CN103480413A - Preparation method of cationic polymer functionalized graphene-loaded platinum nanocomposite - Google Patents
Preparation method of cationic polymer functionalized graphene-loaded platinum nanocomposite Download PDFInfo
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Abstract
The invention belongs to the technical field of catalysts, and provides a preparation method of a cationic polymer functionalized graphene-loaded platinum nanocomposite. The preparation method comprises the following steps: preparing cationic polymer functionalized grapheme; and taking a halogen-containing acid of a precious metal as a metal source, taking a mixed solvent of polyethylene glycol and ethylene glycol as a stabilizer, a reducing agent and a solvent, adjusting the pH of a system by using sodium hydroxide, adding chloroplatinic acid and surface-functionalized graphene in a mass ratio of (1-5): 20, and reacting for 3-6min in a microwave oven at 140 DEG C to obtain a functionalized grapheme-loaded monodisperse platinum nanocomposite catalyst by one step. The functionalized grapheme-loaded monodisperse platinum nanocomposite catalyst prepared with the method has good stability, high load rate and dispersion of metal particles, and high electrocatalytic activity; and the preparation method is low in cost, nontoxic, and simple in process, and has low requirements on equipment; and with the preparation method, the large-scale production can be easily carried out.
Description
Technical field
The present invention relates to a kind of preparation method by cationic polymer functionalization graphene supported platinum nano compound, belong to catalyst technical field.
Technical background
Low-temperature fuel cell, as a kind of novel energy source device, has the multiple advantages such as fuel utilization efficiency is high, pollution-free, is subject to people to pay close attention to greatly the focus that has become countries in the world competitively to study.The active ingredient of low-temperature fuel cell used catalyst still be take platinum as main at present.The resource-constrained of platinum, characteristics expensive, that easily poisoned, greatly limited the commercialization process of low-temperature fuel cell.Development of new eelctro-catalyst, the performance that reduces noble metal dosage and improve eelctro-catalyst seem particularly important.The dispersion of carriers affect noble metal, the transmission of material, antitoxin voltinism energy and stability, the especially carrier of catalyst affect the performance of catalyst greatly on the promoting catalysis of noble metal.
Graphene is by sp
2the cellular two-dimensional nano material with monatomic thickness that the hydridization carbon atom forms, the monoatomic layer structures shape that it is special it there is abundant and novel physical property, there is outstanding heat conductivility and mechanical property, and electron mobility at a high speed under room temperature.Due to its good electric conductivity, Graphene is the desirable carrier of electrocatalysis material.More and more by people, paid close attention at present people (the Graphene nanoplate-Pt composite as a high performance electrocatalyst for direct methanol fuel cells. J Power Sources 2012 such as Hung HuaJie as the carrier of catalysis material with Graphene, 204:46-52) success loads on nano platinum particle on Graphene, and the composite of this platinum/graphen has good catalytic performance, can well be applied in methanol fuel cell, but because the oxy radical on the graphene oxide surface that over oxidation obtains also is reduced when reduction prepares metal nanoparticle, the inertia and the slickness that make the Graphene surface become again to there is graphite, therefore directly at Graphene surface acquisition higher density, reaching is very difficult than the Pt nanoparticle of steady load, so being used as at present the carrier of nano particle also is restricted.For this reason, many researchers attempt Graphene is carried out to modification, by to its functionalization, prepare the graphene nano material after modification, can retain to the full extent the Graphene intrinsic attribute, and introduce some other significant group by functionalization and reduce Graphene reunion between layers and increase its active area (Qu K-G, Wu L, Ren J-S, Qu X-G. Natural DNA-Modified Graphene/Pd Nanoparticles as Highly Active Catalyst for Formic Acid Electro-Oxidation and for the Suzuki Reaction. ACS Appl Mater Interfaces 2012, 4:5001-9, Liu Y-J, Huang Y-Q, Xie Y, Yang Z-H, Huang H-L, Zhou Q-Y. Preparation of highly dispersed CuPt nanoparticles on ionic-liquid-assisted graphene sheets for direct methanol fuel cell. Chem Eng J2012, 197:80-7, Jae Y-P, Seok K. Preparation and electroactivity of polymer functionalized graphene oxide-supported platinum nanoparticles catalysts. Inter J Hydrogen energy 2013, 38:6275 – 82.).
