CN1830108A - Platinum-free electrocatalyst materials - Google Patents
Platinum-free electrocatalyst materials Download PDFInfo
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- CN1830108A CN1830108A CNA038244365A CN03824436A CN1830108A CN 1830108 A CN1830108 A CN 1830108A CN A038244365 A CNA038244365 A CN A038244365A CN 03824436 A CN03824436 A CN 03824436A CN 1830108 A CN1830108 A CN 1830108A
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Abstract
New metal-based catalyst materials, non-containing platinum, for preferred application to form both alcohol-tolerant cathodes for oxygen reduction and anodes for oxidation of various fuel molecules, and methods of making the said catalysts are provided. Methods for preparing anodes and cathodes for fuel cells are also provided.
Description
Technical field
Present invention relates in general to not have platinum transition metal base carrier catalyst and the application in fuel cell thereof, this catalyst is fit to multiple use, as be used for the anode and the negative electrode of fuel cell, as reforming catalyst, oxidation catalyst, water-gas shift catalyst, the anode and the negative electrode that are used for metal-air battery are as lambda sensor and oxygen composite catalyst.Specifically, the present invention relates to be exclusively used in the catalytic oxidation-reduction alcohol-tolerance cathode material or the catalytic oxidation use anode material of fuel.
Background technology
Fuel cell is the electrochemical apparatus that can directly be converted to chemical reaction electric energy.In this class battery, fuel (being generally hydrogen, alcohol or saturated hydrocarbons) and oxidant (being generally airborne oxygen) are supplied with electrode continuously.In theory, as long as to electrode fueling and oxidant, fuel cell just can produce electric energy.In fact, the aging actual life of having limited fuel cell of element with fault.
Various fuel cells are in the different development phases; Particularly, consider that the present invention describes and the claimed applicable battery of eelctro-catalyst, the battery of mentioning below can be used as example: with H
2For the polymer electrolyte fuel cells (PEFC) of fuel, with alcohol (direct alcohol fuel battery, DAFC) or other any hydrogeneous liquid or gaseous fuel (alcohol, glycol, aldehyde, saturated hydrocarbons, carboxylic acid etc.) be direct oxidation fuel cell (DOFC), phosphoric acid fuel cell (PAFC) and the fusion carbonic acid fuel cell (MCFC) of fuel.
The main element of the fuel cell of all the above-mentioned types is electrodes, and it comprises usually by porous carbon materials contained metal or metallic particles, and this porous carbon materials and suitable conductor are affixed.The catalyst that is generally used for oxygen reduction comprises transition metal, and for example platinum, nickel, cobalt, silver have only been said some here.Be generally used for the oxygenated fuel (H among the PEFC for example
2And the methyl alcohol in the direct methanol fuel cell (DMFC)) catalyst is platinum, platinum-ruthenium, platinum-ruthenium-molybdenum and platinum-tin mixture.All generations can accept voltage (＞0.5V) fuel cell contains platinum, its individualism or with other melts combine, it preferably combines with ruthenium at anode, negative electrode is made up of platinum usually, but can adopt other metal too.Generally speaking, usually preferred platiniferous in high load capacity has brought serious restriction economically for a large amount of productions of the fuel cell that is used for communications and transportation, mobile phone and electronic equipment.In fact, expensive (being about 25-30 dollar/gram now) of platinum cause the cost of the electric energy that produces by fuel cell far above cost by the electric energy that other alternative method produced.Compare with the conventional energy production method, obtain the fuel cell of high efficiency and good environment performance, just press for a kind of no platinum fuel cells of exploitation.
Known to the applicant, platinum is the neccessary composition of present obtainable DOFC or PEFC anode.
US-A-4828941 has described methyl alcohol/air-fuel battery, and wherein negative electrode includes Co (salen) compound as catalyst component or contains the polymer of this compound.The catalyst of used oxidation methyl alcohol can not be save platinum in its electrochemical cell required for protection.
Described the synthetic of methyl alcohol-tolerance negative electrode of being used for hydrogen reduction among the US-A-6245707, mixed and heat treatment obtains by the nitrogen complex compound that will two kinds contains different transition metal at least.The nitrogen complex compound comprises metalloporphyrin, and preferred transition metal is iron, cobalt, nickel, copper, manganese, ruthenium, vanadium and zinc.
US-A-5358803 has described the fuel cell catalytic cathode, comprises the mixture of being made up of cobalt acetate and polyacrylonitrile.
US-A-5240893 has described a kind of method for preparing electrode, particularly negative electrode, is made up of metal-assorted carbon-nitrogen pyrolytic material, and wherein metal is cobalt, nickel, iron, copper, vanadium, chromium and manganese and composition thereof.Under the situation that base catalyst exists,, amines and formaldehyde or paraformaldehyde obtain a kind of polymer by being reacted.This polymer separates on the spot or forms, and obtains gum polymers with carbon granule and reacting metal salt, cures 1 hour under 800 ℃.Gained powder and adhesive are mixed for preparing electrode.Although metal dopant is arranged, tens mW/cm are only arranged by the concrete power of this negative electrode supply
2Low current density.
DE-A-2549083 has reported the preparation of no platinum fuel cells with iron-phthalocyanine base negative electrode.
