CN104993160A - Preparing method for non-precious metal ion complexation Schiff base graphene catalyst - Google Patents
Preparing method for non-precious metal ion complexation Schiff base graphene catalyst Download PDFInfo
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- CN104993160A CN104993160A CN201510472904.9A CN201510472904A CN104993160A CN 104993160 A CN104993160 A CN 104993160A CN 201510472904 A CN201510472904 A CN 201510472904A CN 104993160 A CN104993160 A CN 104993160A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a preparing method for a non-precious metal ion complexation Schiff base graphene catalyst and belongs to the technical field of fuel batteries. The preparing method comprises the steps that firstly, amidogen functional groups are grafted to the edge flaw positions of a graphene sheet; secondly, the amidogen functional groups are converted into Schiff base functional groups through amine-aldehyde condensation; finally, complexation is carried out on non-precious metal ions, and the non-precious metal ion complexation Schiff base graphene catalyst of an adjustable three-dimensional stereostructure is obtained. According to the preparing method, the complexation action of the non-precious metal ions and the Schiff base is ingeniously used, a link is formed between layers of graphene, the three-dimensional cross-linked graphene catalyst stereostructure is formed, and the electron conduction capability between layers of the graphene and the mass transfer speed in the layers are increased; meanwhile, a large quantity of metal Schiff base complex catalytic activity sites are generated, concerted catalysis with the graphene is achieved, and the catalytic activity is improved. The operation is simple, industrialization production is easy, and the prepared catalyst can be widely applied to fuel batteries with proton exchange films as electrolytes.
Description
Technical field
The invention belongs to field of fuel cell technology, particularly a kind of preparation method of base metal ion complexation schiff bases graphen catalyst.
Background technology
Fuel cell has the advantages such as energy conversion efficiency is high, environmental friendliness, room temperature start fast, is considered to following electric automobile and the most promising chemical power source of other civilian occasion.At present, main fuel battery cathod catalyst is platinum class catalyst, but its high cost, scarcity of resources and easily the shortcoming such as poisoning seriously constrain the development of fuel cell.Therefore, develop a kind of with low cost and the fuel battery negative pole non-precious metal catalyst of excellent performance is significant.
Just developing efficient non-noble metal fuel cell cathod catalyst has done a large amount of research work both at home and abroad.Wherein, nitrogen-doped graphene material has the characteristics such as the conductivity of unique two-dimensional structure, high-ratio surface and excellence because of it, and receives much attention.Chinese invention patent CN201310586826.6 discloses " a kind of Synthesis and applications of nitrogen-doped graphene fuel-cell catalyst ", and the mixture that the method comprises graphene oxide, base metal salt and nitrogenous organic molecule by high-temperature heat treatment prepares nitrogen-doped graphene catalyst.Catalyst prepared by this method has certain oxygen reduction catalytic activity and with low cost.But Graphene is easily reunited in this method building-up process, cause a large amount of avtive spot to be coated on catalytic inner, still lower being difficult to meets the requirement of natural fuel battery applications to catalytic activity.Chinese invention patent CN201410408484.3 discloses " preparation of the aerogel carried non noble metal oxygen reduction catalyst of a kind of nitrogen-doped graphene ", the method is by freeze drying organic amine, aldehyde, slaine and graphene oxide solution, form organogel, then high-temperature heat treatment prepares load non-noble metal nitrogen-doped graphene aeroge oxygen reduction catalyst.This method adopts gelation effectively can solve the agglomeration traits of Graphene in preparation process.But easily produce uneven pore structure in this method building-up process, limit the conducting power of catalytic inner proton and electronics.Chinese invention patent CN201410568641.7 discloses " a kind of preparation method of three-dimensional nitrogen-doped graphene/CoOx composite material ", the method take graphene oxide as carrier, phthalonitrile is nitrogenous source, cobalt acetate is transition metal precursor, add surfactant, be there is by the preparation of solvent heat technology the nitrogen-doped graphene/CoO of three-dimensional structure
xcomposite nano materials.Co prepared by the method
3o
4granular composite is even, has good hydrogen reduction performance.But it is stacking that the graphene aerogel prepared by this method structurally also exists between a large amount of lamella, cause the mass transfer of sheet interlayer difficulty, conductivity poor.
Summary of the invention
Object of the present invention is lower for the catalytic activity of existing Graphene class non-precious metal catalyst, catalytic inner mass transfer is weak, the shortcoming of graphene layer interlayer electrical conductance difference, provides a kind of preparation method of base metal ion complexation schiff bases graphen catalyst.First the present invention passes through organic amine redox graphene by amidine functional group grafting in graphene film edge defect position, by the condensation of amine aldehyde, amidine functional group is converted into schiff bases functional group again, finally by schiff bases functional group and base metal ion complexation, obtain that have can the base metal ion complexation schiff bases graphen catalyst of modulation 3-D solid structure.The present invention utilizes the complexing of base metal ion and schiff bases dexterously, on the one hand, form tie between layers at Graphene, form three-dimensional cross-linked graphen catalyst stereochemical structure, improve catalysis mass transfer rate in electronic conduction ability between graphene layer and layer; On the other hand, in catalyst three dimensions, complex compound forms a large amount of Metal Schiff _ base active site, reacts, significantly improve catalytic activity with Graphene concerted catalysis.