Cationic polymer is as a kind of water-soluble cationic polymer, have that positive charge density is high, good water solubility, molecular weight are easy to control, high effect nontoxic, the advantage such as cheap, the compound that particularly it can make under various pH conditions all has good anti-salt, alkali resistance, thereby has extremely strong polarity and to the affinity of anionic property material.Therefore be widely used in the fields such as oil exploitation, papermaking, mining, textile printing and dyeing, daily-use chemical industry and water treatment, become a large study hotspot of contemporary region of chemistry.
Advantage of the present invention is: the present invention is the positive charge that utilizes cationic polymer modified Graphene surface uniform to distribute, by electronegative chloroplatinic acid radical ion (PtCl
6 2-) by electrostatic adsorption, evenly absorption profiles is on the surface of Graphene.Direct-reduction PtCl under the polyalcohol microwave condition
6 2-thereby, realize that the Graphene surface in situ generates nano platinum particle (Pt NPs).Platinum (Pt) metallic particles that has overcome Direct precipitation on above-mentioned Graphene this technical barrier that is easy to reunite, realized the higher load factor of Pt NPs, and particle diameter evenly, size is controlled, increased substantially utilization rate and the catalytic performance of Pt catalyst.The prepared product of the present invention not only can be used for DMFC cathode and anode catalyst, can also obviously improve stability and the electro catalytic activity of graphene nanometer composite.
Summary of the invention
The purpose of this invention is to provide a kind of simple to operate, can avoid nano platinum particle to reunite and the preparation method of the cationic polymer functionalization graphene supported platinum nano compound that pattern is controlled.
Method for preparing catalyst of the present invention is at first to prepare the cationic polymer functionalization graphene, and then by the noble metal nano particles microwave reduction to the cationic polymer functionalization graphene, obtain the platinum nano catalyst prepared by the cationic polymer functionalization graphene, concrete steps are as follows:
(1) be in mass ratio 0.5-3:15-20:1000-2000, difference weighing cationic polymer, Graphene and distilled water, first cationic polymer and Graphene are mixed, add together in distilled water again, to mixing, then mixture is stirred to 24h at normal temperatures at ultrasonic lower mixing 0.5h, then carry out suction filtration, use the second distillation water washing, finally, at 40 ℃ of lower vacuum drying 4-8h, obtain surface-functionalized Graphene.
(2) take ultrasonic dispersion in the mixed liquor that chloroplatinic acid adds polyethylene glycol that volume ratio is 1-3:1 and ethylene glycol, disperse the shared ratio of chloroplatinic acid in rear mixed liquor to be: chloroplatinic acid: mixed liquor=0.05-0.08g:100mL obtains yellow platinum acid chloride solution.
(3) the surface-functionalized Graphene of step (1) gained is added in step (2) gained platinum acid chloride solution, wherein the mass ratio of chloroplatinic acid and surface-functionalized Graphene is 1-5:20, after stirring 30min, be transferred in micro-wave oven, in 140 ℃ of reaction 3-6min.
(4) naturally cool to room temperature after having reacted, No. 6 sand core funnel suction filtrations for products therefrom, absolute ethyl alcohol and deionized water are alternately washed 10 times, and products therefrom is dispersed in absolute ethyl alcohol, make cationic polymer functionalization graphene supported platinum nano compound.
Wherein said Graphene is the Graphene that improved Hummers method makes: graphite, sodium nitrate join respectively in three-neck flask, slowly add respectively the concentrated sulfuric acid, potassium permanganate under condition of ice bath, after 35 ℃ of water bath with thermostatic control mechanical agitation 7h, add the potassium permanganate of equivalent to continue to stir 12h, be cooled to room temperature and add the dilution of ice high purity water, adding mass fraction is 30% hydrogen peroxide deep oxidation again, obtains graphene oxide; Clean product with deionized water, concentrated hydrochloric acid, absolute ethyl alcohol, suction filtration, dry;
The cationic polymer of described step (1) is dimethyl diallyl ammonium chloride, diallyl dimethyl ammoniumchloride, polyacrylamide.
