CN101745426A - Compound oxygen reduction electro-catalyst of carbon nano materials modified by macrocyclic compound containing nitrogen and preparation method thereof - Google Patents
Compound oxygen reduction electro-catalyst of carbon nano materials modified by macrocyclic compound containing nitrogen and preparation method thereof Download PDFInfo
- Publication number
- CN101745426A CN101745426A CN201010019500A CN201010019500A CN101745426A CN 101745426 A CN101745426 A CN 101745426A CN 201010019500 A CN201010019500 A CN 201010019500A CN 201010019500 A CN201010019500 A CN 201010019500A CN 101745426 A CN101745426 A CN 101745426A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxygen reduction
- compound
- carbon
- reduction electro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 discloses a compound oxygen reduction electro-catalyst of carbon nano materials modified by macrocyclic compound containing nitrogen and a preparation method thereof, wherein the catalyst is prepared by mixing the macrocyclic compound containing nitrogen and the carbon nano materials completely, and has excellent catalytic activity and stability in cyclic voltammetry. The peak potential of the catalyzing oxygen reduction reaction can reach -0.1V (vs. Ag/Agcl); the peak current density of the oxygen reduction can reach 3.4mA.cm<-2>; the catalyst has stable catalytic activity which is basically not attenuated after 10000 times of cyclic voltammetry; the current generated in the catalyzing oxygen reduction reaction is not affected by the additional organic micromolecules (such as glucose, methanol and formaldehyde) and carbon monoxide. The electro-catalyst has simple preparation process, low cost, and good catalytic activity, selectivity, mithridatism and stability, can be applied to biomembrane electrode reactors, biosensors, fuel cells and other fileds.
Description
Technical field
The invention belongs to catalyst field, be specifically related to compound oxygen reduction electro-catalyst of a kind of nitrogenous macrocyclic compound and carbon nanomaterial and preparation method thereof.
Background technology
In recent years, relevant Oxygen gas diffusion is very active in the application study of various batteries, metal/air electrode, membrane electrode reactor and even sensor, and the catalytic reaction layer of air electrode is its most important component.Molecular oxygen can not pollute as oxidant, is splendid green oxidation agent.
Along with the sharp increase of fossil fuel consumption and the exhaustion day by day of energy reserve, it is extremely important for the mankind to seek eco-friendly sustainable energy in addition.Wherein fuel cell is popular at present research direction, and cathodic oxygen reduction efficient has great significance on its performance of performance, and fuel cell oxygen reduction catalyst system and catalyzing efficiently is indispensable for its practical application.Negative electrode oxygen reduction reaction path is divided into " two electron reaction approach " and " quadrielectron reaction path ", and wherein " quadrielectron reaction path " is more efficient.Discover that the platinum group metal catalysts cell cathode that acts as a fuel is having outstanding effect aspect the catalytic oxygen reduction.
The alloy of platinum black material and platinum and other metals has been widely used in catalytic oxygen reduction field.Studies show that in a large number platinum is all higher than the catalytic activity of other transition metal and metal oxide as the oxygen reduction catalyst of air electrode.Wherein the hydrogen reduction catalytic activity of Pt-Au (50%: 50%) bianry alloy is best, Pt-Ir (50%: 50%) bianry alloy has largest specific surface area and best discharge, and Ir-Pt-Au (33%: 33%: 33%) is the best oxygen reduction catalyst of combination property in the alkaline medium.
Though platinum group catalyst has good oxygen reduction catalytic activity, but the natural reserves of noble metal platinum are few, cost an arm and a leg, the use of platinum group catalyst in various fuel cells increases the production cost of battery greatly, thereby limited fuel cell practical application and commercialization fully; In addition, the catalyst poisoning of irreversibility appears in the influence of intermediate oxidation product when platinum group catalyst is subject to catalysis.Therefore, development and exploitation are cheap, and the strong novel oxygen reduction electro-catalyst of high catalytic activity and anti-poisoning capability is for the large-scale application of various battery technologies and commercially produce and have important practical significance.
The transient metal complex of nitrogenous macrocyclic compound and these molecules is applied to the existing report of catalytic oxygen reduction at home and abroad.The compound that CN 101322948A " a kind of preparation method of carbon supported metalloporphyrin metalloporphyrin oxygen reduction catalyst " and CN 101069857A " a kind of halogen-substituted binuclear phthalocyanine ferrite reduction catacolyst and preparation method thereof " propose to use metal phthalocyanine, porphyrin and metal phthalocyanine, porphyrin and other materials is as oxygen reduction catalyst, and the result shows that metal phthalocyanine, porphyrin have good hydrogen reduction catalytic capability.But the catalyst that nitrogenous macrocyclic compound and common material are compound, catalytic activity is low, and stability and anti-ability of poisoning are all relatively poor.This mainly is that the active force between decorating molecule and the carrier material is not strong because the composite effect of two kinds of materials is poor.In order to improve catalytic effect, after this quasi-molecule and carrier material are compound, just will after high-temperature process under the inert gas shielding, can improve catalytic activity usually.The composite highly effective catalyst that the carrier material of searching new high-efficiency and simple synthesis preparation method preparation contain phthalocyanine and porphyrin molecule is significant.