The object of the present invention is achieved like this: a kind of preparation method of base metal ion complexation schiff bases graphen catalyst, concrete grammar step comprises
(1) preparation of graphene oxide
Take 3 grams of graphite powders, joining 600 milliliters of Nong Lin Suan ︰ concentrated sulfuric acid volume ratios is in the mixed solution of 1 ︰ 9, after mixing, obtains graphite powder mixed liquor; After above-mentioned graphite powder mixed liquor is placed in ice-water bath, slowly adds 18 grams of potassium permanganate pressed powders, be uniformly mixed, obtain potassium permanganate graphite powder mixed liquor; Then above-mentioned potassium permanganate graphite powder mixed liquor is warming up to 50 DEG C, stirring reaction 12 hours, more slowly pours in excessive frozen water, obtain purple green ice water solution; It is last that in the green ice water solution of above-mentioned purple, slowly add mass fraction be continuously 30% hydrogenperoxide steam generator, to solution become golden yellow after stop adding, after filtration, watery hydrochloric acid and ultra-pure water be alternately after washing, freeze drying, obtains graphene oxide.
(2) preparation of amination Graphene
By graphite oxide Xi ︰ organic amine mass ratio for 1 ︰ 89 ~ 186 takes graphene oxide prepared by step (1) and organic amine; First by the graphene oxide dispersion prepared by step (1) in deionized water, the graphene oxide suspension that mass concentration is 0.4 ~ 1.2 mg/ml is formed; Again organic amine is added in above-mentioned graphene oxide dispersion, stirring at room temperature 10 ~ 20 minutes, forms organic amine graphene oxide suspension; Then above-mentioned organic amine graphene oxide suspension is heated to 80 ~ 100 DEG C, stirring and refluxing 4 ~ 6 hours; Finally by suction filtration, ethanol washing 4 ~ 6 times, dry rear acquisition amination Graphene.
Wherein said organic amine be ethylenediamine, p-phenylenediamine (PPD), melamine one of them.
(3) preparation of schiff bases Graphene
Mass ratio 1 ︰ 3.2 ~ 10 ︰ 12.5 ~ 39 gathering cyanogen amine ︰ salicylide by amine functionalized graphene ︰ tri-takes amination Graphene, melamine and salicylide prepared by step (2) respectively; First by amination graphene dispersion in dimethyl formamide or dimethyl sulfoxide (DMSO), ultrasonic 30 ~ 60 minutes, forming mass concentration was the amination graphene suspension of 0.63 ~ 2.3 mg/ml; Salicylide is added in 10 ~ 20 milliliters of dimethyl formamides or dimethyl sulfoxide (DMSO), forms salicylide dimethyl formamide or dimethyl sulphoxide solution; In above-mentioned amination graphene suspension, add melamine pressed powder, stir, be warming up to 135 ~ 180 DEG C, after melamine dissolves completely, drip above-mentioned salicylide dimethyl formamide or dimethyl sulphoxide solution 10 ~ 20 milliliters, condensing reflux 8 ~ 10 hours; After suction filtration, ethanol washing 4 ~ 6 times, drying, obtain schiff bases Graphene.
(4) preparation of base metal ion complexation schiff bases graphen catalyst
Be that 1 ︰ 2 ~ 4.8 takes schiff bases Graphene and base metal ion presoma pressed powder by the mass ratio of schiff bases Shi Mo Xi ︰ base metal ion presoma; First by schiff bases graphene dispersion in dimethyl formamide, form the schiff bases graphene dispersing solution of concentration 0.36 ~ 1.08 mg/ml; Then in above-mentioned schiff bases graphene dispersing solution, add base metal ion presoma pressed powder, ultrasonic agitation, after 30 ~ 60 minutes, is warming up to 135 ~ 150 DEG C, refluxes 4 ~ 6 hours; After suction filtration, ethanol washing 4 ~ 6 times, drying, obtain base metal ion complexation schiff bases graphen catalyst.
Wherein said base metal ion presoma be cobalt acetate, ferric acetate, nickel acetate one of them.
After the present invention adopts technique scheme, mainly contain following advantage:
(1) complexing of base metal ion and schiff bases, forms tie between layers at Graphene, forms three-dimensional cross-linked graphen catalyst stereochemical structure, improves catalysis mass transfer rate in electronic conduction ability between graphene layer and layer.
(2) being formed in catalyst three dimensions of complex compound produces a large amount of Metal Schiff _ base active site, reacts, significantly improve catalytic activity with Graphene concerted catalysis.
(3) the inventive method is simple, low production cost, and operating procedure is simple.
