CN102294250B - Three-dimensional carbon nanotube nano composite catalyst, and preparation method and application thereof - Google Patents
Three-dimensional carbon nanotube nano composite catalyst, and preparation method and application thereof Download PDFInfo
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- CN102294250B CN102294250B CN 201110141023 CN201110141023A CN102294250B CN 102294250 B CN102294250 B CN 102294250B CN 201110141023 CN201110141023 CN 201110141023 CN 201110141023 A CN201110141023 A CN 201110141023A CN 102294250 B CN102294250 B CN 102294250B
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Abstract
Provided are a three-dimensional carbon nanotube nano composite catalyst, and a preparation method and application thereof, which belong to the technical field of nano-material preparation. The nano composite catalyst contains carbon nanotube sponge and cadmium sulfide nano particles. The preparation method includes the step that the carbon nanotube sponge is dipped in an organic solution of the cadmium sulfide nano particles, so that the cadmium sulfide nano particles adhere on a surface and in apertures of the carbon nanotube sponge to form a three-dimensional carbon nanotube nano composite catalyst. The invention also provides application of the catalyst to adsorption-photocatalysis degradation of dye molecules in water. On the one hand, the carbon nanotube sponge has large specific surface area, good adsorption property, and is easily operated and processed; on the other hand, the cadmium sulfide nano particles have high photocatalytic activity, and can catalyze degradation of dye molecules in water under visible light. Therefore, the nano composite catalyst obtained in the invention has advantages of large adsorption quantity, high degradation efficiency, easy operation and processing, and capability of simultaneously degrading a plurality of pollutants in water, etc.
Description
Technical field
The present invention relates to a kind of nano-composite catalyst, particularly nano-composite catalyst of a kind of carbon nanotubes sponge and cadmium sulfide nano-particles and its preparation method and application belongs to the nano material preparing technical field.
Background technology
Along with the development of the modern industry, limited water resource is suffered destruction in various degree on the earth.Dyestuff extensive use in the industries such as weaving, leather, papermaking, plastics has very high solubility in water, become the important sources that water pollutes.
Be used in the market the absorbent charcoal material of water treatment, its action principle mainly is by the mode of physisorption pollutant to be separated with water.CNT is by the curling hollow and layer structure that forms of graphite synusia, has high specific area, and well the characteristics such as thermodynamics and chemical stability are a kind of very promising adsorbents.CNT with respect to traditional active carbon, aspect the organic and inorganic pollution of absorption, has balancing speed faster, higher adsorption capacity and the adjustable advantages such as surface state as adsorbent.Two keys of carbon nano tube surface can with π key System forming pi-pi accumulation effect in the aromatic compound, this makes it show more excellent performance in absorption aromatics dye molecule process.But active carbon, CNT are mainly physical absorption to the dyes Adsorbed molecular, and thoroughly and in use there is not the desorption phenomenon in absorption, easily causes secondary pollution.For overcoming this problem, people adopt nano particle and CNT with catalytic activity compound, and under illumination condition, realization realizes complete, thoroughly removing to the dyes molecule to the chemical catalysis degraded of organic molecule in the water body.
By the CNT sponge that the unordered accumulation of CNT forms, (X.C.Gui, J.Q.Wei, K.L.Wang, A.Y.Cao, H.W.Zhu, Y.Jia, Q.K.Shu, D.H.Wu.Adv.Mater.2010,22,617-621), except the high-specific surface area that possesses CNT self, good macroscopic property, also have flourishing pore structure, shown higher adsorption in the dye molecule process in adsorbed water body.In addition, the more easy to operate and processing of CNT sponge macroscopic body is conveniently used and is reclaimed, and industrial prospect is more arranged.
Summary of the invention
One of purpose of the present invention provides a kind of three-dimensional carbon nanotube nano composite catalyst, and this nano-composite catalyst contains CNT sponge and cadmium sulfide nano-particles; The mass ratio of described CNT sponge and described cadmium sulfide nano-particles is 1～200: 1; Described cadmium sulfide nano-particles is attached to the surface of described CNT sponge and the hole inside of described CNT sponge; The density of described CNT sponge is 5.8～11.6mg/cm
3
Two of purpose of the present invention is a kind of three-dimensional carbon nanotube nano composite catalyst preparation method and application.
Technical scheme of the present invention is as follows:
A kind of three-dimensional carbon nanotube nano composite catalyst is characterized in that, this nano-composite catalyst contains CNT sponge and cadmium sulfide nano-particles; The mass ratio of described CNT sponge and described cadmium sulfide nano-particles is 1～200: 1, and described cadmium sulfide nano-particles is attached to the surface of described CNT sponge and the hole inside of described CNT sponge; The density of described CNT sponge is 5.8～11.6mg/cm
3
Technical characterictic of the present invention also is: the particle diameter of described cadmium sulfide nano-particles is 3～8nm; The mass ratio of CNT sponge and described cadmium sulfide nano-particles is preferably 2～20: 1.
