CN105148995A - Application of PAMAM carboxylated graphene Co nano-composite material in 4-nitroaniline degradation and catalysis - Google Patents
Application of PAMAM carboxylated graphene Co nano-composite material in 4-nitroaniline degradation and catalysis Download PDFInfo
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- CN105148995A CN105148995A CN201510607953.9A CN201510607953A CN105148995A CN 105148995 A CN105148995 A CN 105148995A CN 201510607953 A CN201510607953 A CN 201510607953A CN 105148995 A CN105148995 A CN 105148995A
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Abstract
The invention discloses application of a PAMAM carboxylated graphene Co nano-composite material in 4-nitroaniline degradation and catalysis. A preparation method comprises the steps of 1 synthesizing PAMAM/GO-COOH and 2 synthesizing a PAMAM/GO-COOH/Co nano-composite material. A chemical crosslinking method and polyamidoamine dendrimer modified carboxylated graphene are adopted to successfully obtain the PAMAM/carboxylated graphene/Co nano-composite material with PAMAM carboxylated graphene as a template and sodium borohydride as a reducing agent. The PAMAM/carboxylated graphene/Co nano-composite material is a novel catalytic carrier material having unique performance and has high catalytic activity on the 4-nitroaniline water solution degradation effect only in the presence of air and water under the normal-temperature condition, and a new way is provided for degradation of environmental pollutants in our actual life.
Description
Technical field
The present invention relates to the application of a kind of PAMAM carboxylated Graphene Co nano composite material in 4-nitroaniline degraded catalysis.
Background technology
Graphene (Graphene), as a kind of new material, has caused the extensive concern of all circles researcher from 2004 since being found.Graphene, due to its two-dimentional monoatomic layer crystal structure, large specific area, shows excellent application prospect in fields such as capacitor, sensor, catalysis and nano composite materials.Graphene/dendrimer composite becomes the new study hotspot of field of nanometer material technology one with the stuctures and properties advantage of its uniqueness.
Polyamidoamine Dendrimers (PAMAM) is the novel high polymer of a class three-dimensional, height cladodification, there is controlled relative molecular mass, a large amount of surface functional groups, molecular memory is at cavity, the symmetry of height, and the end group of densification can in conjunction with more active material, these design features make it have unique character.With the Graphene of Polyamidoamine Dendrimers functional modification not only due to the sterically hindered agglomeration reducing interlayer that dendrimer produces between graphene layer, its dispersiveness and dissolubility have also been obtained improvement simultaneously, the more important thing is that it can control to prepare small size due to dendrimer, finely dispersed metal nanoparticle and the algebraically of dendrimer can be utilized to regulate the size of its internal cavities thus control the contact of catalyst and reactant, a wide platform can have been constructed for preparing multifunctional high-performance material as organic functional molecular and the good catalyst carrier of inorganic nano-particle.
Along with dye industry development, organic poison main in waste water is the aromatic compound of nitro or amido functional group, and these are high temperature resistant, and organic matter adopts traditional chemical precipitation method to be difficult to be decomposed.Therefore, if the PAMAM carboxylated Graphene Co nano composite material of preparation can have remarkable effect to 4-nitroaniline degraded catalysis, then there is important practical value, also there is important Eco-environmental Significance.
Summary of the invention
For promoting scientific and technological progress, the present inventor is through lot of experiments, invent a kind of PAMAM carboxylated Graphene Co nano composite material and preparation method thereof, and probe into the degraded catalytic action of PAMAM carboxylated Graphene Co nano composite material (PAMAM/GO-COOH/Co) to 4-nitroaniline.
The preparation of PAMAM carboxylated Graphene Co nano composite material comprises following step:
(1) synthesis of PAMAM/GO-COOH: take carboxylated Graphene 0.42g, add 40mL deionized water, 4gEDC and 4.2gNHS is added after ultrasonic disperse, 4h is stirred at 40 DEG C of lower magnetic forces, product filters, disperse in 40mL deionized water for ultrasonic after centrifugal, washed with de-ionized water, add 10mLPAMAM (the 4.0G concentration 0.1g/mL) aqueous solution, stirring reaction 12h at 35 DEG C, product is drying to obtain through centrifugal, washed with de-ionized water final vacuum;
(2) synthesis of PAMAM/GO-COOH/Co nano composite material: take PAMAM/GO-COOH/Co100mg, adds 20mL deionized water, ultrasonic disperse, adds 10mLCoCl
2solution (0.5mol/L), stirs 1h, then adds 0.5gNaBH
4, stir 4h at 50 DEG C of lower magnetic forces, product is collected in beaker after centrifugal, washed with de-ionized water, and then ultrasonic disperse, removes unnecessary Co
2+, end product, through centrifugal, washed with de-ionized water, filters final vacuum and is drying to obtain.