Adopting the 3 D stereo base metal ion complexation schiff bases graphen catalyst prepared by the present invention to can be applicable to proton exchange membrane is electrolytical fuel cell, as the gas electrode of hydrogen-oxygen proton exchange membrane fuel cell, direct methanol fuel cell etc.With the fuel cell that the present invention manufactures, be widely used in electric automobile, various spacecraft, portable electric appts, as video camera, notebook computer, electronic toy etc.
Accompanying drawing illustrates:
The scanning electron microscope (SEM) photograph of Fig. 1 base metal ion complexation schiff bases graphen catalyst prepared by embodiment 1.
The infrared spectrogram of Fig. 2 base metal ion complexation schiff bases graphen catalyst prepared by embodiment 1.
In figure: curve 1 is the infrared spectrogram of graphene oxide prepared by embodiment 1; Curve 2 is infrared spectrograms of embodiment 1 amination Graphene; Curve 3 is infrared spectrograms of embodiment 1 schiff bases Graphene; Curve 4 is infrared spectrograms of the base metal ion complexation schiff bases graphen catalyst of embodiment 1.
Fig. 3 is base metal ion complexation schiff bases graphen catalyst and the hydrogen reduction linear scan curve of contrast experiment 1 on rotating ring disk electrode (r.r.d.e) of embodiment 2 preparation.
In figure: curve 1 is that the base metal ion complexation schiff bases graphen catalyst prepared of embodiment 2 is at the catalytic oxidation-reduction linear scan curve of 1600 revs/min; Curve 2 is that the base metal ion complexation amination graphen catalyst prepared of contrast experiment 1 is at the catalytic oxidation-reduction linear scan curve of 1600 revs/min.
Fig. 4 is base metal ion complexation schiff bases graphen catalyst and the hydrogen reduction linear scan curve of contrast experiment 2 on rotating ring disk electrode (r.r.d.e) of embodiment 2 preparation.
In figure: curve 1 is that the base metal ion complexation schiff bases graphen catalyst prepared of embodiment 2 is at the catalytic oxidation-reduction linear scan curve of 1600 revs/min; Curve 2 is that the schiff bases graphen catalyst prepared of contrast experiment 2 is at the catalytic oxidation-reduction linear scan curve of 1600 revs/min.
Fig. 5 is the situation of the stability of catalytic activity change of base metal ion complexation schiff bases graphen catalyst prepared by embodiment 3.
In figure: curve 1 is that the base metal ion complexation schiff bases graphen catalyst prepared of embodiment 3 is at the catalytic oxidation-reduction linear scan curve chart of 1600 revs/min; Curve 2 is base metal ion complexation schiff bases graphen catalysts prepared by embodiment 3 is reference electrode in silver/silver chloride electrode, platinum loop is to electrode, the potassium hydroxide solution of saturated 0.1 mol/L of nitrogen is electrolyte, sweep speed is after the cyclic voltammetric 2000 under 50 millivolts of/second conditions encloses, at the catalytic oxidation-reduction linear scan curve chart of 1600 revs/min.
Embodiment:
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1
(1) preparation of graphene oxide
Take 3 grams of graphite powders, joining 600 milliliters of Nong Lin Suan ︰ concentrated sulfuric acid volume ratios is in the mixed solution of 1 ︰ 9, after mixing, obtains graphite powder mixed liquor; After above-mentioned graphite powder mixed liquor is placed in ice-water bath, slowly adds 18 grams of potassium permanganate pressed powders, be uniformly mixed, obtain potassium permanganate graphite powder mixed liquor; Then above-mentioned potassium permanganate graphite powder mixed liquor is warming up to 50 DEG C, stirring reaction 12 hours, more slowly pours in excessive frozen water, obtain purple green ice water solution; It is last that in the green ice water solution of above-mentioned purple, slowly add mass fraction be continuously 30% hydrogenperoxide steam generator, to solution become golden yellow after stop adding, after filtration, watery hydrochloric acid and ultra-pure water be alternately after washing, freeze drying, obtains graphene oxide; Curve 1 in IR Characterization corresponding diagram 2.
(2) preparation of amination Graphene
By graphite oxide Xi ︰ ethylenediamine mass ratio for 1 ︰ 89 takes graphene oxide prepared by step (1) and ethylenediamine; First by the graphene oxide dispersion prepared by step (1) in deionized water, the graphene oxide suspension that mass concentration is 0.4 mg/ml is formed; Again ethylenediamine is added in above-mentioned graphene oxide dispersion, stirring at room temperature 10 minutes, forms ethylenediamine graphene oxide suspension; Then above-mentioned ethylenediamine graphene oxide suspension is heated to 95 DEG C, stirring and refluxing 6 hours; 6 times, dry rear acquisition amination Graphene is washed finally by suction filtration, ethanol; Curve 2 in IR Characterization corresponding diagram 2.