The invention provides a kind of preparation method of three-dimensional carbon nanotube nano composite catalyst, it is characterized in that the method carries out as follows:
1) cadmium sulfide nano-particles is dissolved in the organic solvent, makes the solution that the mass body volume concentrations is 0.01～2mg/mL;
2) the CNT sponge is dipped in the solution of cadmium sulfide nano-particles, CNT and cadmium sulfide nano-particles mass ratio are 1～200: 1, are under 0～50 ℃ of condition in temperature, soak 0.5～24 hour; Make cadmium sulfide nano-particles be attached to the surface of CNT sponge and the hole inside of CNT sponge, form three-dimensional carbon nanotube nano composite catalyst;
3) three-dimensional carbon nanotube nano composite catalyst is taken out vacuum drying.
In the technique scheme, described organic solvent comprises chloroform, n-hexane, oxolane, toluene or ethyl acetate.
The present invention also provides the application of described three-dimensional carbon nanotube nano composite catalyst as photochemical catalyst dye molecule in catalytic degradation water.Described dyestuff is rhodamine B, methyl orange or methyl blue.
The present invention compared with prior art has the following advantages and the high-lighting effect:
1. because CNT sponge and cadmium sulfide nano-particles specific area are large, the CNT sponge has strong adsorption capacity to organic molecule, cadmium sulfide nano-particles can be in the multiple dye molecule degraded of catalysis under the illumination, and therefore prepared three-dimensional carbon nanotube nano composite catalyst has advantages of that adsorption capacity is high, thorough to the dye molecule degraded, non-secondary pollution.
2. because three-dimensional carbon nanotube nano composite catalyst is macroscopic body, have good mechanical characteristic, easy to operate and processing can directly be compressed into filtration membrane and use.
3. three-dimensional carbon nanotube nano composite catalyst Stability Analysis of Structures of the present invention is used also significant change can not occur for a long time, can be repeatedly used.
Description of drawings
Fig. 1 is the photo of three-dimensional carbon nanotube nano composite catalyst.
Fig. 2 is the electron scanning micrograph of three-dimensional carbon nanotube nano composite catalyst.
The specific embodiment
Three-dimensional carbon nanotube nano composite catalyst provided by the invention contains CNT sponge and cadmium sulfide nano-particles; The mass ratio of described CNT sponge and described cadmium sulfide nano-particles is 1～200: 1, and the optimization mass ratio of CNT sponge and cadmium sulfide nano-particles is 2～20: 1; Described cadmium sulfide nano-particles is attached to the surface of described CNT sponge and the hole inside of described CNT sponge; The density of described CNT sponge is 5.8～11.6mg/cm
3The particle diameter of described cadmium sulfide nano-particles is 3～8nm.
The preparation method of this three-dimensional carbon nanotube nano composite catalyst carries out as follows:
1) cadmium sulfide nano-particles is dissolved in the organic solvent that comprises chloroform, n-hexane, oxolane, toluene or ethyl acetate, makes the solution that the mass body volume concentrations is 0.01-2mg/mL;
2) the CNT sponge is dipped in the solution of cadmium sulfide nano-particles, CNT and cadmium sulfide nano-particles mass ratio are 1～200: 1, are under 0～50 ℃ of condition in temperature, soak 0.5～24 hour; Make cadmium sulfide nano-particles be attached to the surface of CNT sponge and the hole inside of CNT sponge, form three-dimensional carbon nanotube nano composite catalyst;
3) three-dimensional carbon nanotube nano composite catalyst is taken out vacuum drying.
Further this three-dimensional carbon nanotube nano composite catalyst of research is as the application of photochemical catalyst dye molecule in catalytic degradation water.Described dyestuff is rhodamine B, methyl orange or methyl blue.
The cadmium sulfide nano-particles that satisfies above-mentioned requirements can be synthetic according to existing method.For example, can be with reference to K.T.Yong, Y.Sahoo, M.T.Swihart, P.N.Prasad, J.Phys.Chem.C 2007,111, and disclosed method is synthetic among the 2447-2458.
Particularly, described cadmium sulfide nano-particles can prepare according to the method that comprises the steps:
Take by weighing 1mM CdCl
2.2.5H
2O is dissolved in the 10mL oleyl amine, under the protection of Ar gas this solution is warming up to 175 ℃, heats 20～35 minutes.6mM sulphur powder is dissolved in the 5mL oleyl amine prepares another part solution.Under stirring condition, with the oleyl amine solution adding CdCl of sulphur powder
2Oleyl amine solution in, under Ar gas protection, continue heating 4 hours.Add ethanol precipitation cadmium sulfide nano-particles after the cooling, centrifugation.Make it precipitation with adding again ethanol behind the n-hexane dissolution cadmium sulfide nano-particles, centrifugal again.Three times so repeatedly.The vacuum drying of gained cadmium sulfide nano-particles is made pressed powder, be distributed to again the solution that is made into variable concentrations in the chloroformic solution.
