CN103072968B - Carbon nano composite and preparation method thereof - Google Patents
Carbon nano composite and preparation method thereof Download PDFInfo
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- CN103072968B CN103072968B CN201310030857.3A CN201310030857A CN103072968B CN 103072968 B CN103072968 B CN 103072968B CN 201310030857 A CN201310030857 A CN 201310030857A CN 103072968 B CN103072968 B CN 103072968B
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Abstract
The invention relates to a carbon nano composite and a preparation method thereof. The carbon nano composite comprises a carbon nano material and metal particles, wherein the carbon nano material is subjected to surface functionalization, and the metal particles are formed on the carbon nano material. The carbon nano composite can be used for removing pollutants in waste water, and a removal effect is significantly better than that of the existing nano material.
Description
Technical field
The present invention relates to carbon nano-composite material and preparation method thereof.
Background technology
Carbon nanomaterial has unique structure because of it and excellent electricity, optics, thermodynamic property and mechanical property are widely used in multiple fields such as electrode, stored energy, support of the catalyst, filtration unit.When carbon material and metal or metal oxide being combined with each other, can be used as magneticsubstance again, catalyzer and chemical sensor etc.
The method preparing carbon nanomaterial at present mainly comprises arc discharge method, Laser vaporization, chemical Vapor deposition process.Wherein arc discharge method and Laser vaporization are because of apparatus expensive, consume energy high, the shortcomings such as impurity in products is many limit its application in the industrial production, chemical Vapor deposition process prepare in carbon nanotube process need first with reducing gas under the high temperature conditions by catalyst reduction out, and easily produce carbon granule in preparation process, impurity such as decolorizing carbon and there is certain problem.Solid-state pyrolysis Organometallic precursor legal system for carbon material because the simple and productive rate high of its preparation becomes the study hotspot of people in recent years.The people such as Zhi deliver many sections of articles and report solid-state pyrolysis organometallic complex and preparing the application in carbon nanotube and nanocarbon/metal nano composite material.As document small2005,1:210 – 212, small2005,1:798 – 801, Adv.Mater.2008,20:1727 – 1731 etc.But the precursor adopted in aforesaid method is complicated organometallic complex, front production procedure is complicated, and the use of organic reagent is to bad environmental, and temperature required height in pyrolytic process, time are long.
In addition, because the consistency of carbon nanotube extreme difference and dispersiveness make it easily produce from being wound around or agglomeration, thus its practical application is limited.For this reason, people are by direct fluoridation, acidification reaction, free radical reaction, the multiple method such as electrochemical reaction carries out modification to carbon nano tube surface, but it is loaded down with trivial details that aforesaid method exists reactions steps all in various degree, reaction time is long, cost is high, environmental-protecting performance is poor, functionalization degree is low, destroy large to carbon nanotube inherent structure and be not suitable for the problems such as scale operation.
Layered double hydroxide (Layered Double Hydroxide, referred to as hydrotalcite), general formula is [M
2+ 1-xm
3+ x(OH)
2]
x+a
n- x/nmH
2o, wherein M
2+, M
3+represent divalence and trivalent metal cation respectively, A
n-represent interlayer exchangeable anions.Such material is that one prepares metal catalyst, effective precursor of support of the catalyst.The people such as Sun with dodecyl sodium sulfonate root intercalation cobalt aluminum hydrotalcite for carbon nano ring (Adv.Mater.2012, DOI:10.1002/adma.201203108) has been prepared in the pyrolysis of precursor one step.The people such as Xu with terephthalic acid intercalation cobalt magnesium aluminum-hydrotalcite for carbon nano-particles/metal oxide nano composite material (Nano Lett., 2001,1:703-706) has been prepared in the pyrolysis of precursor one step.Contain transition metal with laminate, to be organic anion intercalated houghite be interlayer that precursor prepares carbon material attracts attention.
Summary of the invention
The present invention one of is intended to solve the problems of the technologies described above at least to a certain extent or at least provides a kind of useful business to select.
In one aspect of the invention, it comprises to the present invention proposes a kind of carbon nano-composite material: carbon nanomaterial, and described carbon nanomaterial is surface-functionalized; And metallic particles, described metallic particles is formed on described carbon nanomaterial.This carbon nano-composite material may be used for removing the pollutent in waste water, and removal as Congo red in azoic dyestuff, removal effect is significantly higher than existing nano material.Contriver finds, 30mg is joined 50ml according to the carbon nano-composite material of the embodiment of the present invention, in the Congo red solution of 100ppm, 10min and completely adsorbable, now adsorptive capacity is 167mg/g, and by increasing Congo red strength of solution, can to obtain maximum adsorptive capacity be 880mg/g.