WO-A-0196264 has described the Fischer-Tropsch catalyst, constitute by the base-material that comprises polymer (normally polyacrylate or polymethacrylates) and at least two kinds of metals (a kind of is iron, cobalt, nickel and chromium, and another kind is iron, silver, zinc, platinum, zirconium or its mixture).
Description of drawings
Fig. 1 is to use the fuel cell generalized section of a simplification of catalyst of the present invention.
Fig. 2 is that different materials is at 2N H
2SO
4-1N CH
3Anodic polarization curves in the saturation of the air solution of OH.
Fig. 3 is that different materials is at 2N H
2SO
4-1N CH
3Cathodic polarization curve in the saturation of the air solution of OH.
Fig. 4 is that different materials is at 1N KOH-1N CH
3Anodic polarization curves in the saturation of the air solution of OH.
Fig. 5 is that different materials is at 1N KOH-1N CH
3Cathodic polarization curve in the saturation of the air solution of OH.
Fig. 6 represent to adopt the electrode of making by catalyst of the present invention a DMFC performance over time.
Fig. 7 represents the flow chart of various processes that prepared polymer and be used for producing the metal-doped catalysis material of electrode up to preparation by initial reactant.
Detailed Description Of The Invention
The applicant has now found that, by 4-{1-[(2,4-2 (replacement)-phenyl)-hydrazono-]-alkyl }-benzene-1,3-glycol and 3, the fresh sample polymer that 5-disubstituted benzenes phenol and formaldehyde or paraformaldehyde condensation are constituted, with the transition metal salt coordination, handling with appropriate reductant and after carrier material (porous carbon, graphite, metal dust etc.) is upward fixing, producing electrochemical cell catalyst very efficiently, for example, under the normal temperature and pressure, directly can produce during for fuel high to 160mW/cm with methyl alcohol
2Electric energy, when with H
2Height is to 300mW/cm during for fuel
2
Therefore first embodiment of the present invention relates to a kind of nitrogen-oxygen-carbon polymer (after this representing with P) that is fit to slaine coordination except that platinum salt.
According to the present invention, nitrogen-oxygen-carbon polymer is expected by 4-{1-[(2,4-2 (replacement)-phenyl)-hydrazono-]-alkyl }-benzene-1,3-glycol and 3,5-disubstituted benzenes phenol and formaldehyde or paraformaldehyde contain under the situation of alkali (as NaOH) or acid (as HCL) catalyst at the water/alcohol mixture as solvent, and condensation forms under the temperature of a methylol intermediate compound (according to formula I) being enough to form.
According to the present invention, 4-{1-[(2,4-2 (replacement)-phenyl)-hydrazono-]-alkyl }-benzene-1, the 3-glycol is for having the compound of structural formula (A):
Wherein, R
1Be selected from hydrogen, alkyl, be preferably aliphatic group with 1-10 carbon atom, but halogenation, more preferably methyl or ethyl.
R
2And R
3Respectively independently represents electronics-acceptor groups, be preferably selected from hydrogen, halogen, acyl group, ester, carboxylic acid, formoxyl, nitrile, semi-annular jade pendant acid, straight or branched alkyl or aromatic radical (can select with halogen functionalized or utilize phenyl ring to combine to form one or more condensed ring) and nitro with 1-15 carbon atom.
According to the present invention, 3,5-disubstituted benzenes phenol is for having the compound of structural formula (B):
R wherein
4And R
5Respectively independently represents an electronic donor group, be selected from hydrogen, hydroxyl, ether, amine, aromatic radical and have the straight or branched alkyl of 1-15 carbon atom.
According to the present invention, acyl group is group COR ', and wherein R ' is preferably C
1-10Alkyl or aromatic radical, ester is group COOR ', wherein R ' as defined above, ether is group OR ', wherein R ' as defined above, amine is group NR " R , wherein R " and R are identical or different, is H or C
1-10Alkyl, aromatic radical; Aromatic radical is preferably phenyl, naphthyl and more senior homologue in all above-mentioned definition.
The preferred latter in formaldehyde and paraformaldehyde.
See below, gained nitrogen-oxygen-carbon polymer is brick-red solid, dissolves in polar organic solvent usually, as dimethyl sulfoxide (DMSO), dimethyl formamide, 1,4-dioxane, acetone and oxolane.
The most probable similar phenol units of P is by 4-{1-[(2,4-2 (replacement)-phenyl)-hydrazono-]-alkyl }-benzene-1, the phenolic resins (Bakelite) that the 3-diol units is replaced, this helps to adjust the chemistry-physical characteristic of polymer itself.Can both generate macromolecular structure with formolite reaction owing to these two kinds of phenol derivatives (A) with (B), the further adjustment of P can obtain by the initial mol ratio (A/B) that changes them; According to the present invention, this initial mol ratio is preferably 0.5-2, and more preferably 0.7.
Also can represent according to polymer of the present invention by following structural formula (C):
Wherein, y can change between 2-120, and x can change between 1-2, and n can change between 1-3, R
1, R
2, R
3, R
4And R
5As defined above.