Summary of the invention
The objective of the invention is to overcome the prior art above shortcomings, compound oxygen reduction electro-catalyst of nitrogenous carbon nano materials modified by macrocyclic compound and preparation method thereof is provided.The present invention is by nitrogenous macrocyclic compound and carbon nanomaterial, and the abundant mixing by simple to operate can obtain product.Compare with platinum group catalyst, reduction has good catalytic activity to catalytic oxygen to utilize the synthetic composite catalyst of method for preparing, obtain than the better oxygen reduction current potential of platinum group catalyst, can keep original uniqueness, efficient electron transfer characteristic and good chemical stability simultaneously.
The present invention is achieved through the following technical solutions:
A kind of compound oxygen reduction electro-catalyst of nitrogenous carbon nano materials modified by macrocyclic compound is composited by nanometer carbon material supported nitrogenous macrocyclic compound.
In the above-mentioned compound oxygen reduction electro-catalyst, described nitrogenous macrocyclic compound comprises more than one following material: phthalocyanine, porphyrin, dibenzo four azepine annulenes, the metal complex of phthalocyanine, porphyrin, dibenzo four azepine annulenes, the derivative of phthalocyanine, porphyrin, dibenzo four azepine annulenes, the metal complex of the derivative of phthalocyanine, porphyrin, dibenzo four azepine annulenes.
In the above-mentioned compound oxygen reduction electro-catalyst, described carbon nanomaterial is carbon nano-particle, CNT, carbon nano-fiber or nano carbon microsphere.
In the above-mentioned compound oxygen reduction electro-catalyst, described metal complex comprises the metal complex of iron, cobalt, nickel, copper or zinc.
In the above-mentioned compound oxygen reduction electro-catalyst, the structure of described nitrogenous macrocyclic compound is that carbon nitrogen conjugated double bond forms big ring, and the metallic atom at big ring nitrogen and center carries out coordination and the structure of the big ring encirclement metal that forms.
In the above-mentioned compound oxygen reduction electro-catalyst, carbon nanomaterial and nitrogenous macrocyclic compound are composited by one of following complex method: (1) mechanical mixture: in atmosphere by grinding or mixing and ball milling carbon nanomaterial and nitrogenous macrocyclic compound are composited; (2) physical absorption mixes: use the nitrogenous macrocyclic compound of dissolution with solvents, add carbon nanomaterial, fully be composited after the concussion; (3) chemical bonding: utilize the chemical reaction between carbon nanomaterial and the nitrogenous macrocyclic compound to be composited.
In the above-mentioned compound oxygen reduction electro-catalyst, the atmosphere in the mechanical mixture is air, nitrogen or argon gas.
In the above-mentioned compound oxygen reduction electro-catalyst, described physical absorption mixing specifically comprises the steps:
In mass fraction, with 1～10 part of nitrogenous macrocyclic compound of 100～2000 parts of dissolution with solvents, add 10～100 parts of carbon nanomaterials again, in 10～60KHz is ultrasonic, fully mixed 6～24 hours, filter and remove solvent, oven dry obtains described compound oxygen reduction electro-catalyst.
Among the preparation method of above-mentioned compound oxygen reduction electro-catalyst, solvent for use comprises inorganic solvent and organic solvent: described inorganic solvent comprises neutral aqueous solution, acidic aqueous solution or alkaline aqueous solution; Described organic solvent comprises ethanol, chloroform or N, dinethylformamide.The compound oxygen reduction electro-catalyst that described nitrogenous modified by macrocyclic compound composite carbon nano material preparation becomes can be applicable to fields such as biology sensor, biological respinse device, Proton Exchange Membrane Fuel Cells, direct alcohol fuel battery and metal-air battery.
The present invention carries out ultrasonic processing with nitrogenous macrocyclic compound and carbon nanomaterial, utilize the π-πGong Ezuoyong surface that is modified at carbon nanomaterial that nitrogenous macrocyclic compound is firm between the pi-electron of the pi-electron of carbon nanomaterial and nitrogenous macrocyclic compound, synthetic and prepare phthalocyanine porphyrin quasi-molecule and carbon nanomaterial compound oxygen reduction electro-catalyst, to improve the catalytic activity of composite catalyst, stable and anti-poisoning capability.For substituting the platinum group noble metal catalyst, the production cost that reduces fuel cell provides the scheme of solution.
The present invention is with respect to the advantage and the beneficial effect of prior art:
(1) preparation cost of the present invention is cheap, and method is simple to operate, and treatment conditions relax.
(2) the compound oxygen reduction catalyst that synthesizes of preparation method of the present invention has good oxygen reduction catalytic activity, and the spike potential of oxygen reduction is obviously than the current potential corrigendum of platinum group catalyst.In addition, the compound oxygen reducing catalyst that preparation method of the present invention synthesizes has fine stability, and 10000 circular flow is unattenuated.
(3) the compound oxygen reduction catalyst that synthesizes of preparation method of the present invention has good selectivity, and the electric current that the reaction of recall oxygen reduction produces is not subjected to methyl alcohol, the interference of organic molecules such as formaldehyde.
(4) the compound oxygen reduction catalyst that synthesizes of preparation method of the present invention has very strong anti-carbon monoxide poisoning capability, and the electric current that the reaction of recall oxygen reduction produces is not subjected to the influence of CO gas.
Description of drawings
Fig. 1 is 150000 times of sem photographs of blank CNT.
Fig. 2 is the 150000 times sem photographs of phthalocyanine nickel after carbon nano-tube modified.
Fig. 3 is CuPc (a c line among the figure), and carbon nano-particle (a line among the figure) and CuPc are modified Fourier's infrared spectrogram of the composite catalyst (b line among the figure) of carbon nano-particle.
