P/METAL-N-C HYBRID CATALYST

Abstract

A P/Metal-NC hybrid catalyst that includes at least one nitrogen-doped carbonaceous matrix onto which at least one non-precious transition metal is covalently bonded and that includes at least one partially oxidised precious transition metal P of which the weight percentage is less than or equal to 4.0%, and preferably less than or equal to 2.0%, relative to the mass of the P/Metal-NC hybrid catalyst. Further, an electrochemical device that includes such a device, for example a fuel cell with a polymer electrolyte membrane.

Claims

1. A P/Metal-NC type hybrid catalyst which comprises at least one nitrogen-doped carbonaceous matrix on which is bonded in a covalent manner at least one non-precious transition metal, wherein it further comprises at least one precious transition metal P partially oxidized and whose weight percentage is lower than or equal to 4.0% with respect to the weight of the P/Metal-NC type hybrid catalyst.

2. The P/Metal-NC type hybrid catalyst according to claim 1, wherein the precious transition metal P is selected from ruthenium, rhodium, palladium, silver, gold, rhenium, osmium, iridium, platinum and cerium, considered alone or mixed with the latter or in the form of an alloy with at least one precious or non-precious transition metal.

3. The P/Metal-NC type hybrid catalyst according to claim 1, wherein the non-precious transition metal is selected from titanium, vanadium, chromium, manganese, nickel, copper, iron and cobalt, considered alone or mixed with the latter or in the form of an alloy of non-precious transition metals.

4. The P/Metal-NC type hybrid catalyst according to claim 1, wherein the precious transition metal P has an average oxidation state comprised between 0.5 and 4.0.

5. The P/Metal-NC type hybrid catalyst according to claim 1, wherein the weight percentage of the precious transition metal P is comprised between 0.1% and 4.0% with respect to the weight of the P/Metal-NC type hybrid catalyst.

6. The P/Metal-NC type hybrid catalyst according to claim 1, wherein the precious transition metal P is in the form of nanoparticles.

7. The P/Metal-NC type hybrid catalyst according to claim 6, wherein it comprises micropores and/or mesopores in which lie the nanoparticles of the precious transition metal P.

8. A P/Metal-NC type hybrid catalyst which can be obtained by a manufacturing method which comprises at least the following steps of: a) providing a Metal-NC type hybrid catalyst, b) impregnating the Metal-NC type hybrid catalyst with at least one solution of a salt of a precious transition metal P so as to obtain a homogenous mixture, c) performing at least one heat treatment on the homogenous mixture obtained at step b), the heat treatment consisting of a heating at a temperature comprised between 0 and 700 C., in an inert or reducing atmosphere so as to obtain a P/Metal-NC type hybrid catalyst in which the precious transition metal P is partially oxidized, the concentration of the solution of the salt of the precious transition metal P being selected in a determined manner such that the weight percentage of the precious transition metal P is lower than or equal to 4.0% with respect to the weight of the P/Metal-NC type hybrid catalyst obtained upon completion of step c).

9. An electrochemical device which comprises at least one P/Metal-NC type hybrid catalyst according to claim 1.

10. The electrochemical device according to claim 9, wherein it is selected from metal-air batteries, fuel cells operating at low temperature.

Description

[0098] The invention will be better understood from the detailed description which follows, with reference to the appended drawing representing, as a non-limiting example, the experimental results obtained from P/FeNC type hybrid catalysts according to the invention and compared with those obtained with catalysts of the related art.

[0099] FIG. 1 represents polarization curves of the dioxygen reduction at the rotating disk electrode for 6 catalysts.

[0100] FIG. 2 represents the kinetic portion of the curves presented in FIG. 1, after correction of the curves for the limitation due to the diffusion of dioxygen in an acid electrolyte, using the Koutecky-Levich equation.

[0101] FIG. 3 represents the polarization curves of the reduction (the current i being lower than 0) and of the oxidation (the current i being higher than 0) of hydrogen peroxide at the rotating disk electrode for 4 of the tested catalysts.

[0102] FIG. 4 represents the polarization curves of the reduction of protons into dihydrogen (the current i being lower than 0) and of the oxidation of dihydrogen into protons (the current i being higher than 0) at the rotating disk electrode for 4 of the tested catalysts.

[0103] FIG. 5 represents the polarization curves in PEMFC for 5 of the tested catalysts.

[0104] FIG. 6 represents the current density as a function of time with a PEMFC potential set to 0.5 V for 5 of the tested catalysts.

[0105] FIG. 7 represents the polarization curves, after correction in order to take into account the ohmic resistance of the membrane, and that after 50 hours of operation of the PEMFC at 0.5 V for 5 of the tested catalysts.