With reference to the said structure formula, those skilled in the art can understand, and polymer P according to the present invention has available nitrogen and the oxygen atom center as bond, preferably with the complexing mode combination.The IR of P and NMR spectrum show that clearly NH and OH base all exist.The P material can not decompose in air drying several hours under 150 ℃.By the appropriate change experimental condition can about 1000 to about 50000 on a large scale in adjust mean molecule quantity.
According to a preferred manufacturing procedure, polymer P of the present invention is by 4-{1-[(2,4-2 (replacement)-phenyl)-hydrazono-]-alkyl }-benzene-1,3-glycol and 3,5-disubstituted benzenes phenol and formaldehyde or paraformaldehyde contain under the situation of alkali (as NaOH) or acid (as HCL) catalyst at the water/alcohol mixture as solvent, and condensation forms under the temperature of a methylol intermediate compound (according to following formula I) being enough to form:
Formula I
Wherein, R
1, R
2, R
3, R
4And R
5As defined above.
4-{1-[(2,4-2 (replacement)-phenyl)-hydrazono-]-alkyl }-benzene-1, the 3-diol reactant is by suitable 4-acyl group/formoxyl-benzene-1,3-glycol and the hydrazine condensation of 2-4 di-substituted-phenyl and synthesize.
Polymer P also can use independent component 4-acyl group/formoxyl-benzene-1,3-glycol, 2-4 di-substituted-phenyl hydrazine, 3, and 5-disubstituted benzenes phenol and formaldehyde or paraformaldehyde and one step of above-mentioned substituting group or multistep make.
Preferable reaction temperature is that about 20 ℃ to about 150 ℃, pH value are about 1 to about 14.
According to second embodiment, the present invention relates to a kind of complex compound that comprises aforesaid polymer and slaine.
In fact; the complexing characteristic of P excellence allows itself and a variety of slaine to form stable complexation; described slaine is preferably transition metal salt, more preferably iron-, cobalt-and nickel-carboxylate ,-halide ,-alcoholates ,-the pentanedione thing ,-formates ,-oxalates ,-malonate and similar organic salt and composition thereof.
Known according to inorganic chemistry, form co-ordination complex if can be under reaction environment interact with polymer P, inorganic salts such as carbonate, oxide and bicarbonate etc. and composition thereof also are suitable for.
The acetate of preferred especially Fe, Co and Ni (and composition thereof).
Suspension that can be by stirring P according to complex compound of the present invention makes with being preferably dissolved in the slaine in water or the water/ethanol or the mixture of slaine, and slaine is preferably nickel (II), iron (II) and cobalt (II) salt.Reaction has produced a kind of material, and wherein slaine and P have combined and kept the state of oxidation of molecular precursor strongly.
After this metal-doped material of gained uses P-M (M=main group or transition metal) expression, highly stable: the slaine that still can not lose institute's complexing after repeatedly washing with boiling water.
According to above-mentioned preferred steps, the total metal contents in soil in described metal-doped material P-M can change suitably in the 0.5-10wt.% scope.
Particularly, P and two kinds of slaines with predetermined ratio or have the reacting metal salt of predetermined ratio with the n kind, can keep fully add the initial ratio of metal.Therefore, P and for example stoichiometric proportion are 1: 1: 1 Fe (OAc) 2, Ni (OAc) 2 and Co (OAc) 2 (OAc=acetate) reaction, and can make the P-M material comprise mol ratio is 1: 1: 1 iron (II), nickel (II) and cobalt (II) ion.
According to another embodiment, the present patent application relates to catalyst and the electrode for fuel cell that makes from above-mentioned P-M material, and this electrode comprises such catalyst that combines with suitable conductive carrier.
In addition, the invention still further relates to the fuel cell that comprises according to electrode of the present invention.
Metal beyond this catalyst package platiniferous of the present invention, preferred especially nickel, cobalt, iron and composition thereof, and reduction and catalysis all gases or fluid matrix (H that unexpectedly can Catalytic Oxygen
2, methyl alcohol, ethylene glycol and higher glycols, gasoline, formaldehyde, hydrazine, only said some) oxidation.The applicant finds that also this class catalyst formed the active electrode of fuel cells of different types.Particularly, the applicant also is surprised to find, and anode needs the nickel individualism or forms binary and ternary bond with cobalt and iron, yet in a kind of method for optimizing, negative electrode comprises independent nickel or cobalt.
In addition, negative electrode of the present invention tolerates fully to intersecting alcohol, and with respect to platinum-Ji DAFC, it allows to use the alcohol of higher concentration (high to 50% volume).
For preparing catalyst of the present invention, solid-state following in conjunction with H
2Or in the liquid solution system, adopt reducing agent to the P-M material processed.
Therefore, the solid-state sample of PM material is scattered in the solvent, preferred water/alcohol mixture is handled with reductant solution then, preferred water-based hydrazine solution, more preferably at-10-30 ℃ down with tetraphydro-borate [Y] BH
4Handle, wherein Y is an alkali metal cation, Li
+, Na
+, K
+, or be organic cation, as tetraalkyl amine (NR
4)
+With two (the positive phosphorus Ji Yaji of triphenyl) amine (PPN
+), only said some here.