The cationic polymer functionalization graphene supported platinum nano compound that the present invention is prepared, nano platinum particle pattern rule, crystallization is complete, the grain diameter size is between 1nm～3nm, be uniformly dispersed, there is the high capacity rate of metallic, and there is the good electrical catalytic activity.This method has advantages of that reaction condition gentleness, reaction are easy to control, cost is low, technique and simple flow, and good prospects for commercial application is arranged.
The accompanying drawing explanation
The XRD diffraction spectrogram that Fig. 1 is prepared nanometer Pt/ dimethyl diallyl ammonium chloride-Graphene, in figure, diffraction maximum is the characteristic diffraction peak of carbon and platinum.
The transmission electron microscope photo that Fig. 2 is the prepared nanometer Pt/ dimethyl diallyl ammonium chloride-Graphene of embodiment 2.
The transmission electron microscope photo that Fig. 3 is the prepared nanometer Pt/ dimethyl diallyl ammonium chloride-Graphene of embodiment 7.
The specific embodiment
Below in conjunction with concrete embodiment, the present invention will be further described.Following examples are implemented take technical solution of the present invention under prerequisite; provided detailed embodiment; following non-limiting example is used for the present invention that explains; rather than limit the invention; in the protection domain of spirit of the present invention and claim; any modification and change that the present invention is made, all belong to protection scope of the present invention.
example 1
(1) mass ratio by dimethyl diallyl ammonium chloride, Graphene and solvent is 0.5:15:1000, weighing dimethyl diallyl ammonium chloride 5mg, Graphene 150mg and volume ratio are 1:1 polyethylene glycol/ethylene glycol mixture 10g respectively, drip polyethylene glycol/ethylene glycol mixture in dimethyl diallyl ammonium chloride and Graphene, again at ultrasonic lower mixing 0.5h to mixing, then mixture is stirred to 24h at normal temperatures, carry out again suction filtration, use the second distillation water washing, finally, at 40 ℃ of lower vacuum drying 4 h, obtain surface-functionalized Graphene.
(2) taking chloroplatinic acid, to be placed in volume ratio be the ultrasonic dispersion of 1:1 polyethylene glycol/ethylene glycol mixture, chloroplatinic acid shared ratio chloroplatinic acid in whole mixed liquor after disperseing: (polyethylene glycol/ethylene glycol)=0.05:100(g/mL) obtain yellow platinum acid chloride solution.
(3) mass ratio by chloroplatinic acid and surface-functionalized Graphene is 1:20, the surface-functionalized Graphene of step (1) gained is added in step (2) gained platinum acid chloride solution, after stirring 30min, be transferred in micro-wave oven, in 140 ℃ of reaction 3min.
(4) naturally cool to room temperature after having reacted, No. 6 sand core funnel suction filtrations for products therefrom, absolute ethyl alcohol and deionized water are alternately washed 10 times, then are dispersed in absolute ethyl alcohol, make platinum/functionalization graphene nano-complex catalyst.
example 2
(1) mass ratio by dimethyl diallyl ammonium chloride, Graphene and solvent is 1:15:1500, weighing dimethyl diallyl ammonium chloride 10mg, Graphene 150mg and volume ratio are 2:1 polyethylene glycol/ethylene glycol mixture 15g respectively, drip polyethylene glycol/ethylene glycol mixture in dimethyl diallyl ammonium chloride and Graphene, again at ultrasonic lower mixing 0.5h to mixing, then mixture is stirred to 24h at normal temperatures, carry out again suction filtration, use the second distillation water washing, finally, at 40 ℃ of lower vacuum drying 6 h, obtain surface-functionalized Graphene.