[0106] FIG. 8a represents the activity for the dioxygen reduction reaction at 0.8 V in cell, before and after 50 hours of operation of the PEMFC at 0.5 V for 5 of the tested catalysts.

[0107] FIG. 8b represents the current density as a function of time with a PEMFC potential set to 0.5 V for the tested catalyst E over a time period of 200 hours.

[0108] FIG. 8c represents the catalytic activity at a PEMFC potential set to 0.8 V for the tested catalyst E, before and after 200 hours of operation of the PEMFC at a potential of 0.5 V.

[0109] FIG. 9 represents the X-ray absorption spectra around the absorption threshold L.sub.3 of platinum of the catalysts C and E and of a platinum metallic sheet.

[0110] FIG. 10 represents an enlargement of the spectra of FIG. 9 around the absorption threshold L.sub.3 of platinum.

[0111] FIG. 11 is a graph of the Fourier transform of the X-ray absorption signal in fine structure (hereinafter abbreviated as EXAFS) of the platinum of the catalysts C and E according to the invention in comparison with the Fourier transform of the EXAFS signal of the platinum of the platinum metallic sheet.

[0112] FIG. 12 represents curves of an electrochemical detection test of carbon monoxide, a probe molecule well known for characterizing metallic platinum particles (platinum atoms having a zero oxidation state inside the particle); and the comparison of such curves before and after a 50 hour test in a PEMFC cell at 0.5 V carried out with the catalyst D.

[0113] FIG. 13 represents the X-ray absorption spectra around the absorption threshold L.sub.3 of platinum of the catalyst D, before and after a test in cell at 0.5 V for 50 hours.

[0114] The following experimentations have been carried out so as to compare the properties and the performances of three hybrid catalysts according to the invention with respect to those of precious transition metal based catalysts known in the related art.

[0115] The technical characteristics of the tested catalysts were as follows: [0116] catalyst A: FeNC type catalyst, namely a catalyst comprising a nitrogen-doped carbonaceous matrix and on which iron atoms are bonded in a covalent manner; [0117] catalyst B: the catalyst A which has been subjected to a heat treatment detailed hereinafter. This treatment had the effect of increasing the specific surface of the catalyst B with respect to that of the catalyst A. This catalyst B was the platinum-free FeNC reference catalyst; [0118] catalyst C: 1.sup.st catalyst according to the invention which has been obtained after post-functionalization of the catalyst A. The post-functionalization has consisted of the same heat treatment as that of the catalyst B but with the additional presence of a metallic platinum salt which has been reduced. The weight content of platinum in the catalyst C was 0.5% with respect to the total weight of the catalyst C; [0119] catalyst D: 2.sup.nd catalyst according to the invention which has been obtained after post-functionalization of the catalyst A. The post-functionalization has consisted of the same heat treatment as that of the catalyst B but with the additional presence of a platinum salt which has been partially reduced. The weight content of platinum in the catalyst D was 1.0% with respect to the total weight of the catalyst D; [0120] catalyst E: 3.sup.rd catalyst according to the invention which has been obtained after post-functionalization of the catalyst A. The post-functionalization has consisted of the same heat treatment as that of the catalyst B but with the additional presence of a platinum salt which has been partially reduced. The weight content of platinum in the catalyst E was 2.0% with respect to the total weight of the catalyst E; [0121] catalyst F: a Pt/C type commercial catalyst, namely a catalyst comprising a carbonaceous matrix and on which platinum nanoparticles have been synthesized. The weight percentage of platinum was 46% with respect to the total weight of the catalyst F. This catalyst is commercialized by the Japanese company Tanaka Kikinzoku.

[0122] The precursor of the FeNC type catalyst A has been manufactured in a planetary mill from: [0123] a crystalized porous hybrid solid comprising Zn(II) cations and methyl-imidazolate ligands, of formula ZnN.sub.4C.sub.8H.sub.12, commercialized by the company BASF under the commercial name Basolite Z1200, abbreviated hereinafter as ZIF-8, [0124] a Fe(II) salt, namely non-hydrated iron acetate, [0125] a second nitrogenous ligand for the Fe(II) ions, namely 1,10-phenanthroline.

[0126] The dry powders of ZIF-8, of iron salt and of phenanthroline have been weighted into the desired proportions and then deposited into a zirconium oxide crucible. The catalyst precursor before grinding contained 1 weight % of iron and the weight ratio of phenanthroline on ZIF-8 was 20/80. Afterwards, 100 balls of zirconium oxide with a diameter of 5 mm have been added into the crucible which has been sealed and disposed into a planetary mill commercialized by the company FRITSCH under the commercial name Pulverisette 7 Premium. 4 cycles of 30 minutes at a speed of 400 rpm have been performed in order to mix the powders. The catalyst A precursor obtained accordingly has been pyrolyzed at 1050 C. under argon for one hour so as to obtain the catalyst A.