According to the preparation catalyst of the present invention another kind of method, under inert gas shielding (as N
2, argon gas), solid P-M material sample at 500-1000 ℃, is preferably under 800 ℃ the suitable temperature and cured about 2 hours.
In a method for optimizing of preparation catalyst of the present invention, particularly form fuel cell anode as illustrated in Figure 1, with before the reducing agent processing, the P-M material can be stated from porous carbon carrier material (Vulkan XC-72, active carbon RBDA earlier in solid-state or liquid solution system, the R-5000 standard, NSM-III, Ketjen carbon black and Raven-1020, graphite etc.) on, or also can be stated from other conductive carrier material, as silver, nickel and other fine powder.The reduction of metal center forms with assorted carbon-carrier metal particle (HC-P-M), and wherein M is made of monometallic except that platinum or metal mixture.
With in another method for optimizing of anode, under 350-400 ℃, use H at the preparation fuel cell
2Air-flow was to solid P-M material processed about 1-2 hour.
Because P has excellent compatibility to slaine, by in suitable solvent, mixing P, a kind of slaine or multiple different metal salt and carbon carrier, and with the gained mixture with reducing agent (as hydrazine or tetraphydro-borate, here only said some) handle, described assorted carbon-carried catalyst HC-P-M also can a step or multistep make.
The preparation catalyst HC-P-M of the present invention a method for optimizing in, particularly form cathode for fuel cell, under the inert gas shielding (as N
2, argon gas), 500-1000 ℃, be preferably cure about 2 hours heat treatment under 800 ℃ the suitable temperature before, the P-M material can be stated from porous carbon carrier material (Vulkan XC-72 earlier, active carbon RBDA, R-5000 standard, NSM-III, Ketjen carbon black and Raven-1020, graphite etc.) on, or also can be stated from other conductive carrier material, as silver, nickel and other fine powder.
The general step that is prepared anode and negative electrode by catalyst of the present invention is as follows:
Section H C-P-M is suspended in water/alcohol mixture of 1: 1, strong agitation under the room temperature.Stir adding non wettability preparation in this suspension down, (60wt% is scattered in water, Aldrich) (is about 20wt% for HC-P-M) as polytetrafluoroethylene (PTFE).Keep under the strong agitation and produced a kind of flocculate in about 10 minutes.The sonicated reaction vessel drains separation until forming the rubber-like material with it.With this material rolling to carbon paper, sintering graphite or wire netting (steel, nickel etc.), at about 100Kg/cm
2Be rolled under the pressure.Inert atmosphere (N
2, Ar) electrode that will form so down cures under 350-400 ℃.
The present invention is further described by the following examples, yet it only plays illustration purpose, does not limit the total scope of invention itself.
Three kinds of preferred steps of preparation polymer P have been described in embodiment 1,2 and 3.
Embodiment 1
32g 4-{1-[(2,4-dinitro benzene)-hydrazono-]-ethyl-benzene-1, the 3-glycol is uniformly dispersed and forms suspension in 200mL water, under the room temperature to wherein adding 10g phenol and 10ml aqueous formaldehyde (40wt.%).Stir and in this mixture, add solid NaOH (0.5g) down.Gained crineous suspension obtains the crineous solid in 110 ℃ of backflows 8 hours.Filter out solid, repeatedly wash, join then in the 500ml distilled water with cold water.With concentrated hydrochloric acid (37%) gradually in and gained suspension to pH value be 7.The polymer P that separates is the kermesinus solid, collects back with cold water/acetone mixture (1: 1 v: v) repeatedly wash to remove unreacted monomer and low molecular weight part.Behind the purifying, with P in 60 ℃ of dry 3-4 hours, output 38g.
Embodiment 2
32g 4-{1-[(2,4-dinitro benzene)-hydrazono-]-ethyl-benzene-1, the 3-glycol is uniformly dispersed and forms suspension in 200mL water, under the room temperature to wherein adding 10g phenol and 10ml aqueous formaldehyde (40wt.%).Stir and in this mixture, add dense (37%) HCl (10mL) down.Gained crineous suspension obtains the crineous solid in 110 ℃ of backflows 8 hours.Filter out solid, repeatedly wash, join then in the 500ml distilled water with cold water.With the 1N NaOH aqueous solution gradually in and gained suspension to pH value be 7.The polymer P that separates is the kermesinus solid, collects back with cold water/acetone mixture (1: 1 v: v) repeatedly wash to remove unreacted monomer and low molecular weight part.Behind the purifying, with P in 60 ℃ of dry 3-4 hours, output 36g.
Embodiment 3
In the 1000ml methanol solution that contains 5.0g (2, the 4-dichloro-benzenes) hydrazine, slowly add the 10ml concentrated sulfuric acid.After the dissolving, add 1 molar equivalent (2, the 4-dihydroxy)-benzophenone under the room temperature.After 5 minutes, solution becomes orange and has the crineous solid to begin precipitation.Filter out solid and repeatedly wash, suspend in water then with cold water.With dense NaOH gradually in and suspension to pH value be 7.The crineous solid of collecting is repeatedly washed with cold water, join then in the 500ml distilled water.Add equivalent 3, the 5-xylenol and with solution with 10mL HCl (37%) acidifying.After the dissolving, stir down slowly adding 1 molar equivalent formaldehyde (solution of 40wt%) fully.Stir down in 110 ℃ of backflow gained solution.After 8 hours, P is separated into the kermesinus solid, collects back with cold water/acetone mixture (1: 1 v: v) repeatedly wash to remove unreacted monomer and low molecular weight part.Behind the purifying, with P in 60 ℃ of dry 3-4 hours, output 3.9g.