Fig. 4 is that blank glass-carbon electrode and the carbon nano-tube modified composite catalyst of FePC are at the saturated 0.1mol.L of oxygen
-1Cyclic voltammogram in the KOH solution, dotted line are that blank glass-carbon electrode is at the saturated 0.1mol.L of oxygen gas
-1Cyclic voltammogram in the KOH solution, solid line are that the carbon nano-tube modified composite catalyst electrode of FePC is at the saturated 0.1mol.L of oxygen
-1Cyclic voltammogram in the KOH solution.
Fig. 5 is that the carbon nano-tube modified compound oxygen reduction electro-catalyst of FePC is at 0.1mol.L
-1Cyclic voltammogram in the KOH solution, dotted line are the saturated 0.1mol.L of nitrogen
-1Cyclic voltammogram in the KOH solution, solid line are the saturated 0.1mol.L of oxygen
-1Cyclic voltammogram in the KOH solution.
Fig. 6 is that the oxygen reduction electro-catalyst of the cobalt porphyrin of amino functional group and carboxylic CNT bonding is at 0.1mol.L
-1Cyclic voltammogram in the KOH solution.Dotted line is the saturated 0.1mol.L of nitrogen
-1Cyclic voltammogram in the KOH solution, solid line are the saturated 0.1mol.L of oxygen
-1Cyclic voltammogram in the KOH solution.
Fig. 7 a is the cyclic voltammogram of commercial Pt/C catalyst, and dotted line is the saturated 0.1mol.L of nitrogen
-1Cyclic voltammogram in the KOH solution, solid line are the saturated 0.1mol.L of oxygen
-1Cyclic voltammogram in the KOH solution.
Fig. 7 b is the cyclic voltammogram of the carbon nano-tube modified compound oxygen reduction electro-catalyst of FePC, and dotted line is the saturated 0.1mol.L of nitrogen
-1Cyclic voltammogram in the KOH solution, solid line are the saturated 0.1mol.L of oxygen
-1Cyclic voltammogram in the KOH solution.
Fig. 8 a is that commercial Pt/C catalyst is at 0.1mol.L
-1Scheme current density in the KOH solution-time response, and Fig. 8 b is that the carbon nano-tube modified compound oxygen reduction electro-catalyst of ferriporphyrin is at 0.1mol.L
-1Scheme current density in the KOH solution-time response.Nitrogen saturated after 300 seconds aerating oxygen, the reduction current that produces oxygen, current density is stablized after 200 seconds and is added glucose one by one, methyl alcohol and formaldehyde.
Fig. 9 is that commercial Pt/C catalyst and CuPc are modified the Nano carbon balls compound oxygen reduction electro-catalyst at 0.1mol.L
-1Scheme current density in the KOH solution-time response, and wherein curve e is that commercial Pt/C catalyst is at 0.1mol.L
-1Current density in the KOH solution-time response curve, curve d are that CuPc is modified the Nano carbon balls compound oxygen reduction electro-catalyst at 0.1mol.L
-1Scheme current density in the KOH solution-time response, the saturated conduit that after 300 seconds, carbon monoxide is inserted aerating oxygen of oxygen, and current ratio is among the figure: the initial current of recall oxygen reduction on the current value ratio of recall oxygen reduction process.
Figure 10 a is that commercial Pt/C catalyst is at 0.1mol.L
-1Cyclic voltammogram in the KOH solution, dotted line are primary cyclic voltammogram, and solid line is through the cyclic voltammogram after 10000 cyclic voltammetric tests.
Figure 10 b is that the carbon nano-tube modified compound oxygen reduction electro-catalyst of phthalocyanine cobalt is at 0.1mol.L
-1Cyclic voltammogram in the KOH solution, dotted line are primary cyclic voltammogram, and solid line is through the cyclic voltammogram after 10000 cyclic voltammetric tests.
The specific embodiment
Below in conjunction with embodiment concrete enforcement of the present invention is described further, but enforcement of the present invention is not limited thereto.
Embodiment 1:
0.1mg phthalocyanine nickel is dissolved in 10mlN, in the dinethylformamide, add the 1mg CNT again, fully shake up, 60KHz ULTRASONIC COMPLEX 24 hours, decompress filter also spends deionised water filtrate to colourless, and filter cake was 80 ℃ of dryings 12 hours, and cooling obtains the carbon nano-tube modified compound oxygen reduction electro-catalyst of phthalocyanine nickel.Fig. 1 is the sem photograph of blank CNT, and Fig. 2 is the sem photograph of the CNT behind the modification phthalocyanine nickel.Can find out obviously that from Fig. 2 phthalocyanine nickel can be adsorbed on carbon nano tube surface well and form the carbon nano-tube modified compound oxygen reduction electro-catalyst of phthalocyanine nickel.
Embodiment 2:
The 0.2mg CuPc is dissolved in the 40ml chloroform, add the 4mg carbon nano-particle again, fully shake up, 60KHz ULTRASONIC COMPLEX 24 hours, decompress filter also spends deionised water filtrate to colourless, filter cake was 80 ℃ of dryings 12 hours, and cooling obtains the compound oxygen reducing catalyst that CuPc is modified carbon nano-particle.Fig. 3 is CuPc (a c line among the figure), and carbon nano-particle (a line among the figure) and CuPc are modified Fourier's infrared spectrogram of the composite catalyst (b line among the figure) of carbon nano-particle.Kong Bai CNT (a line among the figure) does not have absworption peak substantially as can be seen from Figure.When CuPc modify on the carbon nano-particle form compound after, the characteristic absorption peak of CuPc obviously appears at CuPc and modifies on the compound oxygen reducing catalyst of carbon nano-particle (b line among the figure).Hence one can see that, and CuPc can be compounded to form the composite catalyst that CuPc is modified carbon nano-particle with carbon nano-particle.