(2) taking chloroplatinic acid, to be placed in volume ratio be the ultrasonic dispersion of 2:1 polyethylene glycol/ethylene glycol mixture, chloroplatinic acid shared ratio chloroplatinic acid in whole mixed liquor after disperseing: (polyethylene glycol/ethylene glycol)=0.06:100(g/mL) obtain yellow platinum acid chloride solution.
(3) mass ratio by chloroplatinic acid and surface-functionalized Graphene is 1:10, the surface-functionalized Graphene of step (1) gained is added in step (2) gained platinum acid chloride solution, after stirring 30min, be transferred in micro-wave oven, in 140 ℃ of reaction 5min.
(4) naturally cool to room temperature after having reacted, No. 6 sand core funnel suction filtrations for products therefrom, absolute ethyl alcohol and deionized water are alternately washed 10 times, then are dispersed in absolute ethyl alcohol, make platinum/functionalization graphene nano-complex catalyst.
example 3
(1) mass ratio by dimethyl diallyl ammonium chloride, Graphene and solvent is 1.5:16:1500, weighing dimethyl diallyl ammonium chloride 15mg, Graphene 160mg and volume ratio are 3:1 polyethylene glycol/ethylene glycol mixture 15g respectively, drip polyethylene glycol/ethylene glycol mixture in dimethyl diallyl ammonium chloride and Graphene, again at ultrasonic lower mixing 0.5h to mixing, then mixture is stirred to 24h at normal temperatures, carry out again suction filtration, use the second distillation water washing, finally, at 40 ℃ of lower vacuum drying 8 h, obtain surface-functionalized Graphene.
(2) taking chloroplatinic acid, to be placed in volume ratio be the ultrasonic dispersion of 3:1 polyethylene glycol/ethylene glycol mixture, chloroplatinic acid shared ratio chloroplatinic acid in whole mixed liquor after disperseing: (polyethylene glycol/ethylene glycol)=0.07:100(g/mL) obtain yellow platinum acid chloride solution.
(3) mass ratio by chloroplatinic acid and surface-functionalized Graphene is 3:20, the surface-functionalized Graphene of step (1) gained is added in step (2) gained platinum acid chloride solution, after stirring 30min, be transferred in micro-wave oven, in 140 ℃ of reaction 6min.
(4) naturally cool to room temperature after having reacted, No. 6 sand core funnel suction filtrations for products therefrom, absolute ethyl alcohol and deionized water are alternately washed 10 times, then are dispersed in absolute ethyl alcohol, make platinum/functionalization graphene nano-complex catalyst.
example 4
(1) mass ratio by dimethyl diallyl ammonium chloride, Graphene and solvent is 2.5:18:1800, weighing dimethyl diallyl ammonium chloride 25mg, Graphene 180mg and volume ratio are 2:1 polyethylene glycol/ethylene glycol mixture 18g respectively, drip polyethylene glycol/ethylene glycol mixture in dimethyl diallyl ammonium chloride and Graphene, again at ultrasonic lower mixing 0.5h to mixing, then mixture is stirred to 24h at normal temperatures, carry out again suction filtration, use the second distillation water washing, finally, at 40 ℃ of lower vacuum drying 7 h, obtain surface-functionalized Graphene.
(2) taking chloroplatinic acid, to be placed in volume ratio be the ultrasonic dispersion of 2:1 polyethylene glycol/ethylene glycol mixture, chloroplatinic acid shared ratio chloroplatinic acid in whole mixed liquor after disperseing: (polyethylene glycol/ethylene glycol)=0.08:100(g/mL) obtain yellow platinum acid chloride solution.
(3) mass ratio by chloroplatinic acid and surface-functionalized Graphene is 4:20, the surface-functionalized Graphene of step (1) gained is added in step (2) gained platinum acid chloride solution, after stirring 30min, be transferred in micro-wave oven, in 140 ℃ of reaction 8min.