According to embodiments of the invention, above-mentioned carbon nano-composite material can also have following additional technical feature one of at least:
According to embodiments of the invention ,-OH and-COO-functional group are carried in the surface of described carbon nanomaterial.
According to embodiments of the invention, described metallic particles for be selected from Co, Ni, Fe, Cu metal simple-substance or consisting of alloy form at least one of group, and be selected from Mg, Zn, Al oxide compound form at least one of group.
According to embodiments of the invention, described carbon nanomaterial is the form of multi-walled carbon nano-tubes, in the pipe that described metal simple-substance or alloying pellet are formed at described multi-walled carbon nano-tubes and tube head one of at least.
According to embodiments of the invention, described carbon nanomaterial is the form of carbon nanometer layer, and described metal simple-substance or alloying pellet are coated on described carbon nanometer layer.According to embodiments of the invention, when adopting this clad structure, this carbon-clad metal simple substance or alloying pellet are optionally scattered among metal oxide.
In a second aspect of the present invention, the present invention proposes a kind of method preparing carbon nano-composite material.According to embodiments of the invention, the method comprises: a) form the salicylate intercalation layered metal hydroxides precursor that laminate contains transition metal; And b) roasting is carried out to described precursor, to obtain described carbon nano-composite material, wherein, described carbon nano-composite material comprises: carbon nanomaterial, and described carbon nanomaterial is surface-functionalized; And metallic particles, described metallic particles is formed on described carbon nanomaterial.The method is utilized can effectively to prepare foregoing carbon nano-composite material.
According to embodiments of the invention, the above-mentioned method preparing carbon nano-composite material can also have following additional technical feature one of at least:
According to embodiments of the invention, the salicylate intercalation layered metal hydroxides precursor described in step a) adopts at least one in coprecipitation method, hydrothermal method, calcine-recovering method, ion exchange method to prepare.Wherein, reacting pH scope in coprecipitation method and hydrothermal method is 6.5-8.5, and crystallization temperature scope is room temperature-100 DEG C.According to a concrete example of the present invention, metal salt solution, alkaline solution are mixed with salicylate solution, and lower than at the temperature of 100 degrees Celsius, carry out Crystallizing treatment, to obtain the salicylate intercalation layered metal hydroxides precursor that this laminate contains metallic element.
According to embodiments of the invention, described metal-salt is at least one being selected from metal nitrate, metal sulfate and metal chloride, described salicylate preferably water poplar acid sodium and potassium salicylate.
According to embodiments of the invention, described alkaline solution is at least one being selected from NaOH, KOH, urea.
According to embodiments of the invention, roasting is carried out to described precursor and comprises:
Described precursor is placed in tube-type atmosphere furnace, and in nonoxidizing atmosphere, after 500 DEG C ~ 1000 DEG C roasting 0.2h ~ 10h, Temperature fall is to room temperature.Preferably, contain Co element system for laminate, maturing temperature is 600-1000 degree Celsius, and roasting time is 1h-10h, and laminate contains Ni element system, and maturing temperature is 500-1000 degree Celsius, and roasting time is 0.2h-10h.
According to embodiments of the invention, described nonoxidizing atmosphere is made up of at least one of hydrogen, rare gas element.
According to embodiments of the invention, described rare gas element is for being selected from N
2, He or Ar at least one.
In a third aspect of the present invention, the present invention also proposes the purposes of above-mentioned carbon nano-composite material.
Technological method of the present invention can have following advantages one of at least:
1, according to embodiments of the invention; prepare carbon nano-composite material layered hydroxide precursor used and there is even structure; composition can modulation; preparation process is simple, can be applicable to the features such as industrial scale production, provides the salicylate of carbon source to be organic molecule; degradation production is single; be conducive to preparing high purity carbon material, and raw material is easy to get, environmentally safe.
2, according to embodiments of the invention, due to employing is layered hydroxide presoma, the dispersion of its laminate metallic element atomic level makes metal in its product of roasting have higher catalytic activity, thus effectively reduce the temperature of carbon nano-tube matrix material in pyrolytic process, and substantially reduce roasting time.
3, according to embodiments of the invention, the carbon nanotube prepared/metal nanometer composite material even structure, purity is high, can be mass-produced, and achieves without any chemically modified one step that it is surface-functionalized.