Embodiment 3:
The 0.2mg FePC is dissolved in the 20ml water, adds the 4mg CNT again, fully shake up, 50KHz ULTRASONIC COMPLEX 18 hours, decompress filter also spends deionised water filtrate to colourless, and filter cake was 80 ℃ of dryings 12 hours, and cooling obtains compound oxygen reducing catalyst.The compound oxygen reduction electro-catalyst of 2mg preparation is scattered in the Nafion solution of 1ml0.1%, obtains 2mg.mL
-1Oxygen reduction electro-catalyst solution.Get 5 μ L solution and drip to the surface of glass-carbon electrode (diameter 3mm), electrode at room temperature after the drying, obtains containing the modified electrode of compound oxygen reduction electro-catalyst.With this modified electrode as working electrode, use electrochemical workstation (Shanghai China in morning electrochemical apparatus Co., Ltd, CHI660C) and the standard three-electrode system (platinum filament is as auxiliary electrode, interior reference liquid be the Ag/AgCl electrode of 3M KCl as reference electrode, modified electrode is as working electrode) at 0.1mol.L
-1In the KOH solution with 100mV.s
-1Sweep speed carry out cyclic voltammetric test.Fig. 4 is blank glass-carbon electrode and has modified the electrode of compound oxygen reducing catalyst at the saturated 0.1mol.L of oxygen
-1Cyclic voltammogram in the KOH solution.As can be seen from the figure, blank glass-carbon electrode is very poor to the catalytic capability of oxygen reduction, and the spike potential of oxygen reduction is-0.4V (Fig. 4 dotted line).After blank glass-carbon electrode had been modified compound oxygen reducing catalyst, the reducing power of oxygen obviously strengthened, and the current density of oxygen reduction obviously increases, and the spike potential of oxygen reduction has just moved on to-0.1V (Fig. 4 solid line).The carbon nano-tube modified composite catalyst of FePC has good catalytic activity
Embodiment 4:
The 0.1mg FePC is dissolved in the 20ml water, adds the 2mg CNT again, fully shake up, 40KHz ULTRASONIC COMPLEX 18 hours, decompress filter also spends deionised water filtrate to colourless, and filter cake was 80 ℃ of dryings 12 hours, and cooling obtains compound oxygen reducing catalyst.The compound oxygen reduction electro-catalyst of 2mg preparation is scattered in the Nafion solution of 1ml 0.1%, obtains 2mg.mL
-1Oxygen reduction electro-catalyst solution.Get 5 μ L solution and drip to the surface of glass-carbon electrode (diameter 3mm), electrode at room temperature after the drying, obtains containing the modified electrode of compound oxygen reduction electro-catalyst.With this modified electrode as working electrode, use electrochemical workstation (Shanghai China in morning electrochemical apparatus Co., Ltd, CHI660C) and the standard three-electrode system (platinum filament is as auxiliary electrode, interior reference liquid be the Ag/AgCl electrode of 3M KCl as reference electrode, modified electrode is as working electrode) at 0.1mol.L
-1In the KOH solution with 100mV.s
-1Sweep speed carry out cyclic voltammetric test.Fig. 5 is the cyclic voltammogram of the carbon nano-tube modified compound oxygen reduction electro-catalyst of FePC in 0.1mol.L-1KOH solution.Fig. 5 dotted line is the saturated 0.1mol.L of nitrogen
-1Cyclic voltammogram in the KOH solution, Fig. 5 solid line are the saturated 0.1mol.L of oxygen
-1Cyclic voltammogram in the KOH solution.As can be seen from the figure, the carbon nano-tube modified compound oxygen reduction electro-catalyst of FePC has good catalytic activity to the reduction of oxygen.The strong peak of redox at-0.1V place is the reduction peak of dissolved oxygen.Oxygen reduction peak current density reaches 3.4mA.cm simultaneously
-2
Embodiment 5:
The cobalt porphyrin that 1mg is contained amino functional group is dissolved in 100ml 0.1mol.L
-1In the NaOH solution, add the carboxylic CNT of 2mg again, fully shake up, 30KHz ultrasonic reaction 12 hours, decompress filter also spend deionised water filtrate to colourless, and filter cake was 80 ℃ of dryings 12 hours, and cooling obtains compound oxygen reducing catalyst.The compound oxygen reduction electro-catalyst of 2mg preparation is scattered in the Nafion solution of 1ml 0.2%, obtains 2mg.mL
-1Oxygen reduction electro-catalyst solution.Get 5 μ L solution and drip to the surface of glass-carbon electrode (diameter 3mm), electrode at room temperature after the drying, obtains containing the modified electrode of compound oxygen reduction electro-catalyst.With this modified electrode as working electrode, use electrochemical workstation (Shanghai China in morning electrochemical apparatus Co., Ltd, CHI660C) and the standard three-electrode system (platinum filament is as auxiliary electrode, interior reference liquid be the Ag/AgCl electrode of 3MKCl as reference electrode, modified electrode is as working electrode) at 0.1mol.L
-1In the KOH solution with 100mV.s
-1Sweep speed carry out cyclic voltammetric test.Fig. 6 is that the oxygen reduction electro-catalyst of the cobalt porphyrin of amino functional group and carboxylic CNT bonding is at 0.1mol.L
-1Cyclic voltammogram in the KOH solution.Dotted line is the saturated 0.1mol.L of nitrogen
-1Cyclic voltammogram in the KOH solution, solid line are the saturated 0.1mol.L of oxygen