The degraded catalysis of PAMAM carboxylated Graphene Co nano composite material to 4-nitroaniline is probed into: obtain the PAMAM/GO-COOH/Co ultrasonic disperse of 10mg in 30mL5.8 × 10
-5in the aqueous solution of mol/L4-nitroaniline, mixture stirs room temperature (25 DEG C) in atmosphere, measures at set intervals with ultraviolet-visual spectrometer.The ultraviolet absorption peak of 4-nitroaniline is 378nm, illustrates that composite is to the degraded catalytic capability of 4-nitroaniline by absworption peak peak intensity.
Compared with prior art, beneficial effect of the present invention is:
The present invention adopts chemical crosslink technique that Polyamidoamine Dendrimers (PAMAM4.0G) is modified carboxylated Graphene, it is template that success obtains PAMAM carboxylated Graphene, the PAMAM/ carboxylated Graphene/Co nano composite material using sodium borohydride as reducing agent.After measured, Co nano-particles size size is dispersed in PAMAM/ carboxylated graphenic surface.
PAMAM/ carboxylated Graphene/Co nano composite material prepared by the present invention is a kind of new catalytic carrier material with special performance, under normal temperature condition, as long as have air and water to there is the aqueous solution degradation of PAMAM/GO-COOH/Co to 4-nitroaniline show high catalytic activity, this degraded to environmental pollutants in our real life provides a kind of new path.
Accompanying drawing explanation
Fig. 1 is that PAMAM/GO-COOH/Co is at the indoor aqueous solution degradation figure to 4-nitroaniline of normal temperature.
Detailed description of the invention
Now by reference to the accompanying drawings 1, the application of PAMAM carboxylated Graphene Co nano composite material in 4-nitroaniline degraded catalysis is described in detail.
The preparation of PAMAM carboxylated Graphene Co nano composite material comprises following step:
(1) synthesis of PAMAM/GO-COOH: take carboxylated Graphene 0.42g, add 40mL deionized water, 4gEDC and 4.2gNHS is added after ultrasonic disperse, 4h is stirred at 40 DEG C of lower magnetic forces, product filters, disperse in 40mL deionized water for ultrasonic after centrifugal, washed with de-ionized water, add 10mLPAMAM (the 4.0G concentration 0.1g/mL) aqueous solution, stirring reaction 12h at 35 DEG C, product is drying to obtain through centrifugal, washed with de-ionized water final vacuum;
(2) synthesis of PAMAM/GO-COOH/Co nano composite material: take PAMAM/GO-COOH/Co100mg, adds 20mL deionized water, ultrasonic disperse, adds 10mLCoCl
2solution (0.5mol/L), stirs 1h, then adds 0.5gNaBH
4, stir 4h at 50 DEG C of lower magnetic forces, product is collected in beaker after centrifugal, washed with de-ionized water, and then ultrasonic disperse, removes unnecessary Co
2+, end product, through centrifugal, washed with de-ionized water, filters final vacuum and is drying to obtain.
The degraded catalysis of PAMAM carboxylated Graphene Co nano composite material to 4-nitroaniline is probed into: obtain the PAMAM/GO-COOH/Co ultrasonic disperse of 10mg in 30mL5.8 × 10
-5in the aqueous solution of mol/L4-nitroaniline, mixture stirs room temperature (25 DEG C) in atmosphere, measures at set intervals with ultraviolet-visual spectrometer.The ultraviolet absorption peak of 4-nitroaniline is 378nm, illustrates that composite is to the degraded catalytic capability of 4-nitroaniline by absworption peak peak intensity.