Additional aspect of the present invention and advantage will part provide in the following description, and part will become obvious from the following description, or be recognized by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from accompanying drawing below combining to the description of embodiment, wherein:
Fig. 1 is the X-ray crystalline diffraction spectrogram of the cobalt aluminium lamination shape hydroxide precursor of salicylate intercalation prepared by the embodiment of the present invention 1;
Fig. 2 is the stereoscan photograph of carbon nanotube/metal nanometer composite material prepared by the embodiment of the present invention 1;
Fig. 3 is the XRD spectra of carbon nanotube/metal nanometer composite material prepared by the embodiment of the present invention 1;
Fig. 4 is the fourier-transform infrared data of carbon nanotube/metal nanometer composite material prepared by the embodiment of the present invention 1.
Embodiment
Be described below in detail embodiments of the invention, these embodiments are exemplary, are intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.In addition, unless stated otherwise, the starting material adopted below and equipment are commercially available.
Embodiment 1:
Steps A: the Co (NO taking 11.64g
3)
26H
2al (the NO of O and 7.5g
3)
39H
2o adds deionized water and is configured to 50ml mixing solutions, and the sodium salicylate separately taking 12.81g is dissolved in 100mL deionized water, takes 8g NaOH and adds deionized water and be configured to the alkaline solution that 100mL concentration is 2M.Be added drop-wise in sodium salicylate solution by mixing salt solution and NaOH solution under mechanical stirring, dropping process keeps pH value of solution to be 7, is transferred in autoclave by gained slurries simultaneously, at 100 DEG C, and crystallization 24 hours.After crystallization terminates, treat that temperature drops to room temperature, with deionized water wash, centrifugal 4 times, at 60 DEG C dry 12 hours, obtain the cobalt aluminum hydrotalcite presoma of salicylate intercalation.
Step B: take 1.5g hydrotalcite precursor after grinding, evenly divides in porcelain boat and is placed in tube furnace, at N
2in atmosphere, gas cross section flow 40ml/cm
2be warming up to 600 DEG C with 5 DEG C/min under the condition of min, be incubated 2 hours.Detect through SEM and TEM, gained pyrolysis product is the matrix material of multi-walled carbon nano-tubes and cobalt, wherein length of carbon nanotube is about 1 μm, diameter is about 24nm, cobalt metal is mainly arranged in tube head and the caliber of carbon nanotube, characterize through FT-IR and find, this composite material surface is with the carboxyl of hydroxyl and deprotonation.It the results are shown in Fig. 1-4.
Wherein, Fig. 1 is the X-ray crystalline diffraction spectrogram of the cobalt aluminium lamination shape hydroxide precursor of salicylate intercalation prepared by the present embodiment; Fig. 2 is the stereoscan photograph of carbon nanotube/metal nanometer composite material prepared by the present embodiment, shows that the product morphology obtained is the carbon nanotube of even structure; Fig. 3 is the XRD spectra of carbon nanotube/metal nanometer composite material prepared by the present embodiment, shows that the product obtained is the nano composite material of carbon nanotube and metal Co; Fig. 4 is the fourier-transform infrared data of carbon nanotube/metal nanometer composite material prepared by the present embodiment, and showing that the carbon nano tube surface obtained is with a large amount of hydroxyls and carboxyl, is functionalized carbon nano-tube.
Embodiment 2:
Steps A: the Ni (NO taking 11.63g
3)
26H
2al (the NO of O and 7.5g
3)
39H
2o adds deionized water and is configured to 50ml mixing solutions, and the sodium salicylate separately taking 12.81g is dissolved in 100mL deionized water, takes 8g NaOH and adds deionized water and be configured to the alkaline solution that 100mL concentration is 2M.Be added drop-wise in sodium salicylate solution by mixing salt solution and NaOH solution under mechanical stirring, dropping process keeps pH value of solution to be 7, is transferred in autoclave by gained slurries simultaneously, at 100 DEG C, and crystallization 24 hours.After crystallization terminates, treat that temperature drops to room temperature, with deionized water wash, centrifugal 4 times, at 60 DEG C dry 12 hours, obtain the nickel aluminum hydrotalcite presoma of salicylate intercalation.
Step B: take 1.5g hydrotalcite precursor after grinding, evenly divides in porcelain boat and is placed in tube furnace, at N
2in atmosphere, flow area flow 60ml/cm
2be warming up to 500 DEG C with 5 DEG C/min under the condition of min, be incubated 2 hours.Detect through SEM and TEM, gained pyrolysis product is the nanocarbon/metal nano composite material that surface coverage has a large amount of multi-walled carbon nano-tubes, and wherein length of carbon nanotube is about 400nm, and caliber is about 25nm, characterize through FT-IR and find, this composite material surface is with the carboxyl of hydroxyl and deprotonation.