By 4-{1-[(2,4-dinitro benzene)-hydrazono-]-ethyl-benzene-1, the typical polymer P sample characteristics of for example that 3-glycol, phenol and paraformaldehyde make: adopt elementary analysis, Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectrum (UV-Vis) with
1H and
13C{
1H}NMR spectrum.
Element: C, 58.60%; H, 4.24%; N:12.15%. (this analysis coincide the well polymer of structural formula C, wherein x=1 and n=1; Be calculated as: C, 58.67%; H, 4.00%; N:12.44%)
FT-IR:3600-3200 (vO-H); 3290 (vN-H); 3100 (v aromatics C-H); 1620 (v C=N); 1615 (v aromatics C=C); 1590 (δ N-H); 1530 (vs.NO
2); 1514 (Vas.NO
2); 1330 (δ O-H); 830 (v aromatics C-NO
2); 710 (δ aromatics C-H) cm
-1
UV-Vis: λ
Max=390nm; The peak is 420nm.
1H NMR (400.13MHz, 298K): (CD
3COCD
3): δ=2.4-2.6 (N=C-CH
3); 3.7-4.1 (Ar-CH
2-Ar); (6.4-6.3 C-H, aromatics); (7.0-6.8 C-H, phenol ring); (7.6-7.4 C-H, aromatics); (8.5-8.3 H, phenol ring); (9.0-8.9 H, aromatics), 9.1-9.0 (Ar-NH-N), 11.4-11.2 (Ar-OH), 12.0-11.8 (Ar-OH).
13C NMR:(CD
3COCD
3): δ=40 (Ar-CH
2-Ar); 102-130 (aromatics); 137 (O
2N-C aromatics); 143 (HN-C aromatics); 159 (Ar-C=N-); 160-161 (HO-C aromatics) ppm.
Polymer P decomposes before fusion when being higher than 300 ℃.
Embodiment 4 and 5 has described two method for optimizing of preparation catalyst of the present invention.
Embodiment 4
In 100ml acetone, dissolve 0.50g P and 0.30g acetate four hydration nickel (II) under the room temperature (Aldrich).Agitating solution evaporates fully until acetone under the room temperature, stays red residue.This solid, described P-M is introduced into quartz reactor, the following 800 ℃ of heating of nitrogen protection air-flow 2 hours.Obtain 0.30g black powder material, comprise nickel 7.1wt.% (ICP-AES analysis).
Embodiment 5
Under the room temperature in 100ml acetone dissolving 0.5g P, 0.13g acetate four hydration nickel (II) (Aldrich), 0.08g acetate four hydrated irons (II) (Aldrich) and 0.08g acetate four hydration cobalts (II) (Aldrich).Stir gained solution under the room temperature and evaporate fully, stay the purple residue until acetone.This crude product, described P-M is introduced into quartz reactor, H
2The following 360 ℃ of heating of air-flow 2 hours.Obtain 0.6g black powder material, total metal content is 9.2wt.% in the product, and the ratio of iron, cobalt and nickel is about 1: 1: 1 (ICP-AES analysis).
Embodiment 6 has described a method for optimizing that is prepared negative electrode by HC-P-M material of the present invention.
Embodiment 6
In 100ml acetone, dissolve 0.50g P, 0.30g acetate four hydration nickel (II) (Aldrich) under the room temperature.In the mixture that contains described P-M, add 5.0g Vulkan XC-72R (earlier at N
2Following 800 ℃ of heating activated in 2 hours, used HNO then
3(50%) aqueous solution refluxes).Stir gained solution under the room temperature and evaporate fully, stay the black residue until acetone.Remove all acetone under the decompression.This solid residue is introduced into quartz reactor, the following 800 ℃ of heating of nitrogen current 2 hours.
Stir down solid product is scattered in 1: the 1 water/alcohol mixture of (vv).(60wt% is scattered in water, Aldrich) to add 2.5g PTFE under stirring in this suspension.Keep under the strong agitation and produced a kind of flocculate in about 10 minutes.The sonicated reaction vessel drains separation until forming the rubber-like material with it.With this material rolling to Teflon
On the carbon paper (Toray) of-processing, at 100Kg/cm
2Be rolled under the pressure.The electrode that will form like this under the dinitrogen atmosphere cures under 350 ℃.
Embodiment 7 and 8 has described two method for optimizing of preparation anode of the present invention.
Embodiment 7
Under the room temperature in 100ml acetone dissolving 0.5g P, 0.10g acetate four hydration nickel (II) (Aldrich), 0.065g acetate four hydrated irons (II) (Aldrich) and 0.065g acetate four hydration cobalts (II) (Aldrich).In the mixture that contains described P-M, add 5.0g Vulkan XC-72R (earlier at N
2Following 800 ℃ of heating activated in 2 hours, used HNO then
3(50%) aqueous solution refluxes).Remove all acetone under the decompression.This solid residue is introduced into quartz reactor, the following 360 ℃ of heating of hydrogen stream 2 hours.