But the preparation reference literature X.C.Gui of CNT sponge disclosed by the invention, J.Q.Wei, K.L.Wang, A.Y.Cao, H.W.Zhu, Y.Jia, Q.K.Shu, D.H.Wu.Adv.Mater.2010, disclosed method is synthetic among 22, the 617-621.
Particularly, the synthetic of described CNT sponge can prepare according to the method that comprises the steps:
1) takes by weighing 6.0g ferrocene powder and be dissolved in the 100mL dichlorobenzene solution, be made into the reaction solution that ferrocene concentration is 0.06g/mL;
2) quartz plate that cleans up is pushed reaction zone, the sealed silica envelope two ends;
3) pass into flow be the argon gas of 800mL/min getting rid of residual air in the quartz ampoule, heating reaction zone temperature to 820～940 ℃ are heated preheating zone temperature to 250 ℃ simultaneously;
4) adjust argon flow amount to 2000mL/min, and pass into the hydrogen that flow is 100～500mL/min;
5) open the precise injection pump, reaction solution is injected quartz ampoule through capillary, feed rate is 0.10～0.25mL/min; Reaction time is 0.5～4h.
6) after reaction reaches the scheduled time, stop the carbon source feeding and close hydrogen, stopped heating is also adjusted argon flow amount to 20mL/min, makes product cool to room temperature with the furnace in argon gas atmosphere, collects product and describes the present invention in detail below in conjunction with embodiment.
Embodiment 1-4 is used for explanation prepares three-dimensional carbon nanotube nano composite catalyst of the present invention by method load cadmium sulfide nano-particles on the CNT sponge of immersion deposition method.
Embodiment 1
The preparation of three-dimensional carbon nanotube nano composite catalyst:
Getting density is 7.3mg/cm
3CNT sponge 3.8mg at room temperature immerse in the toluene solution that 3mL concentration is the 1mg/mL cadmium sulfide nano-particles, soak 24h and take out.Vacuum drying gets three-dimensional block product.Wherein the mass ratio of CNT sponge and cadmium sulfide is 2: 1.Observe by SEM (model is Hitachi S4800 FESEM), cadmium sulfide nano-particles is positioned at surface and the hole inside of CNT sponge.The particle diameter that records cadmium sulfide nano-particles by transmission electron microscope (model is Tecnai T20) is 4～6nm.
The photo of the three-dimensional carbon nanotube nano composite catalyst that the present embodiment prepares as shown in Figure 1.The electron scanning micrograph of the three-dimensional carbon nanotube nano composite catalyst that the present embodiment prepares as shown in Figure 2.
Embodiment 2
The preparation of three-dimensional carbon nanotube nano composite catalyst:
Getting density is 5.8mg/cm
3CNT sponge 3.8mg lower to immerse 3mL concentration be in the chloroformic solution of 0.01mg/mL cadmium sulfide nano-particles at 0 ℃, soak 0.5h and take out.Vacuum drying gets three-dimensional block product.Wherein the mass ratio of CNT sponge and cadmium sulfide is 200: 1.Observe by SEM (model is Hitachi S4800FESEM), cadmium sulfide nano-particles is positioned at surface and the hole inside of CNT sponge.The particle diameter that records cadmium sulfide nano-particles by transmission electron microscope (model is Tecnai T20) is 3～5nm.
Embodiment 3
The preparation of three-dimensional carbon nanotube nano composite catalyst:
Getting density is 7.3mg/cm
3CNT sponge 3.8mg lower to immerse the 3mL concentration be in the tetrahydrofuran solution of 2mg/mL cadmium sulfide nano-particles at 50 ℃, soak 12h and take out.Vacuum drying chamber gets three-dimensional block product.Wherein the mass ratio of CNT sponge and cadmium sulfide is 1: 1.Observe by SEM (model is Hitachi S4800 FESEM), cadmium sulfide nano-particles is positioned at surface and the hole inside of CNT sponge.The particle diameter that records cadmium sulfide nano-particles by transmission electron microscope (model is Tecnai T20) is 6～8nm.