(3) preparation of schiff bases Graphene
Mass ratio 1 ︰ 3.2 ︰ 12.5 gathering cyanogen amine ︰ salicylide by amine functionalized graphene ︰ tri-takes amination Graphene, melamine and salicylide prepared by step (2) respectively; First by amination graphene dispersion in dimethyl formamide, ultrasonic 30 minutes, forming mass concentration was the amination graphene suspension of 0.63 mg/ml; Salicylide is added in 20 milliliters of dimethyl formamides, forms salicylide dimethyl formamide solution; In above-mentioned amination graphene suspension, add melamine pressed powder, stir, be warming up to 150 DEG C, after melamine dissolves completely, drip above-mentioned salicylide dimethyl formamide solution 20 milliliters, condensing reflux 10 hours; Wash 6 times, after drying finally by suction filtration, ethanol, obtain schiff bases Graphene; Curve 3 in IR Characterization corresponding diagram 2.
(4) preparation of base metal ion complexation schiff bases graphen catalyst
Be that 1 ︰ 4.8 takes schiff bases Graphene and cobalt acetate pressed powder by the mass ratio of schiff bases Shi Mo Xi ︰ cobalt acetate; First by schiff bases graphene dispersion in dimethyl formamide, form the schiff bases graphene dispersing solution of concentration 0.72 mg/ml; Then in above-mentioned schiff bases graphene dispersing solution, add cobalt acetate pressed powder, ultrasonic agitation, after 30 minutes, is warming up to 150 DEG C, refluxes 6 hours; Wash 6 times, after drying finally by suction filtration, ethanol, obtain base metal ion complexation schiff bases graphen catalyst; ESEM characterizes corresponding diagram 1; Curve 4 in IR Characterization corresponding diagram 2.
Embodiment 2
Step (1) is with step (1) in embodiment 1.
(2) preparation of amination Graphene
By graphite oxide Xi ︰ p-phenylenediamine (PPD) mass ratio for 1 ︰ 140 takes graphene oxide prepared by step (1) and p-phenylenediamine (PPD); First by the graphene oxide dispersion prepared by step (1) in deionized water, the graphene oxide suspension that mass concentration is 0.8 mg/ml is formed; Again p-phenylenediamine (PPD) is added in above-mentioned graphene oxide dispersion, stirring at room temperature 15 minutes, forms p-phenylenediamine (PPD) graphene oxide suspension; Then above-mentioned p-phenylenediamine (PPD) graphene oxide suspension is heated to 80 DEG C, stirring and refluxing 4 hours; 4 times, dry rear acquisition amination Graphene is washed finally by suction filtration, ethanol;
(3) preparation of schiff bases Graphene
Mass ratio 1 ︰ 4.9 ︰ 19.1 gathering cyanogen amine ︰ salicylide by amine functionalized graphene ︰ tri-takes amination Graphene, melamine and salicylide prepared by step (2) respectively; First by amination graphene dispersion in dimethyl sulfoxide (DMSO), ultrasonic 45 minutes, forming mass concentration was the amination graphene suspension of 1.2 mg/ml; Salicylide is added in 10 milliliters of dimethyl sulfoxide (DMSO)s, forms salicylide dimethyl sulphoxide solution; In above-mentioned amination graphene suspension, add melamine pressed powder, stir, be warming up to 180 DEG C, after melamine dissolves completely, drip above-mentioned salicylide dimethyl sulphoxide solution 10 milliliters, condensing reflux 8 hours; Wash 4 times, after drying finally by suction filtration, ethanol, obtain schiff bases Graphene;
(4) preparation of base metal ion complexation schiff bases graphen catalyst
Be that 1 ︰ 2 takes schiff bases Graphene and ferric acetate pressed powder by the mass ratio of schiff bases Shi Mo Xi ︰ ferric acetate; First by schiff bases graphene dispersion in dimethyl formamide, form the schiff bases graphene dispersing solution of concentration 0.36 mg/ml; Then in above-mentioned schiff bases graphene dispersing solution, add ferric acetate pressed powder, ultrasonic agitation, after 60 minutes, is warming up to 135 DEG C, refluxes 5 hours; Wash 5 times, after drying finally by suction filtration, ethanol, obtain base metal ion complexation schiff bases graphen catalyst.
(5) the oxygen reduction catalytic activity test of base metal ion complexation schiff bases graphen catalyst
Adopt three-electrode system, electrode prepared by the base metal ion complexation schiff bases graphen catalyst obtained by step (4) is work electrode, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, under the rotating speed that rotating ring disk electrode (r.r.d.e) is 1600 revs/min, linear scan is carried out, the oxygen reduction catalytic activity of evaluate catalysts, curve 1 in curve 1 and Fig. 4 in corresponding diagram 3 in the potassium hydroxide solution of saturated 0.1 mol/L of oxygen.
Embodiment 3
Step (1) is with step (1) in embodiment 1.