Stir down solid product is scattered in 1: the 1 water/alcohol mixture of (vv).(60wt% is scattered in water, Aldrich) to add 2.5g PTFE in gained suspension.Keep under the strong agitation and produced a kind of flocculate in about 10 minutes.The sonicated reaction vessel drains separation until forming the rubber-like material with it.400Kg/cm
2Under the pressure that this material rolling is online to circular steel, the thick 0.2mm of this steel mesh line, mesh size 0.2mm, radius 1.75cm.
Embodiment 8
Under the room temperature in 100ml acetone dissolving 0.5g P, 0.10g acetate four hydration nickel (II) (Aldrich), 0.065g acetate four hydrated irons (II) (Aldrich) and 0.065g acetate four hydration cobalts (II) (Aldrich).In the mixture that contains described P-M, add 5.0g Vulkan XC-72R (earlier at N
2Following 800 ℃ of heating activated in 2 hours, used HNO then
3(50%) aqueous solution refluxes).0 ℃ is stirred after 10 minutes down, dropwise adds 10ml NaBH
4(10wt.%) aqueous solution (note: the hydrogen of emitting can react with the solid catalyst that is deposited on the reactor wall).Stirred 30 minutes under the room temperature.The isolated by filtration solid product, and water/ethanol (1: 1, vv) repeatedly washing.Stir the water/alcohol mixture that down solid product is added 1: 1 (w).(60wt% is scattered in water, Aldrich) to add 2.5g PTFE in gained suspension.Keep under the strong agitation and produced a kind of flocculate in about 10 minutes.The sonicated reaction vessel drains separation until forming the rubber-like material with it.400Kg/cm
2Under the pressure that this material rolling is online to circular steel, the thick 0.2mm of this steel mesh line, mesh size 0.2mm, radius 1.75cm.
Electro-chemical test
According to electrode sample of the present invention, be prepared as 0.5cm
2Square plate.Adopt cyclic voltammetry to test the oxidation of anode, test the reduction of negative electrode simultaneously tetracyanoethylene (TCNE) to ferrocene (FcH).All adopt under two kinds of situations and contain [NBu
4] [PF
6] (0.2M) CH
2Cl
2Solution is as supporting electrolyte.
Table 1 has been summed up from the Fe-Co-Ni of containing of the present invention and has been the anode of 1: 1: 1 mol ratio and contains the electrochemical results that the Ni negative electrode is obtained, and has also reported itself and the comparison of normally used known electrodes material in fuel cell.The electrochemical data that is provided only plays illustration purpose, does not limit the chemical property of catalyst of the present invention.
Table 1: different electrode material (CH
2Cl
2Solution; [NBu
4] [PF
6] the FcH one-electron oxidation on (0.2M) and the apparent electrode potential of TCNE single electron reduction (V, vs.SCE) and peak-to-peak separation (mV).
| Electrode | The FcH oxidation | The TCNE reduction | ||
| E o′ | ΔE p a | E o′ | ΔE p a | |
| Fe-Co-Ni-base anode anode Pt-Ru of the present invention bGraphite vitreous carbon Ni base of the present invention negative electrode Pr cNegative electrode graphite vitreous carbon | +0.41 +0.38 +0.39 +0.42 | 60 180 150 85 | +0.21 +0.21 +0.22 +0.23 | 60 133 152 65 |
aMeasure in 0.05nVs
-1 bIn fuel cell system
cIn fuel cell system
Because at room temperature the electrochemical reversibility of single electron process is shown as the peak-to-peak 59mV of being divided into, electrode clearly of the present invention can be used as the efficent electronic interchanger, and is better than the commercial Pt base electrode tested on this meaning.
Electrode test of the present invention under typical operation of fuel cells condition, for example, 2N H
2SO
4With 1N KOH, 25 ℃, CH
3The OH 1M and the saturation of the air.
Shown in Fig. 1-4, in acidity or alkaline solution, electrode material of the present invention show with the commercially available material investigated quite even be better than its high current density.
Fig. 2 and 3 shows the H by single scanning voltammetry record 2N respectively
2SO
4The polarization curve of different anodes and cathode material in the solution.
Under degassing aqueous conditions, carried out the comparison of individual features.Current characteristic meets the IUPAC stipulations.
Fig. 3 and 4 shows the corresponding polarization curve that writes down in KOH solution.
Electrode by Preparation of Catalyst of the present invention, preferred anodes is by the Fe that places on the conductive carrier material, the ternary of Co and Ni or binary bond form, negative electrode contains independent Ni or the Co that places on the conductive carrier material, can be used for single, breathe direct oxidation fuel cell (DOFC), preferred directly alcohol fuel battery (DAFC), more preferably direct methanol fuel cell (DMFC) certainly, or can be used for polymer electrolyte fuel cells known in the art (PEFC), (H under the normal temperature
2Being fuel) open circuit voltage (OCV) is high to 1.18V.Under the normal temperature and pressure in the catalyst of the present invention suitable melts combine can provide high to 300mW/cm
2Concrete power.Negative electrode of the present invention tolerates fully to alcohol, therefore the intersection alcohol among the DAFC is tolerated fully.Can use commercially available cation or anionic membrane equally.