Embodiment 3:
Steps A: the Co (NO taking 11.64g
3) 26H
2al (the NO of O and 7.5g
3)
39H
2o adds deionized water and is configured to 50ml mixing solutions, and the sodium salicylate separately taking 12.81g is dissolved in 100mL deionized water, takes 8g NaOH and adds deionized water and be configured to the alkaline solution that 100mL concentration is 2M.Be added drop-wise in sodium salicylate solution by mixing salt solution and NaOH solution under mechanical stirring, dropping process keeps pH value of solution to be 7, is transferred in autoclave by gained slurries simultaneously, at 100 DEG C, and crystallization 24 hours.After crystallization terminates, treat that temperature drops to room temperature, with deionized water wash, centrifugal 4 times, at 60 DEG C dry 12 hours, obtain the cobalt aluminum hydrotalcite presoma of salicylate intercalation.
Step B: take 1.5g hydrotalcite precursor after grinding, evenly divides in porcelain boat and is placed in tube furnace, at N
2/ H
2in atmosphere, flow area flow 60ml/cm
2be warming up to 600 DEG C with 5 DEG C/min under the condition of min, be incubated 2 hours.Detect through SEM and TEM, gained pyrolysis product is the matrix material of multi-walled carbon nano-tubes and cobalt, wherein length of carbon nanotube is about 2 μm, diameter is about 27nm, cobalt metal is mainly arranged in tube head and the caliber of carbon nanotube, characterize through FT-IR and find, this composite material surface is with the carboxyl of hydroxyl and deprotonation.
In the description of this specification sheets, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, identical embodiment or example are not necessarily referred to the schematic representation of above-mentioned term.And the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention when not departing from principle of the present invention and aim, revising, replacing and modification.
Claims (5)
1. a carbon nano-composite material, is characterized in that, comprises:
Carbon nanomaterial, described carbon nanomaterial is surface-functionalized; And
Metal simple-substance or alloying pellet, described metal simple-substance or alloying pellet are formed on described carbon nanomaterial,
Wherein,
Described carbon nanomaterial is the form of multi-walled carbon nano-tubes, in the pipe that described metal simple-substance or alloying pellet are formed at described multi-walled carbon nano-tubes and tube head one of at least; Or
Described carbon nanomaterial is the form of carbon nanometer layer, and described metal simple-substance or alloying pellet are coated on described carbon nanometer layer, and wherein, carbon-clad metal simple substance or alloying pellet are scattered among metal oxide,
-OH and-COO-functional group are carried in the surface of described carbon nanomaterial,
Described metal simple-substance or alloying pellet for be selected from Co, Ni, Fe, Cu metal simple-substance or consisting of alloy form at least one of group, and be selected from Mg, Zn, Al oxide compound form at least one of group.
2. prepare a method for carbon nano-composite material according to claim 1, it is characterized in that, comprising:
A) the salicylate intercalation layered metal hydroxides precursor that laminate contains transition metal is formed; And
B) roasting is carried out to described precursor, to obtain described carbon nano-composite material,
Wherein,
Described carbon nano-composite material comprises:
Carbon nanomaterial, described carbon nanomaterial is surface-functionalized; And
Metal simple-substance or alloying pellet, described metal simple-substance or alloying pellet are formed on described carbon nanomaterial.
3. the method preparing carbon nano-composite material according to claim 2, is characterized in that,
Step a) described in salicylate intercalation layered metal hydroxides precursor be adopt coprecipitation method, hydrothermal method, calcine-recovering method, prepared by least one in ion exchange method,
Wherein, reacting pH scope in described coprecipitation method and hydrothermal method is 6.5-8.5, and crystallization temperature scope is room temperature-100 DEG C,
Metal salt solution, alkaline solution are mixed with salicylate solution, and lower than at the temperature of 100 degrees Celsius, carries out Crystallizing treatment, to obtain the salicylate intercalation layered metal hydroxides precursor that described laminate contains metallic element.
4. the method preparing carbon nano-composite material according to claim 3, it is characterized in that, described metal-salt is at least one being selected from metal nitrate, metal sulfate and metal chloride, described salicylate is selected from sodium salicylate and potassium salicylate, and described alkaline solution is at least one being selected from NaOH, KOH, urea.
5. the method preparing carbon nano-composite material according to claim 3, is characterized in that, carries out roasting comprise described precursor:
Described precursor is placed in tube-type atmosphere furnace, in nonoxidizing atmosphere, after 500 DEG C ~ 1000 DEG C roasting 0.2h ~ 10h, Temperature fall to room temperature,
Wherein, described nonoxidizing atmosphere is made up of at least one of hydrogen, rare gas element.
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| CN110203904A (en) * | 2019-06-06 | 2019-09-06 | 东北大学 | It is used to prepare the precursor material and method of nanostructured carbon material |
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