As shown in Figure 1, under normal temperature condition, as long as have air and water to there is the aqueous solution degradation of PAMAM/GO-COOH/Co to 4-nitroaniline show high catalytic activity.After 8h, the aqueous solution catalytic degradation peak value of PAMAM/GO-COOH/Co to 4-nitroaniline is almost 0, illustrates that the aqueous solution catalytic degradation of PAMAM/GO-COOH/Co to 4-nitroaniline shows high catalytic performance.This take PAMAM/GO-COOH as the polymerization that template fabricated in situ cobalt nanometer particle provides more steric restriction cobalt nanometer particle, and pollutant is adsorbed onto surface by the huge specific surface energy of PAMAM/GO-COOH carries out catalytic degradation.More, just can carrying out in normal temperature indoor of PAMAM/GO-COOH/Co catalytic degradation reaction, any increase oxidant etc. are not (as H
2o
2).
Above-mentioned just preferred embodiment of the present invention, not does any pro forma restriction to the present invention.Any those of ordinary skill in the art, when not departing from technical solution of the present invention scope, can utilize the technology contents of above-mentioned announcement to make many possible variations and modification to technical solution of the present invention, or being revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to the technology of the present invention essence to any simple modification made for any of the above embodiments, equivalent variations and modification, all should drop in the scope of technical solution of the present invention protection.
Claims (2)
1. a preparation method for PAMAM carboxylated Graphene Co nano composite material, is characterized in that comprising following step:
(1) synthesis of PAMAM/GO-COOH: take carboxylated Graphene 0.42g, add 40mL deionized water, 4gEDC and 4.2gNHS is added after ultrasonic disperse, 4h is stirred at 40 DEG C of lower magnetic forces, product filters, disperse in 40mL deionized water for ultrasonic after centrifugal, washed with de-ionized water, add 10mLPAMAM (the 4.0G concentration 0.1g/mL) aqueous solution, stirring reaction 12h at 35 DEG C, product is drying to obtain through centrifugal, washed with de-ionized water final vacuum;
(2) synthesis of PAMAM/GO-COOH/Co nano composite material: take PAMAM/GO-COOH/Co100mg, adds 20mL deionized water, ultrasonic disperse, adds 10mLCoCl
2solution (0.5mol/L), stirs 1h, then adds 0.5gNaBH
4, stir 4h at 50 DEG C of lower magnetic forces, product is collected in beaker after centrifugal, washed with de-ionized water, and then ultrasonic disperse, removes unnecessary Co
2+, end product, through centrifugal, washed with de-ionized water, filters final vacuum and is drying to obtain.
2. the application that the PAMAM carboxylated Graphene Co nano composite material that according to claim 1 prepared by method is degraded in catalysis at 4-nitroaniline, is characterized in that: degraded catalytic process has water and air to participate in.
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| CN107501500A (en) * | 2017-08-16 | 2017-12-22 | 陕西科技大学 | Daiamid functionalization graphene/hyperbranched aqueous polyurethane and preparation method thereof |
| CN108014132A (en) * | 2016-11-03 | 2018-05-11 | 湖南师范大学 | With selective cytotoxicity graphene complex and preparation method thereof |
| CN110194451A (en) * | 2019-05-15 | 2019-09-03 | 华东理工大学 | There is grapheme material and its preparation method and the application of the macromolecule covalent modification of donor and acceptor groups simultaneously |
| CN110882724A (en) * | 2019-12-09 | 2020-03-17 | 万华化学集团股份有限公司 | Platinum-supported catalyst, preparation method thereof and application thereof in cyclododecanol synthesis |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107501500A (en) * | 2017-08-16 | 2017-12-22 | 陕西科技大学 | Daiamid functionalization graphene/hyperbranched aqueous polyurethane and preparation method thereof |
| CN107501500B (en) * | 2017-08-16 | 2020-05-19 | 陕西科技大学 | Polyamide-amine functionalized graphene/hyperbranched waterborne polyurethane and preparation method thereof |
| CN110194451A (en) * | 2019-05-15 | 2019-09-03 | 华东理工大学 | There is grapheme material and its preparation method and the application of the macromolecule covalent modification of donor and acceptor groups simultaneously |
| CN110882724A (en) * | 2019-12-09 | 2020-03-17 | 万华化学集团股份有限公司 | Platinum-supported catalyst, preparation method thereof and application thereof in cyclododecanol synthesis |
| CN110882724B (en) * | 2019-12-09 | 2022-11-08 | 万华化学集团股份有限公司 | Platinum-supported catalyst, preparation method thereof and application thereof in cyclododecanol synthesis |
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