As an example, Fig. 6 shows performance (the Ni-base negative electrode of a DMFC who is formed by electrode of the present invention; Fe-Co-Ni-base anode).
Claims (33)
1. nitrogen-oxygen-carbon polymer, by 4-{1-[(2,4-2 (replacement)-phenyl)-hydrazono-]-alkyl }-benzene-1,3-glycol and 3,5-disubstituted benzenes phenol and formaldehyde or paraformaldehyde contain under the situation of alkali (as NaOH) or acid (as HCL) catalyst at the water/alcohol mixture as solvent, and condensation makes under 20-150 ℃ temperature, and mean molecule quantity is 1000-50000.
2. polymer according to claim 1, wherein, described 4-{1-[(2,4-2 (replacement)-phenyl)-hydrazono-]-alkyl }-benzene-1, the 3-glycol is for having the compound of structural formula (A):
Wherein, R
1Be selected from hydrogen and alkyl with 1-10 carbon atom, but halogenation; R
2And R
3Independent respectively representative is selected from the electronics-acceptor groups of hydrogen, halogen, acyl group, ester, carboxylic acid, formoxyl, nitrile, semi-annular jade pendant acid, the straight or branched alkyl with 1-15 carbon atom or aromatic radical (can select with halogen functionalized or utilize phenyl ring to combine to form one or more condensed ring) and nitro.
3. according to the polymer of claim 1 and 2, wherein described 3,5-disubstituted benzenes phenol is for having the compound of structural formula (B):
R wherein
4And R
5Independent respectively representative is selected from hydrogen, hydroxyl, ether, amine, aromatic radical and has the electronic donor group of the straight or branched alkyl of 1-15 carbon atom.
4. according to the polymer of claim 1-3, have general formula (C):
Wherein, y can change between 2-120, and x can change between 1-2, and n can change between 1-3, R
1, R
2, R
3, R
4And R
5As defined above.
5. metal complex is made up of polymer and slaine according to claim 1-4.
6. according to the metal complex of claim 5; wherein; the slaine chosen from Fe-, cobalt-and nickel-carboxylate ,-halide ,-alcoholates ,-the pentanedione thing ,-formates ,-oxalates ,-malonate and similar organic salt and composition thereof, or be selected from carbonate, oxide and bicarbonate and composition thereof.
7. according to the complex compound of claim 6, be selected from Fe, Co and Ni acetate (and composition thereof).
8. the catalyst of forming according to the complex compound of claim 5-7, wherein, solid-state down in conjunction with H
2Or in the liquid solution system, adopt appropriate reductant that described metal is reduced processing.
9. the catalyst of forming according to the complex compound of claim 5-7, wherein, metal complex under inert gas shielding (as N
2, argon gas), at 500-1000 ℃, be preferably under 800 ℃ the temperature pyrolysis about 2 hours.
10. electrode (anode and negative electrode) is made up of according to Claim 8-9 catalyst and suitable conductive carrier.
11. anode is by according to Claim 8-9 and comprise the binary of Fe, Co and Ni or the catalyst of ternary bond and suitable conductive carrier and form.
12. negative electrode is by described and comprise the catalyst of Ni or Co and suitable conductive carrier is formed according to Claim 8-9.
13. method for preparing according to nitrogen-oxygen-carbon polymer of claim 1-4, wherein, described reaction is by 4-{1-[(2,4-2 (replacement)-phenyl)-hydrazono-]-alkyl }-benzene-1, the condensation under the situation that base catalyst exists of 3-glycol and 3,5-disubstituted benzenes phenol and formaldehyde or paraformaldehyde is finished.
14. according to the method for claim 13, wherein, described being reflected under the situation that acid catalyst exists finished.
15. according to the method for claim 13 and 14, wherein, the temperature range of reaction is about 150 ℃ of about 20-, pH value scope is about 1-about 14.
16. according to the method for claim 13-15, wherein, independent component 4-acyl group/formoxyl-benzene-1 is used in reaction, 3-glycol, 2-4 di-substituted-phenyl hydrazine, 3, and 5-disubstituted benzenes phenol and formaldehyde or one step of paraformaldehyde or multistep are finished.
17. a method for preparing according to the complex compound of claim 5-7 will be dissolved in the suitable solvent or solvent mixture according to polymer and one or more salt of claim 1-3, preferred acetone, and temperature range is about 20-about 60 ℃ and reduction products therefrom.
18. according to the method for claim 17, wherein, the metal salt mixture of use is selected from independent nickel (II), iron (II) and cobalt (II) salt or it has the binary or the ternary bond of preferred stoichiometric proportion.
19. according to the method for claim 18, wherein, metal filled amount account for all elements and weight metal and about 0.5% to 10%.
20. according to the method for claim 17-19, wherein, reduction step is 350-400 ℃ of following H
2Air-flow 1-2 hour.