(2) preparation of amination Graphene
By graphite oxide Xi ︰ melamine mass ratio for 1 ︰ 186 takes graphene oxide prepared by step (1) and melamine; First by the graphene oxide dispersion prepared by step (1) in deionized water, the graphene oxide suspension that mass concentration is 1.2 mg/ml is formed; Again melamine is added in above-mentioned graphene oxide dispersion, stirring at room temperature 20 minutes, forms melamine graphene oxide suspension; Then above-mentioned melamine graphene oxide suspension is heated to 100 DEG C, stirring and refluxing 5 hours; 5 times, dry rear acquisition amination Graphene is washed finally by suction filtration, ethanol;
(3) preparation of schiff bases Graphene
Mass ratio 1 ︰ 10 ︰ 39 gathering cyanogen amine ︰ salicylide by amine functionalized graphene ︰ tri-takes amination Graphene, melamine and salicylide prepared by step (2) respectively; First by amination graphene dispersion in dimethyl formamide, ultrasonic 60 minutes, forming mass concentration was the amination graphene suspension of 2.3 mg/ml; Salicylide is added in 15 milliliters of dimethyl formamides, forms salicylide dimethyl formamide solution; In above-mentioned amination graphene suspension, add melamine pressed powder, stir, be warming up to 135 DEG C, after melamine dissolves completely, drip above-mentioned salicylide dimethyl formamide solution 15 milliliters, condensing reflux 9 hours; Wash 5 times, after drying finally by suction filtration, ethanol, obtain schiff bases Graphene;
(4) preparation of base metal ion complexation schiff bases graphen catalyst
Be that 1 ︰ 3.6 takes schiff bases Graphene and nickel acetate pressed powder by the mass ratio of schiff bases Shi Mo Xi ︰ nickel acetate; First by schiff bases graphene dispersion in dimethyl formamide, form the schiff bases graphene dispersing solution of concentration 1.08 mg/ml; Then in above-mentioned schiff bases graphene dispersing solution, add nickel acetate pressed powder, ultrasonic agitation, after 45 minutes, is warming up to 145 DEG C, refluxes 4 hours; Wash 4 times, after drying finally by suction filtration, ethanol, obtain base metal ion complexation schiff bases graphen catalyst.
(5) the stability of catalytic activity test of base metal ion complexation schiff bases graphen catalyst
Adopt three-electrode system, electrode prepared by the base metal ion complexation schiff bases graphen catalyst obtained with step (4) is for work electrode, silver/silver chloride electrode is reference electrode, platinum loop is to electrode, linear scan is carried out in the potassium hydroxide solution of saturated 0.1 mol/L of oxygen, then in the potassium hydroxide solution of saturated 0.1 mol/L of nitrogen, carry out cyclic voltammetry scan 2000 to enclose, linear scan is carried out in the potassium hydroxide solution of last 0.1 mol/L saturated at oxygen, contrast the linear scan of the former brand-new electrode, by the stability of the recession level evaluate catalysts of oxygen reduction catalytic activity, corresponding diagram 5.
Contrast test 1
Step (1) is with step (1) in embodiment 1.
(2) preparation of amination Graphene
By graphite oxide Xi ︰ ethylenediamine mass ratio for 1 ︰ 89 takes graphene oxide prepared by step (1) and ethylenediamine; First by the graphene oxide dispersion prepared by step (1) in deionized water, the graphene oxide suspension that mass concentration is 0.4 mg/ml is formed; Again ethylenediamine is added in above-mentioned graphene oxide dispersion, stirring at room temperature 10 minutes, forms ethylenediamine graphene oxide suspension; Then above-mentioned ethylenediamine graphene oxide suspension is heated to 95 DEG C, stirring and refluxing 6 hours; 6 times, dry rear acquisition amination Graphene is washed finally by suction filtration, ethanol;
(3) preparation of base metal ion complexation amination graphen catalyst
Be that 1 ︰ 3.6 takes amination Graphene and nickel acetate pressed powder by the mass ratio of amine functionalized graphene ︰ ferric acetate; First by amination graphene dispersion in dimethyl formamide, form the amination graphene dispersing solution of concentration 1.08 mg/ml; Then add ferric acetate pressed powder to above-mentioned adding in amination graphene dispersing solution, ultrasonic agitation, after 45 minutes, is warming up to 145 DEG C, refluxes 4 hours; Wash 4 times, after drying finally by suction filtration, ethanol, obtain base metal ion complexation amination graphen catalyst.
(4) the hydrogen reduction performance test of base metal ion complexation amination graphen catalyst
Base metal ion complexation amination graphen catalyst hydrogen reduction performance test is with step (5) in embodiment 2, and hydrogen reduction linear scan curve is as shown in curve in Fig. 32.
Contrast test 2
Step (1) is with step (1) in embodiment 1.