-1Cyclic voltammogram in the KOH solution.From two figure as can be seen, this compound oxygen reduction electro-catalyst has good catalytic effect to the reduction of oxygen.The strong peak of redox at-0.12V place is the reduction peak of dissolved oxygen.Oxygen reduction peak current density reaches 1.8mA.cm simultaneously
-2
Embodiment 6:
The 0.1mg FePC is dissolved in the 20ml water, adds the 3mg CNT again, fully shake up, 20KHz ULTRASONIC COMPLEX 12 hours, decompress filter and with absolute ethanol washing filtrate to colourless, filter cake was 80 ℃ of dryings 12 hours, cooling obtains compound oxygen reducing catalyst.The compound oxygen reduction electro-catalyst of 2mg preparation is scattered in the Nafion solution of 1ml 0.2%, obtains the oxygen reduction electro-catalyst solution of 2mg.mL-1.Get 5 μ L solution and drip to the surface of glass-carbon electrode (diameter 3mm), electrode at room temperature after the drying, obtains containing the modified electrode of compound oxygen reduction electro-catalyst.1mg Pt/C (commerce is used the platinum black VPO catalysts, and mass ratio is 40%, purchases the Johnson-Matthey company in Britain) is scattered in the Nafion solution of 1ml 0.2%, obtains the Pt/C solution of 2mg.mL-1.Get 5ml Pt/C solution and drip to the surface of glass-carbon electrode (diameter 3mm), electrode at room temperature after the drying, obtains Pt/C catalyst modified glassy carbon.Respectively with the carbon nano-tube modified composite catalyst modified glassy carbon of FePC, Pt/C catalyst modified glassy carbon is as working electrode, use electrochemical workstation (Shanghai China in morning electrochemical apparatus Co., Ltd, CHI660C) and the standard three-electrode system (platinum filament is as auxiliary electrode, interior reference liquid be the Ag/AgCl electrode of 3MKCl as reference electrode, modified electrode is as working electrode) at 0.1mol.L
-1In the KOH solution with 100mV.s
-1Sweep speed carry out cyclic voltammetric test.Fig. 7 is that (Fig. 7 is a) at 0.1mol.L for the carbon nano-tube modified composite catalyst of FePC (Fig. 7 b) and Pt/C catalyst
-1Cyclic voltammogram in the KOH solution.Among Fig. 7 a, the b, dotted line is the saturated 0.1mol.L of nitrogen
-1Cyclic voltammogram in the KOH solution, solid line are the saturated 0.1mol.L of oxygen
-1Cyclic voltammogram in the KOH solution.From two figure as can be seen, (Fig. 7 a) compares with the Pt/C catalyst of commercialization, the carbon nano-tube modified composite catalyst of FePC (Fig. 7 b) has good catalytic activity to the reduction of oxygen, the spike potential of oxygen reduction is-0.1V, the oxygen reduction spike potential is obviously shuffled, the electric current that oxygen reduction produces obviously increases, and peak current density is brought up to 3.2mA.cm
-2
Embodiment 7:
The 0.2mg FePC is dissolved in the 50ml water, adds the 4mg CNT again, fully shake up, 15KHz ULTRASONIC COMPLEX 9 hours, decompress filter and with absolute ethanol washing filtrate to colourless, filter cake was 80 ℃ of dryings 12 hours, cooling obtains compound oxygen reducing catalyst.The compound oxygen reduction electro-catalyst of 2mg preparation is scattered in the Nafion solution of 1ml 0.2%, obtains 2mg.mL
-1Oxygen reduction electro-catalyst solution.Get 5 μ L solution and drip to the surface of glass-carbon electrode (diameter 3mm), electrode at room temperature after the drying, obtains containing the modified electrode of compound oxygen reduction electro-catalyst.1mg Pt/C (commerce is used the platinum black VPO catalysts, and mass ratio is 40%, purchases the Johnson-Matthey company in Britain) is scattered in the Nafion solution of 1ml 0.2%, obtains 2mg.mL
-1Pt/C solution.Get 5ml Pt/C solution and drip to the surface of glass-carbon electrode (diameter 3mm), electrode at room temperature after the drying, obtains the Pt/C modified glassy carbon.Respectively with the carbon nano-tube modified composite catalyst modified glassy carbon of FePC, Pt/C catalyst modified glassy carbon is as working electrode, use electrochemical workstation (Shanghai China in morning electrochemical apparatus Co., Ltd, CHI660C) and the standard three-electrode system (platinum filament is as auxiliary electrode, interior reference liquid be the Ag/AgCl electrode of 3MKCl as reference electrode, modified electrode is as working electrode) at 0.1mol.L
-1Carry out constant potential electric current-test time response in the KOH solution.The current potential that applies is :-0.1V.Fig. 8 be commercial Pt/C catalyst (Fig. 8 a) and the carbon nano-tube modified compound oxygen reduction electro-catalyst of ferriporphyrin (Fig. 8 b) at 0.1mol.L
-1Scheme current density in the KOH solution-time response.As can be seen from the figure, the reduction current of commercial Pt/C catalyst oxygen reduction is less, and adds glucose one by one when solution, and behind methyl alcohol and the formaldehyde, the reduction current of oxygen descends one by one, and selection of catalysts is relatively poor.Compare with the Pt/C catalyst of commercialization, the carbon nano-tube modified composite catalyst of FePC, the reduction current of oxygen reduction are the twices of Pt/C catalyst, and add glucose one by one when solution, and behind methyl alcohol and the formaldehyde, the reduction current of oxygen does not descend.The carbon nano-tube modified composite catalyst of FePC has very high selectivity to the catalytic action of oxygen reduction.