(4) naturally cool to room temperature after having reacted, No. 6 sand core funnel suction filtrations for products therefrom, absolute ethyl alcohol and deionized water are alternately washed 10 times, then are dispersed in absolute ethyl alcohol, make platinum/functionalization graphene nano-complex catalyst.
example 5
(1) mass ratio by polyacrylamide, Graphene and solvent is 0.5:15:1000, weighing polyacrylamide 5mg, Graphene 150mg and volume ratio are 1:1 polyethylene glycol/ethylene glycol mixture 10g respectively, drip polyethylene glycol/ethylene glycol mixture in dimethyl diallyl ammonium chloride and Graphene, again at ultrasonic lower mixing 0.5h to mixing, then mixture is stirred to 24h at normal temperatures, carry out again suction filtration, use the second distillation water washing, finally, at 40 ℃ of lower vacuum drying 6 h, obtain surface-functionalized Graphene.
(2) taking chloroplatinic acid, to be placed in volume ratio be the ultrasonic dispersion of 1:1 polyethylene glycol/ethylene glycol mixture, chloroplatinic acid shared ratio chloroplatinic acid in whole mixed liquor after disperseing: (polyethylene glycol/ethylene glycol)=0.05:100(g/mL) obtain yellow platinum acid chloride solution.
(3) mass ratio by chloroplatinic acid and surface-functionalized Graphene is 3:20, the surface-functionalized Graphene of step (1) gained is added in step (2) gained platinum acid chloride solution, after stirring 30min, be transferred in micro-wave oven, in 140 ℃ of reaction 5min.
(4) naturally cool to room temperature after having reacted, No. 6 sand core funnel suction filtrations for products therefrom, absolute ethyl alcohol and deionized water are alternately washed 10 times, then are dispersed in absolute ethyl alcohol, make platinum/functionalization graphene nano-complex catalyst.
example 6
(1) mass ratio by dimethyl diallyl ammonium chloride, Graphene and solvent is 0.5:20:2000, weighing dimethyl diallyl ammonium chloride 5mg, Graphene 150mg and volume ratio are 2:1 polyethylene glycol/ethylene glycol mixture 20g respectively, drip polyethylene glycol/ethylene glycol mixture in dimethyl diallyl ammonium chloride and Graphene, again at ultrasonic lower mixing 0.5h to mixing, then mixture is stirred to 24h at normal temperatures, carry out again suction filtration, use the second distillation water washing, finally, at 40 ℃ of lower vacuum drying 8 h, obtain surface-functionalized Graphene.
(2) taking chloroplatinic acid, to be placed in volume ratio be the ultrasonic dispersion of 2:1 polyethylene glycol/ethylene glycol mixture, chloroplatinic acid shared ratio chloroplatinic acid in whole mixed liquor after disperseing: (polyethylene glycol/ethylene glycol)=0.07:100(g/mL) obtain yellow platinum acid chloride solution.
(3) mass ratio by chloroplatinic acid and surface-functionalized Graphene is 3:20, the surface-functionalized Graphene of step (1) gained is added in step (2) gained platinum acid chloride solution, after stirring 30min, be transferred in micro-wave oven, in 140 ℃ of reaction 5min.
(4) naturally cool to room temperature after having reacted, No. 6 sand core funnel suction filtrations for products therefrom, absolute ethyl alcohol and deionized water are alternately washed 10 times, then are dispersed in absolute ethyl alcohol, make platinum/functionalization graphene nano-complex catalyst.
example 7
(1) mass ratio by dimethyl diallyl ammonium chloride, Graphene and solvent is 2:15:2000, weighing dimethyl diallyl ammonium chloride 20mg, Graphene 150mg and volume ratio are 2:1 polyethylene glycol/ethylene glycol mixture 20g respectively, drip polyethylene glycol/ethylene glycol mixture in dimethyl diallyl ammonium chloride and Graphene, again at ultrasonic lower mixing 0.5h to mixing, then mixture is stirred to 24h at normal temperatures, carry out again suction filtration, use the second distillation water washing, finally, at 40 ℃ of lower vacuum drying 4 h, obtain surface-functionalized Graphene.