(2) preparation of amination Graphene
By graphite oxide Xi ︰ ethylenediamine mass ratio for 1 ︰ 89 takes graphene oxide prepared by step (1) and ethylenediamine; First by the graphene oxide dispersion prepared by step (1) in deionized water, the graphene oxide suspension that mass concentration is 0.4 mg/ml is formed; Again ethylenediamine is added in above-mentioned graphene oxide dispersion, stirring at room temperature 10 minutes, forms ethylenediamine graphene oxide suspension; Then above-mentioned ethylenediamine graphene oxide suspension is heated to 95 DEG C, stirring and refluxing 6 hours; 6 times, dry rear acquisition amination Graphene is washed finally by suction filtration, ethanol;
(3) preparation of schiff bases graphen catalyst
Mass ratio 1 ︰ 3.2 ︰ 12.5 gathering cyanogen amine ︰ salicylide by amine functionalized graphene ︰ tri-takes amination Graphene, melamine and salicylide prepared by step (2) respectively; First by amination graphene dispersion in dimethyl formamide, ultrasonic 30 minutes, forming mass concentration was the amination graphene suspension of 0.63 mg/ml; Salicylide is added in 20 milliliters of dimethyl formamides, forms salicylide dimethyl formamide solution; In above-mentioned amination graphene suspension, add melamine pressed powder, stir, be warming up to 150 DEG C, after melamine dissolves completely, drip above-mentioned salicylide dimethyl formamide solution 20 milliliters, condensing reflux 10 hours; Wash 6 times, after drying finally by suction filtration, ethanol, obtain schiff bases graphen catalyst.
(4) the hydrogen reduction performance test of schiff bases graphen catalyst
Schiff bases graphen catalyst hydrogen reduction performance test is with step (5) in embodiment 2, and hydrogen reduction linear scan curve is as shown in curve in Fig. 42.
Result of the test of the present invention:
As can be seen from Fig. 1 and Fig. 2, the complexing of base metal ion and schiff bases, forms tie between layers at Graphene, defines three-dimensional cross-linked graphen catalyst stereochemical structure.
As can be seen from Fig. 3 and Fig. 4, compare with schiff bases graphen catalyst with base metal ion complexation amination graphen catalyst, adopt the hydrogen reduction take-off potential of the base metal ion complexation schiff bases graphen catalyst obtained by the present invention and half wave potential to have and significantly improve.
As can be seen from Figure 5, the base metal ion complexation schiff bases graphen catalyst of employing obtained by the present invention is after electrochemistry cyclic voltammetric 2000 encloses, the catalytic performance of catalytic oxidation-reduction is not decayed, still remain higher catalytic activity, adopt the base metal ion complexation schiff bases graphen catalyst obtained by the present invention show excellent electrochemical stability and remain higher catalytic activity as can be seen here.
Claims (5)
1. a preparation method for base metal ion complexation schiff bases graphen catalyst, its concrete grammar step comprises
(1) preparation of graphene oxide
Take 3 grams of graphite powders, joining 600 milliliters of Nong Lin Suan ︰ concentrated sulfuric acid volume ratios is in the mixed solution of 1 ︰ 9, after mixing, obtains graphite powder mixed liquor; After above-mentioned graphite powder mixed liquor is placed in ice-water bath, slowly adds 18 grams of potassium permanganate pressed powders, be uniformly mixed, obtain potassium permanganate graphite powder mixed liquor; Then above-mentioned potassium permanganate graphite powder mixed liquor is warming up to 50 DEG C, stirring reaction 12 hours, more slowly pours in excessive frozen water, obtain purple green ice water solution; It is last that in the green ice water solution of above-mentioned purple, slowly add mass fraction be continuously 30% hydrogenperoxide steam generator, to solution become golden yellow after stop adding, after filtration, watery hydrochloric acid and ultra-pure water be alternately after washing, freeze drying, obtains graphene oxide;
It is characterized in that:
(2) preparation of amination Graphene
By graphite oxide Xi ︰ organic amine mass ratio for 1 ︰ 89 ~ 186 takes graphene oxide prepared by step (1) and organic amine; First by the graphene oxide dispersion prepared by step (1) in deionized water, the graphene oxide suspension that mass concentration is 0.4 ~ 1.2 mg/ml is formed; Again organic amine is added in above-mentioned graphene oxide dispersion, stirring at room temperature 10 ~ 20 minutes, forms organic amine graphene oxide suspension; Then above-mentioned organic amine graphene oxide suspension is heated to 80 ~ 100 DEG C, stirring and refluxing 4 ~ 6 hours; Finally by suction filtration, ethanol washing 4 ~ 6 times, dry rear acquisition amination Graphene;
(3) preparation of schiff bases Graphene
Mass ratio 1 ︰ 3.2 ~ 10 ︰ 12.5 ~ 39 gathering cyanogen amine ︰ salicylide by amine functionalized graphene ︰ tri-takes amination Graphene, melamine and salicylide prepared by step (2) respectively; First by amination graphene dispersion in dimethyl formamide or dimethyl sulfoxide (DMSO), ultrasonic 30 ~ 60 minutes, forming mass concentration was the amination graphene suspension of 0.63 ~ 2.3 mg/ml; Salicylide is added in 10 ~ 20 milliliters of dimethyl formamides or dimethyl sulfoxide (DMSO), forms salicylide dimethyl formamide or dimethyl sulphoxide solution; In above-mentioned amination graphene suspension, add melamine pressed powder, stir, be warming up to 135 ~ 180 DEG C, after melamine dissolves completely, drip above-mentioned salicylide dimethyl formamide or dimethyl sulphoxide solution 10 ~ 20 milliliters, condensing reflux 8 ~ 10 hours; After suction filtration, ethanol washing 4 ~ 6 times, drying, obtain schiff bases Graphene;
(4) preparation of base metal ion complexation schiff bases graphen catalyst
Be that 1 ︰ 2 ~ 4.8 takes schiff bases Graphene and base metal ion presoma pressed powder by the mass ratio of schiff bases Shi Mo Xi ︰ base metal ion presoma; First by schiff bases graphene dispersion in dimethyl formamide, form the schiff bases graphene dispersing solution of concentration 0.36 ~ 1.08 mg/ml; Then in above-mentioned schiff bases graphene dispersing solution, add base metal ion presoma pressed powder, ultrasonic agitation, after 30 ~ 60 minutes, is warming up to 135 ~ 150 DEG C, refluxes 4 ~ 6 hours; After suction filtration, ethanol washing 4 ~ 6 times, drying, obtain base metal ion complexation schiff bases graphen catalyst.