Embodiment 8:
The 0.2mg CuPc is dissolved in the 50ml water, adds the 4mg Nano carbon balls again, fully shake up, 10KHz ULTRASONIC COMPLEX 9 hours, decompress filter and with absolute ethanol washing filtrate to colourless, filter cake was 80 ℃ of dryings 12 hours, cooling obtains compound oxygen reducing catalyst.The compound oxygen reduction electro-catalyst of 2mg preparation is scattered in the Nafion solution of 1ml 0.2%, obtains 2mg.mL
-1Oxygen reduction electro-catalyst solution.Get 5 μ L solution and drip to the surface of glass-carbon electrode (diameter 3mm), electrode at room temperature after the drying, obtains containing the modified electrode of compound oxygen reduction electro-catalyst.1mg Pt/C (commerce is used the platinum black VPO catalysts, and mass ratio is 40%, purchases the Johnson-Matthey company in Britain) is scattered in the Nafion solution of 1ml 0.2%, obtains 2mg.mL
-1Pt/C solution.Get 5ml Pt/C solution and drip to the surface of glass-carbon electrode (diameter 3mm), electrode at room temperature after the drying, obtains the Pt/C modified glassy carbon.Modify Nano carbon balls composite catalyst modified glassy carbon with CuPc respectively, Pt/C catalyst modified glassy carbon is as working electrode, use electrochemical workstation (Shanghai China in morning electrochemical apparatus Co., Ltd, CHI660C) and the standard three-electrode system (platinum filament is as auxiliary electrode, interior reference liquid be the Ag/AgCl electrode of 3M KCl as reference electrode, modified electrode is as working electrode) at 0.1mol.L
-1Carry out constant potential electric current-test time response in the KOH solution.The current potential that applies is :-0.15V.Fig. 9 is that commercial Pt/C catalyst (curve e) and CuPc are modified Nano carbon balls compound oxygen reduction electro-catalyst (curve d) at 0.1mol.L
-1Scheme electric current in the KOH solution-time response.As can be seen from Figure, when CO gas fed solution, the electric current of commercial Pt/C catalyst oxygen reduction was obviously decayed, and serious intoxicating phenomenon occurred.Compare with the Pt/C catalyst of commercialization, the catalytic activity of CuPc modification Nano carbon balls composite catalyst is subjected to the influence of carbon monoxide hardly, and the current stabilization of catalytic oxygen reduction has very strong anti-carbon monoxide poisoning capability.
Embodiment 9:
1g phthalocyanine cobalt and 5g CNT are put into ball grinder, add iron ball and feed the argon gas good seal, implemented ball milling 12 hours, take out the powder cooling and obtain compound oxygen reducing catalyst.The compound oxygen reduction electro-catalyst of 2mg preparation is scattered in the Nafion solution of 1ml 0.2%, obtains 2mg.mL
-1Oxygen reduction electro-catalyst solution.Get 5 μ L solution and drip to the surface of glass-carbon electrode (diameter 3mm), electrode at room temperature after the drying, obtains containing the modified electrode of compound oxygen reduction electro-catalyst.1mg Pt/C (commerce is used the platinum black VPO catalysts, and mass ratio is 40%, purchases the Johnson-Matthey company in Britain) is scattered in the Nafion solution of 1ml 0.2%, obtains 2mg.mL
-1Pt/C solution.Get 5ml Pt/C solution and drip to the surface of glass-carbon electrode (diameter 3mm), electrode at room temperature after the drying, obtains the Pt/C modified glassy carbon.Respectively with the carbon nano-tube modified composite catalyst modified glassy carbon of phthalocyanine cobalt, Pt/C catalyst modified glassy carbon is as working electrode, use electrochemical workstation (Shanghai China in morning electrochemical apparatus Co., Ltd, CHI660C) and the standard three-electrode system (platinum filament is as auxiliary electrode, interior reference liquid be the Ag/AgCl electrode of 3M KCl as reference electrode, modified electrode is as working electrode) at 0.1mol.L
-1In the KOH solution with 100mV.s
-1Sweep speed carry out the test of 10000 cyclic voltammetrics.Figure 10 is that (Figure 10 is a) at the saturated 0.1mol.L of oxygen for the carbon nano-tube modified composite catalyst modified glassy carbon of phthalocyanine cobalt (Figure 10 b) and Pt/C catalyst modified glassy carbon
-110000 cyclic voltammograms in the KOH solution.As can be seen from the figure, after 10000 times cyclic voltammetric test, the catalytic capability of Pt/C catalyst is seriously decayed, and does not almost have the reduction current of oxygen.Compare with the Pt/C catalyst of commercialization, the catalytic activity of the carbon nano-tube modified composite catalyst of phthalocyanine cobalt is subjected to the influence of 10000 cyclic voltammetric tests hardly, and the not decay of the electric current of catalytic oxygen reduction has good stability.
