limits, its reflectance peak is below-10dB(and namely absorbs
The electromagnetic wave energy of more than 90%), this illustrates that this magnetic porous carbon has preferable electro-magnetic wave absorption performance.
Claims (10)
1. the preparation method of a magnetic porous carbon based on native cellulose, it is characterised in that comprise the following steps:
(1) native cellulose is placed in strong base solution, soaks 0.5 ~ 24 hour, be then washed to neutrality, filter, be dried,
To activated cellulose；
(2) being placed in the metal salt solution with catalytic action by step (1) gained activated cellulose, stirring reaction 0.5 ~ 24 is little
Time, through filtering, being dried, obtain cellulose/metal salt mixture presoma；
(3) by step (2) gained cellulose/metal salt mixture presoma under reducing atmosphere 400 ~ 1000 DEG C calcining 0.5 ~
12 hours, naturally cool to room temperature, to obtain final product；
Wherein, the one during described native cellulose is cotton fiber, linen, straw, bagasse and paper.
The preparation method of magnetic porous carbon based on native cellulose the most according to claim 1, it is characterised in that: step
(1) highly basic described in is the one in sodium hydroxide, potassium hydroxide and Lithium hydrate.
The preparation method of magnetic porous carbon based on native cellulose the most according to claim 2, it is characterised in that: described
The molar concentration of strong base solution is 0.5 ~ 10 mol/L.
The preparation method of magnetic porous carbon based on native cellulose the most according to claim 1, it is characterised in that: step
(2) slaine described in is Nickel dichloride., nickel sulfate, nickel nitrate, cobalt nitrate, ferric nitrate, iron chloride, cobaltous chloride, iron sulfate, sulphuric acid
One or more in cobalt, ferric acetyl acetonade, nickel acetate, cobalt acetate and sodium iron ethylenediaminetetraacetate.
The preparation method of magnetic porous carbon based on native cellulose the most according to claim 4, it is characterised in that: described
The molar concentration of metal salt solution is 0.1 ~ 1.5 mol/L.
The preparation method of magnetic porous carbon based on native cellulose the most according to claim 1, it is characterised in that: step
(2) it is dried described in and uses normal heating to be dried or atmospheric freeze drying.
The preparation method of magnetic porous carbon based on native cellulose the most according to claim 1, it is characterised in that: step
(3) reducing atmosphere described in is hydrogen-argon-mixed atmosphere or ammonia atmosphere.
8. use based on native cellulose the magnetic porous carbon that the arbitrary described preparation method of claim 1 to 7 obtains.
Magnetic porous carbon based on native cellulose the most according to claim 8, it is characterised in that: described magnetic porous carbon
Aperture be 10 nm ~ 3 μm, in magnetic porous carbon, the particle diameter of magnetic metal particle is 50 ~ 200 nm.
10. based on native cellulose the magnetic porous carbon described in claim 8 is as wave absorbing agent answering in electro-magnetic wave absorption
With.
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| CN111303833B (en) * | 2020-03-12 | 2022-12-16 | 西安工程大学 | Preparation method of cobalt-iron alloy/porous carbon electromagnetic wave absorption composite material |
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