2. according to the preparation method of a kind of base metal ion complexation schiff bases graphen catalyst according to claim 1, it is characterized in that described organic amine be ethylenediamine, p-phenylenediamine (PPD), melamine one of them; Wherein said base metal ion presoma be cobalt acetate, ferric acetate, nickel acetate one of them.
3., according to the preparation method of a kind of base metal ion complexation schiff bases graphen catalyst according to claim 1, it is characterized in that step (2) ~ (4) of concrete preparation method:
(2) preparation of amination Graphene
By graphite oxide Xi ︰ ethylenediamine mass ratio for 1 ︰ 89 takes graphene oxide prepared by step (1) and ethylenediamine; First by the graphene oxide dispersion prepared by step (1) in deionized water, the graphene oxide suspension that mass concentration is 0.4 mg/ml is formed; Again ethylenediamine is added in above-mentioned graphene oxide dispersion, stirring at room temperature 10 minutes, forms ethylenediamine graphene oxide suspension; Then above-mentioned ethylenediamine graphene oxide suspension is heated to 95 DEG C, stirring and refluxing 6 hours; 6 times, dry rear acquisition amination Graphene is washed finally by suction filtration, ethanol;
(3) preparation of schiff bases Graphene
Mass ratio 1 ︰ 3.2 ︰ 12.5 gathering cyanogen amine ︰ salicylide by amine functionalized graphene ︰ tri-takes amination Graphene, melamine and salicylide prepared by step (2) respectively; First by amination graphene dispersion in dimethyl formamide, ultrasonic 30 minutes, forming mass concentration was the amination graphene suspension of 0.63 mg/ml; Salicylide is added in 20 milliliters of dimethyl formamides, forms salicylide dimethyl formamide solution; In above-mentioned amination graphene suspension, add melamine pressed powder, stir, be warming up to 150 DEG C, after melamine dissolves completely, drip above-mentioned salicylide dimethyl formamide solution 20 milliliters, condensing reflux 10 hours; Wash 6 times, after drying finally by suction filtration, ethanol, obtain schiff bases Graphene;
(4) preparation of base metal ion complexation schiff bases graphen catalyst
Be that 1 ︰ 4.8 takes schiff bases Graphene and cobalt acetate pressed powder by the mass ratio of schiff bases Shi Mo Xi ︰ cobalt acetate; First by schiff bases graphene dispersion in dimethyl formamide, form the schiff bases graphene dispersing solution of concentration 0.72 mg/ml; Then in above-mentioned schiff bases graphene dispersing solution, add cobalt acetate pressed powder, ultrasonic agitation, after 30 minutes, is warming up to 150 DEG C, refluxes 6 hours; Wash 6 times, after drying finally by suction filtration, ethanol, obtain base metal ion complexation schiff bases graphen catalyst.