Claims (9)
1. the compound oxygen reduction electro-catalyst of a nitrogenous carbon nano materials modified by macrocyclic compound is characterized in that being composited by nanometer carbon material supported nitrogenous macrocyclic compound.
2. compound oxygen reduction electro-catalyst according to claim 1, it is characterized in that nitrogenous macrocyclic compound comprises more than one following material: phthalocyanine, porphyrin, dibenzo four azepine annulenes, the metal complex of phthalocyanine, porphyrin, dibenzo four azepine annulenes, the derivative of phthalocyanine, porphyrin, dibenzo four azepine annulenes, the metal complex of the derivative of phthalocyanine, porphyrin, dibenzo four azepine annulenes.
3. compound oxygen reduction electro-catalyst according to claim 1 is characterized in that described carbon nanomaterial is carbon nano-particle, CNT, carbon nano-fiber or nano carbon microsphere.
4. compound oxygen reduction electro-catalyst according to claim 3 is characterized in that described metal complex comprises the metal complex of iron, cobalt, nickel, copper or zinc.
5. compound oxygen reduction electro-catalyst according to claim 1, the structure that it is characterized in that described nitrogenous macrocyclic compound is that carbon nitrogen conjugated double bond forms big ring, and the metallic atom at big ring nitrogen and center carries out coordination and the structure of the big ring encirclement metal that forms.
6. the preparation method of compound oxygen reduction electro-catalyst according to claim 1 is characterized in that carbon nanomaterial and nitrogenous macrocyclic compound are composited by one of following complex method: (1) mechanical mixture: in atmosphere by grinding or mixing and ball milling carbon nanomaterial and nitrogenous macrocyclic compound are composited; (2) physical absorption mixes: use the nitrogenous macrocyclic compound of dissolution with solvents, add carbon nanomaterial, fully be composited after the concussion; (3) chemical bonding: utilize the chemical reaction between carbon nanomaterial and the nitrogenous macrocyclic compound to be composited.
7. the preparation method of compound oxygen reduction electro-catalyst according to claim 6 is characterized in that the atmosphere in the mechanical mixture is air, nitrogen or argon gas.
8. the preparation method of compound oxygen reduction electro-catalyst according to claim 6 is characterized in that described physical absorption mixing specifically comprises the steps:
In mass fraction, with 1～10 part of nitrogenous macrocyclic compound of 100～2000 parts of dissolution with solvents, add 10～100 parts of carbon nanomaterials again, in 10～60KHz is ultrasonic, fully mixed 6～24 hours, filter and remove solvent, oven dry obtains described compound oxygen reduction electro-catalyst.
9. the preparation method of compound oxygen reduction electro-catalyst according to claim 8, it is characterized in that solvent for use comprises inorganic solvent and organic solvent: described inorganic solvent comprises neutral aqueous solution, acidic aqueous solution or alkaline aqueous solution; Described organic solvent comprises ethanol, chloroform or N, dinethylformamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010019500A CN101745426A (en) | 2010-01-19 | 2010-01-19 | Compound oxygen reduction electro-catalyst of carbon nano materials modified by macrocyclic compound containing nitrogen and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010019500A CN101745426A (en) | 2010-01-19 | 2010-01-19 | Compound oxygen reduction electro-catalyst of carbon nano materials modified by macrocyclic compound containing nitrogen and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101745426A true CN101745426A (en) | 2010-06-23 |
Family
ID=42473417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010019500A Pending CN101745426A (en) | 2010-01-19 | 2010-01-19 | Compound oxygen reduction electro-catalyst of carbon nano materials modified by macrocyclic compound containing nitrogen and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101745426A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569831A (en) * | 2012-03-07 | 2012-07-11 | 东华大学 | Carbon load copper phthalocyanine fuel cell catalyst CuPc/C and preparation method and application thereof |
| CN102637882A (en) * | 2012-04-13 | 2012-08-15 | 东华大学 | Metal-free nitrogen- functionalized carbon catalyst as well as preparation method and application thereof |
| CN102872895A (en) * | 2012-10-23 | 2013-01-16 | 江西师范大学 | Natural plant based preparation method for low-cost high-efficiency catalyst for oxygen reduction reaction |
| CN106784893A (en) * | 2016-12-16 | 2017-05-31 | 中国石油大学(华东) | A kind of high activity for fuel cell anode is without metal N, P codope conjugated backbone material |
| CN108172847A (en) * | 2017-12-08 | 2018-06-15 | 南方科技大学 | FePC base carbon nanotube composite electrocatalyst and its preparation method and application |
| CN109718855A (en) * | 2018-12-22 | 2019-05-07 | 中国科学院山西煤炭化学研究所 | A kind of package metals complex is in the method for material surface |
| CN110176607A (en) * | 2019-05-14 | 2019-08-27 | 清华大学 | A kind of fuel battery cathod catalyst and preparation method thereof |
| CN111146457A (en) * | 2019-12-27 | 2020-05-12 | 大连理工大学 | Preparation and application of porous composite material electrocatalyst based on bimetallic macrocyclic compound |
| CN111370712A (en) * | 2020-02-24 | 2020-07-03 | 中南大学 | Preparation method of high-activity electrochemical oxygen reduction catalyst |