21. according to the method for claim 17-19, wherein, reduction step is for to be scattered in a kind of solvent and water-based hydrazine solution or tetraphydro-borate [Y] BH with complex compound
4Solution, wherein Y is Li
+, Na
+, K
+, NR
+, PPN
+, R
4Such as claim 3 definition, PPN
+Be two (the positive phosphorus Ji Yaji of triphenyl) amine, temperature is 0 ℃-20 ℃, and the time is 30 minutes-1 hour.
22. a method for preparing according to Claim 8-9 catalyst, wherein, metal-doped polymer P-M under inert gas shielding (as N
2, argon gas), at 500-1000 ℃ of pyrolysis 1-2 hour.
23. the preparation method according to the fuel cell usefulness anode electrode of claim 10-11 before handling according to the reduction of claim 20-21, is in the same place metal-doped polymeric material and porous carbon carrier material or other conductive carrier material mixing.
24. according to the method for claim 23, wherein, the binary or the ternary bond that use independent nickel, iron and cobalt metal or its to have preferred stoichiometric proportion, metal filled amount account for all elements and weight metal and about 0.5% to 10%.
25. the fuel cell according to claim 10 and 12 preparation method of alcohol tolerance cathode electrode is included under the inert gas shielding (as N
2, argon gas), before the heat treatment of about 500 ℃-Yue 1000 ℃ of pyrolysis 1-2 hour, metal-doped polymeric material and porous carbon carrier material or other conductive carrier material mixing are in the same place.
26. according to the method for claim 25, wherein, metal-doped polymer comprises metal or metal mixture, wherein metal filled amount accounts for about 0.5% to 10% of carbon and weight metal summation.
27. direct oxidation fuel cell (DOFC) or direct alcohol fuel battery (DAFC) are used anode, are formed by the catalyzed carbon matrix that comprises chosen from Fe, cobalt and nickel metal according to claim 23-24.
28. direct oxidation fuel cell (DOFC) or direct alcohol fuel battery (DAFC) are formed by the nickeliferous catalyzed carbon matrix according to claim 25-26 with alcohol tolerance negative electrode.
29. direct oxidation fuel cell (DOFC) or directly alcohol fuel battery (DAFC) use anode, normal temperature and pressure can produce down height to the open circuit voltage (OCV) of 1.13V and height to 160mW/cm
2Power.
30. direct oxidation fuel cell (DOFC) or directly alcohol fuel battery (DAFC) use negative electrode, normal temperature and pressure can produce down height to the open circuit voltage (OCV) of 1.13V and height to 160mW/cm
2Power.
31.H
2The polymer electrolyte fuel cells that acts as a fuel (PEFC) is used anode, comprises iron, cobalt and nickel with preferred stoichiometric proportion, and total metal filled amount is 0.5-8wt%, can produce high to 1.18V open circuit voltage (OCV) and height to 300mW/cm
2Power.
32.H
2The polymer electrolyte fuel cells that acts as a fuel (PEFC) is used negative electrode, comprises the nickel that loading is 0.5-7wt%, can produce high to 1.18V open circuit voltage (OCV) and height to 300mW/cm
2Power.
33. fuel cell comprises the electrode according to claim 10-12 and 27-32.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT002229A ITMI20022229A1 (en) | 2002-10-21 | 2002-10-21 | COMPLEX COPOLYMER FOR METALS. |
| ITMI2002A002229 | 2002-10-21 | ||
| ITMI2002A002230 | 2002-10-21 |
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| Publication Number | Publication Date |
|---|---|
| CN1830108A true CN1830108A (en) | 2006-09-06 |
Family
ID=36947574
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA038244365A Pending CN1830108A (en) | 2002-10-21 | 2003-06-23 | Platinum-free electrocatalyst materials |
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| IT (1) | ITMI20022229A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102362382A (en) * | 2009-03-24 | 2012-02-22 | 大发工业株式会社 | Fuel cell |
| CN108963273A (en) * | 2018-06-27 | 2018-12-07 | 华南理工大学 | A kind of branch shape platinum elctro-catalyst and the preparation method and application thereof |
| CN113613783A (en) * | 2019-04-15 | 2021-11-05 | 日本瑞翁株式会社 | Catalyst, electrode, membrane electrode assembly, and air cell |
-
2002
- 2002-10-21 IT IT002229A patent/ITMI20022229A1/en unknown
-
2003
- 2003-06-23 CN CNA038244365A patent/CN1830108A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102362382A (en) * | 2009-03-24 | 2012-02-22 | 大发工业株式会社 | Fuel cell |
| CN108963273A (en) * | 2018-06-27 | 2018-12-07 | 华南理工大学 | A kind of branch shape platinum elctro-catalyst and the preparation method and application thereof |
| CN108963273B (en) * | 2018-06-27 | 2022-01-18 | 华南理工大学 | Branch-shaped platinum electrocatalyst and preparation method and application thereof |
| CN113613783A (en) * | 2019-04-15 | 2021-11-05 | 日本瑞翁株式会社 | Catalyst, electrode, membrane electrode assembly, and air cell |
| CN113613783B (en) * | 2019-04-15 | 2023-12-15 | 日本瑞翁株式会社 | Catalyst, electrode, membrane electrode assembly and air battery |
Also Published As
| Publication number | Publication date |
|---|---|
| ITMI20022229A1 (en) | 2004-04-22 |
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