(2) taking chloroplatinic acid, to be placed in volume ratio be the ultrasonic dispersion of 2:1 polyethylene glycol/ethylene glycol mixture, chloroplatinic acid shared ratio chloroplatinic acid in whole mixed liquor after disperseing: (polyethylene glycol/ethylene glycol)=0.08:100(g/mL) obtain yellow platinum acid chloride solution.
(3) mass ratio by chloroplatinic acid and surface-functionalized Graphene is 5:20, the surface-functionalized Graphene of step (1) gained is added in step (2) gained platinum acid chloride solution, after stirring 30min, be transferred in micro-wave oven, in 140 ℃ of reaction 6min.
(4) naturally cool to room temperature after having reacted, No. 6 sand core funnel suction filtrations for products therefrom, absolute ethyl alcohol and deionized water are alternately washed 10 times, then are dispersed in absolute ethyl alcohol, make platinum/functionalization graphene nano-complex catalyst.
Claims (3)
1. the preparation method of a cationic polymer functionalization graphene supported platinum nano compound is characterized in that making as follows:
(1) be in mass ratio 0.5-3:15-20:1000-2000, difference weighing cationic polymer, Graphene and distilled water, first cationic polymer and Graphene are mixed, add together in distilled water again, to mixing, then mixture is stirred to 24h at normal temperatures at ultrasonic lower mixing 0.5h, then carry out suction filtration, use the second distillation water washing, finally, at 40 ℃ of lower vacuum drying 4-8h, obtain surface-functionalized Graphene;
(2) take ultrasonic dispersion in the mixed liquor that chloroplatinic acid adds polyethylene glycol that volume ratio is 1-3:1 and ethylene glycol, disperse the shared ratio of chloroplatinic acid in rear mixed liquor to be: chloroplatinic acid: mixed liquor=0.05-0.08g:100mL obtains yellow platinum acid chloride solution;
(3) the surface-functionalized Graphene of step (1) gained is added in step (2) gained platinum acid chloride solution, wherein the mass ratio of chloroplatinic acid and surface-functionalized Graphene is 1-5:20, after stirring 30min, be transferred in micro-wave oven, in 140 ℃ of reaction 3-6min;
(4) naturally cool to room temperature after having reacted, No. 6 sand core funnel suction filtrations for products therefrom, absolute ethyl alcohol and deionized water are alternately washed 10 times, and products therefrom is dispersed in absolute ethyl alcohol, make cationic polymer functionalization graphene supported platinum nano compound.
2. the preparation method of a kind of cationic polymer functionalization graphene supported platinum nano compound according to claim 1, it is characterized in that: described Graphene makes by improved Hummers method.
3. the preparation method of a kind of cationic polymer functionalization graphene supported platinum nano compound according to claim 1, it is characterized in that: the cationic polymer of described step (1) is dimethyl diallyl ammonium chloride, diallyl dimethyl ammoniumchloride, polyacrylamide.
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| CN104841482A (en) * | 2015-04-01 | 2015-08-19 | 沈阳理工大学 | Polymer-modified nano precious metal catalyst and preparation method therefor |
| CN105215352A (en) * | 2015-10-26 | 2016-01-06 | 吉林大学 | By the preparation method of the cationic polymer modified gold nanoclusters of coated with silica |
| CN105576257A (en) * | 2015-12-21 | 2016-05-11 | 太原理工大学 | Method using underwater arc discharge to prepare graphene supported Pt catalyst |
| CN107858661A (en) * | 2017-11-02 | 2018-03-30 | 中国科学院山西煤炭化学研究所 | A kind of methanol electro-oxidizing-catalyzing agent and its preparation method and application |
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| CN104841482A (en) * | 2015-04-01 | 2015-08-19 | 沈阳理工大学 | Polymer-modified nano precious metal catalyst and preparation method therefor |
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| CN105215352A (en) * | 2015-10-26 | 2016-01-06 | 吉林大学 | By the preparation method of the cationic polymer modified gold nanoclusters of coated with silica |
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