4., according to the preparation method of a kind of base metal ion complexation schiff bases graphen catalyst according to claim 1, it is characterized in that step (2) ~ (4) of concrete preparation method:
(2) preparation of amination Graphene
By graphite oxide Xi ︰ p-phenylenediamine (PPD) mass ratio for 1 ︰ 140 takes graphene oxide prepared by step (1) and p-phenylenediamine (PPD); First by the graphene oxide dispersion prepared by step (1) in deionized water, the graphene oxide suspension that mass concentration is 0.8 mg/ml is formed; Again p-phenylenediamine (PPD) is added in above-mentioned graphene oxide dispersion, stirring at room temperature 15 minutes, forms p-phenylenediamine (PPD) graphene oxide suspension; Then above-mentioned p-phenylenediamine (PPD) graphene oxide suspension is heated to 80 DEG C, stirring and refluxing 4 hours; 4 times, dry rear acquisition amination Graphene is washed finally by suction filtration, ethanol;
(3) preparation of schiff bases Graphene
Mass ratio 1 ︰ 4.9 ︰ 19.1 gathering cyanogen amine ︰ salicylide by amine functionalized graphene ︰ tri-takes amination Graphene, melamine and salicylide prepared by step (2) respectively; First by amination graphene dispersion in dimethyl sulfoxide (DMSO), ultrasonic 45 minutes, forming mass concentration was the amination graphene suspension of 1.2 mg/ml; Salicylide is added in 10 milliliters of dimethyl sulfoxide (DMSO)s, forms salicylide dimethyl sulphoxide solution; In above-mentioned amination graphene suspension, add melamine pressed powder, stir, be warming up to 180 DEG C, after melamine dissolves completely, drip above-mentioned salicylide dimethyl sulphoxide solution 10 milliliters, condensing reflux 8 hours; Wash 4 times, after drying finally by suction filtration, ethanol, obtain schiff bases Graphene;
(4) preparation of base metal ion complexation schiff bases graphen catalyst
Be that 1 ︰ 2 takes schiff bases Graphene and ferric acetate pressed powder by the mass ratio of schiff bases Shi Mo Xi ︰ ferric acetate; First by schiff bases graphene dispersion in dimethyl formamide, form the schiff bases graphene dispersing solution of concentration 0.36 mg/ml; Then in above-mentioned schiff bases graphene dispersing solution, add ferric acetate pressed powder, ultrasonic agitation, after 60 minutes, is warming up to 135 DEG C, refluxes 5 hours; Wash 5 times, after drying finally by suction filtration, ethanol, obtain base metal ion complexation schiff bases graphen catalyst.
5., according to the preparation method of a kind of base metal ion complexation schiff bases graphen catalyst according to claim 1, it is characterized in that step (2) ~ (4) of concrete preparation method:
(2) preparation of amination Graphene
By graphite oxide Xi ︰ melamine mass ratio for 1 ︰ 186 takes graphene oxide prepared by step (1) and melamine; First by the graphene oxide dispersion prepared by step (1) in deionized water, the graphene oxide suspension that mass concentration is 1.2 mg/ml is formed; Again melamine is added in above-mentioned graphene oxide dispersion, stirring at room temperature 20 minutes, forms melamine graphene oxide suspension; Then above-mentioned melamine graphene oxide suspension is heated to 100 DEG C, stirring and refluxing 5 hours; 5 times, dry rear acquisition amination Graphene is washed finally by suction filtration, ethanol;
(3) preparation of schiff bases Graphene
Mass ratio 1 ︰ 10 ︰ 39 gathering cyanogen amine ︰ salicylide by amine functionalized graphene ︰ tri-takes amination Graphene, melamine and salicylide prepared by step (2) respectively; First by amination graphene dispersion in dimethyl formamide, ultrasonic 60 minutes, forming mass concentration was the amination graphene suspension of 2.3 mg/ml; Salicylide is added in 15 milliliters of dimethyl formamides, forms salicylide dimethyl formamide solution; In above-mentioned amination graphene suspension, add melamine pressed powder, stir, be warming up to 135 DEG C, after melamine dissolves completely, drip above-mentioned salicylide dimethyl formamide solution 15 milliliters, condensing reflux 9 hours; Wash 5 times, after drying finally by suction filtration, ethanol, obtain schiff bases Graphene;
(4) preparation of base metal ion complexation schiff bases graphen catalyst
Be that 1 ︰ 3.6 takes schiff bases Graphene and nickel acetate pressed powder by the mass ratio of schiff bases Shi Mo Xi ︰ nickel acetate; First by schiff bases graphene dispersion in dimethyl formamide, form the schiff bases graphene dispersing solution of concentration 1.08 mg/ml; Then in above-mentioned schiff bases graphene dispersing solution, add nickel acetate pressed powder, ultrasonic agitation, after 45 minutes, is warming up to 145 DEG C, refluxes 4 hours; Wash 4 times, after drying finally by suction filtration, ethanol, obtain base metal ion complexation schiff bases graphen catalyst.
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| CN108212217B (en) * | 2018-01-18 | 2020-09-29 | 南京大学 | Catalyst for degrading chlorophenol pollutants, preparation method and application |
| CN108585711A (en) * | 2018-05-15 | 2018-09-28 | 苏州太星新材料科技有限公司 | A kind of schiff bases modified graphene oxide cementitious capillary waterproofing material and its preparation and application |
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| CN110981651A (en) * | 2019-12-02 | 2020-04-10 | 西安近代化学研究所 | graphene-Schiff base nickel compound for solid propellant and preparation method thereof |
| CN110981651B (en) * | 2019-12-02 | 2021-11-23 | 西安近代化学研究所 | graphene-Schiff base nickel compound for solid propellant and preparation method thereof |
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