Embodiment 4
The preparation of three-dimensional carbon nanotube nano composite catalyst:
Getting density is 11.6mg/cm
3CNT sponge 3.8mg at room temperature immerse in the chloroformic solution that 3mL concentration is the 0.1mg/mL cadmium sulfide nano-particles, soak 4h and take out.Vacuum drying gets three-dimensional block product.Wherein the mass ratio of CNT sponge and cadmium sulfide is 20: 1.Observe by SEM (model is Hitachi S4800 FESEM), cadmium sulfide nano-particles is positioned at surface and the hole inside of CNT sponge.The particle diameter that records cadmium sulfide nano-particles by transmission electron microscope (model is Tecnai T20) is 3～5nm.
Embodiment 5-8 is used for three-dimensional carbon nanotube nano composite catalyst of the present invention being described in the application of the water treatment that contains dyestuff, uses the sample among the embodiment 1.
Embodiment 5-8
The three-dimensional carbon nanotube nano composite catalyst of embodiment 1 preparation of 3.9mg respectively is dipped in the aqueous solution of rhodamine B of 2mL variable concentrations, the optical filter that uses the xenon source of 300W to add 420nm carries out visible illumination reaction.The concentration of rhodamine B adopts uv-visible absorption spectra (UV-Vis) to detect in the solution after the illumination.Catalyst is as shown in table 1 to the degradation efficiency of rhodamine B under different condition.
As can be seen from Table 1, the three-dimensional carbon nanotube nano composite catalyst dye molecule in the catalytic degradation water efficiently.
Claims (6)
1. a three-dimensional carbon nanotube nano composite catalyst is characterized in that, this nano-composite catalyst contains CNT sponge and cadmium sulfide nano-particles; The mass ratio of described CNT sponge and described cadmium sulfide nano-particles is 1～200:1; Described cadmium sulfide nano-particles is attached to the surface of described CNT sponge and the hole inside of described CNT sponge; The density of described CNT sponge is 5.8～11.6mg/cm
3The particle diameter of described cadmium sulfide nano-particles is 3～8nm.
2. a kind of three-dimensional carbon nanotube nano composite catalyst according to claim 1 is characterized in that, the mass ratio of CNT sponge and described cadmium sulfide nano-particles is 2～20:1.
3. the preparation method of a three-dimensional carbon nanotube nano composite catalyst is characterized in that the method carries out as follows:
1) cadmium sulfide nano-particles is dissolved in the organic solvent, makes the solution that the mass body volume concentrations is 0.01-2mg/mL;
2) the CNT sponge is dipped in the solution of cadmium sulfide nano-particles, CNT and cadmium sulfide nano-particles mass ratio are 1～200:1, are under 0～50 ℃ of condition in temperature, soak 0.5～24 hour; Make cadmium sulfide nano-particles be attached to the surface of CNT sponge and the hole inside of CNT sponge, form three-dimensional carbon nanotube nano composite catalyst;
3) three-dimensional carbon nanotube nano composite catalyst is taken out vacuum drying.
4. the preparation method of a kind of three-dimensional carbon nanotube nano composite catalyst according to claim 3, it is characterized in that: described organic solvent comprises chloroform, n-hexane, oxolane, toluene or ethyl acetate.
5. three-dimensional carbon nanotube nano composite catalyst as claimed in claim 1 is as the application of photochemical catalyst dye molecule in catalytic degradation water.
6. three-dimensional carbon nanotube nano composite catalyst as claimed in claim 5 is characterized in that as the application of photochemical catalyst dye molecule in catalytic degradation water: described dyestuff is rhodamine B, methyl orange or methyl blue.
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| CN103316692A (en) * | 2013-06-24 | 2013-09-25 | 江苏大学 | Preparation method and application of CdS/CNTs composite photocatalyst |
| CN103736475B (en) * | 2014-01-08 | 2015-08-19 | 国家纳米科学中心 | A kind of three-dimensional porous titanium dioxide nano tube catalyst, preparation method and its usage |
| CN103979523B (en) * | 2014-04-28 | 2015-04-01 | 中国石油大学(北京) | Method for filling multi-walled carbon nano-tubes with cadmium sulfide |
| CN103980668B (en) * | 2014-05-30 | 2016-05-18 | 哈尔滨工业大学 | A kind of preparation method of CNT/amorphous carbon/epoxy resin composite material |
| CN105056974B (en) * | 2015-08-03 | 2017-05-03 | 南京信息工程大学 | Flower-shaped cadmium sulfide-antimony sulfide compound, preparation method and application thereof |
| CN105833840A (en) * | 2016-06-10 | 2016-08-10 | 苏州巨联环保科研有限公司 | Preparation method of carbon nanometer tube sponge base adsorption material |
| CN106513017A (en) * | 2016-10-26 | 2017-03-22 | 华南理工大学 | Compound photocatalytic material and preparation method and application thereof |
| CN111229268B (en) * | 2020-02-13 | 2021-06-08 | 中国石油大学(华东) | Full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for well drilling waste liquid treatment, and preparation method and application thereof |
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