| CN113178585A (en) * | 2021-04-09 | 2021-07-27 | 常熟理工学院 | Nano carbon material modified by cobalt-containing nitrogen-oxygen complex and preparation method thereof |
-
2010
- 2010-01-19 CN CN201010019500A patent/CN101745426A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569831A (en) * | 2012-03-07 | 2012-07-11 | 东华大学 | Carbon load copper phthalocyanine fuel cell catalyst CuPc/C and preparation method and application thereof |
| CN102569831B (en) * | 2012-03-07 | 2015-10-28 | 东华大学 | Carbon supported copper phthalocyanine dyestuffs cell catalyst CuPc/C and Synthesis and applications |
| CN102637882A (en) * | 2012-04-13 | 2012-08-15 | 东华大学 | Metal-free nitrogen- functionalized carbon catalyst as well as preparation method and application thereof |
| CN102637882B (en) * | 2012-04-13 | 2014-11-05 | 东华大学 | Metal-free nitrogen- functionalized carbon catalyst as well as preparation method and application thereof |
| CN102872895A (en) * | 2012-10-23 | 2013-01-16 | 江西师范大学 | Natural plant based preparation method for low-cost high-efficiency catalyst for oxygen reduction reaction |
| CN106784893A (en) * | 2016-12-16 | 2017-05-31 | 中国石油大学(华东) | A kind of high activity for fuel cell anode is without metal N, P codope conjugated backbone material |
| CN108172847A (en) * | 2017-12-08 | 2018-06-15 | 南方科技大学 | FePC base carbon nanotube composite electrocatalyst and its preparation method and application |
| CN109718855A (en) * | 2018-12-22 | 2019-05-07 | 中国科学院山西煤炭化学研究所 | A kind of package metals complex is in the method for material surface |
| CN110176607A (en) * | 2019-05-14 | 2019-08-27 | 清华大学 | A kind of fuel battery cathod catalyst and preparation method thereof |
| CN111146457A (en) * | 2019-12-27 | 2020-05-12 | 大连理工大学 | Preparation and application of porous composite material electrocatalyst based on bimetallic macrocyclic compound |
| CN111146457B (en) * | 2019-12-27 | 2021-05-04 | 大连理工大学 | Preparation and application of porous composite material electrocatalyst based on bimetallic macrocyclic compound |
| CN111370712A (en) * | 2020-02-24 | 2020-07-03 | 中南大学 | Preparation method of high-activity electrochemical oxygen reduction catalyst |
| CN113178585A (en) * | 2021-04-09 | 2021-07-27 | 常熟理工学院 | Nano carbon material modified by cobalt-containing nitrogen-oxygen complex and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101745426A (en) | Compound oxygen reduction electro-catalyst of carbon nano materials modified by macrocyclic compound containing nitrogen and preparation method thereof | |
| CN101773855B (en) | Oxygen reduction catalyst prepared from grapheme modified by macrocyclic compound, and preparation method thereof | |
| CN102637882B (en) | Metal-free nitrogen- functionalized carbon catalyst as well as preparation method and application thereof | |
| CN103227334B (en) | Carbon-containing metal catalyst, preparation method and application thereof | |
| CN103143378B (en) | Preparation method of non-noble metal oxygen reduction electrocatalyst for cathode of fuel cell | |
| Wang et al. | Surface-oxidized Fe–Co–Ni alloys anchored to N-doped carbon nanotubes as efficient catalysts for oxygen reduction reaction | |
| CN107863538B (en) | Electrode for ethanol catalysis and application thereof | |
| CN107029772A (en) | A kind of non-precious metal catalyst and preparation method thereof | |
| CN105413730A (en) | Preparation method of cobalt electro-catalysis oxygen reduction material wrapping nitrogen-doped carbon nanotube | |
| CN101890365B (en) | Oxygen reduction catalyst serving as non-noble metal and preparation method thereof | |
| CN102024955B (en) | Three-dimensional mesh nano porous palladium-ruthenium electrode material for fuel cell and preparation method thereof | |
| CN102569831B (en) | Carbon supported copper phthalocyanine dyestuffs cell catalyst CuPc/C and Synthesis and applications | |
| CN103515624A (en) | Carbon supported non-noble metal oxygen reduction compound catalyst, and preparation method and application thereof | |
| CN102324531A (en) | Carbon-supported CoN fuel-cell catalyst as well as preparation method and application thereof | |
| CN105817240A (en) | Pt doped phosphatizing cobalt bead catalyst carried by methanol carbon dioxide and preparation method of Pt doped phosphatizing cobalt bead catalyst | |
| CN103296292B (en) | Alkaline fuel cell cathode carbon catalyst and preparation method thereof | |
| CN103165914B (en) | Pt/Au/PdCo/C catalyst, and preparation and application thereof | |
| CN102810678B (en) | Direct methanol fuel cell catalyst and preparation method thereof | |
| CN109873174B (en) | Preparation method of three-dimensional carrier supported platinum-palladium-cobalt alloy structure catalyst for low-temperature fuel cell | |
| Han et al. | Noncovalent interactions on the electrocatalytic oxidation of ethanol on a Pt/C electrocatalyst | |
| WO2022099793A1 (en) | Orr catalyst material, preparation method therefor, and use thereof | |
| CN109037717A (en) | A kind of ferrum-based catalyst and preparation method of alkaline fuel cell | |
| CN102104154B (en) | Nitrogenous transition metal microbial fuel-cell catalyst and preparation method thereof | |
| CN103594718A (en) | Preparation and usage of nanoribbon-shaped Cucurbit[6]uril carried cubic palladium nanoparticles | |
| CN101916868B (en) | Method for stabilizing palladium catalyst by montmorillonite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20100623 |