[0127] The hybrid catalysts C to E according to the invention have been obtained in the following manner:

[0128] 300 mg of the catalyst A have been impregnated with a solution of a platinum salt, namely a platinum salt of formula [Pt(NH.sub.3).sub.4]Cl.sub.2*H.sub.2O with 99% purity, commercialized by the company INTERCHIM, which was dissolved in water.

[0129] To do so, for each of the catalysts C to E, a total of 550 L of the platinum salt solution has been poured, per portion of 100 L, on the catalyst powder, while pounding the mixture obtained accordingly with a mortar between each pour of 100 L. At the end of the impregnation, the obtained mixture presented a slightly muddy aspect which is characteristic of a complete filling of the pores of the FeNC type catalyst A by the platinum salt solution.

[0130] In order to obtain the contents by weight of the catalysts C to E detailed hereinabove, the concentration of the platinum salt solution has been appropriately adjusted.

[0131] The impregnated samples obtained accordingly have been dried in an oven under air for 2 hours at 80 C.

[0132] The powder that has been obtained upon completion of this drying has been disposed into a quartz nacelle which has in turn been placed into a quartz tube. The set has been introduced into a tubular furnace in order to undergo a heat treatment consisting of a heating for 2 hours at 560 C. in an atmosphere comprising a mixture of dihydrogen and dinitrogen (5% of dihydrogen and 95% of dinitrogen, expressed in molar percentages).

[0133] Afterwards, upon completion of the heat treatment, the powder has been cooled in a dinitrogen atmosphere.

[0134] The catalyst B has been prepared from a catalyst A which has not been impregnated with the platinum salt solution but has undergone this same heat treatment and this cooling step detailed hereinabove.

[0135] The specific surface of the catalysts A to E has been determined by dinitrogen adsorption and by analysis of the adsorption isotherm with the Brunauer-Emmett-Teller equation.

[0136] Table 1 hereinbelow details the specific surface of the catalysts A to E measured by dinitrogen adsorption, as well as the surface increase percentage of the catalysts B to E with respect to the surface of the catalyst A, in other words the increase percentage of the surface after the heat treatment detailed hereinabove.

TABLE-US-00001 TABLE 1 specific surface of the catalysts A to E and relative increase of the specific surface of the catalysts B to E after the heat treatment surface in % of surface catalyst m.sup.2/g increase A 370 0 B 520 40 C 560 51 D 530 43 E 550 49

[0137] As seen in Table 1, we note that the heat treatment has considerably increased the surface of the catalysts and that the amount of platinum has not had any great influence on the increase of the surface, as demonstrated by the catalyst B (without platinum). Thus, only the heat treatment under dihydrogen/dinitrogen has induced an increase of the surface of the catalysts.

[0138] Catalytic films comprising the catalysts A to E have been deposited over the rotating disk electrodes in the following manner:

[0139] A catalytic ink has been prepared with 10 mg of the concerned catalyst, 108 L of a Nafion solution (5 weight % of Nafion polymer scattered into an alcohols based solution) commercialized by the company DuPont, 300 L of ethanol with 99% purity commercialized by the company API France and 36 L of ultra-pure water. The catalytic ink has been homogenized in an ultrasonic bath for at least 30 minutes. Afterwards, 7 L of this ink have been deposited over a disk with a diameter of 5 mm made of glossy carbon so as to obtain a rotating disk electrode with a catalytic film whose catalyst load was 800 g/cm.sup.2.

[0140] For each of the tested electrodes, the catalyst total load was 800 g/cm.sup.2.

[0141] Hence, the platinum content at the electrode comprising: [0142] the catalyst C was 4 g/cm.sup.2 [0143] the catalyst D was 8 g/cm.sup.2 [0144] the catalyst E was 16 g/cm.sup.2.

[0145] As regards the electrode comprising the catalyst F, the platinum load at this electrode was 20 g/cm.sup.2. To do so, 1.4 mg of the catalyst F have been scattered into 3 mL of water by an ultrasonic treatment, and 20 L have been deposited onto a glassy carbon electrode tip and dried under air.

[0146] The electrochemical device comprising the rotating disk electrode further included: [0147] a glass cell, [0148] a pH1 acid electrolyte containing HClO.sub.4 at a concentration of 0.1 mol/L, [0149] a carbon counter-electrode, [0150] a hydrogen reference electrode (hereinafter abbreviated as HRE), constituted by a platinum wire immersed into a separate compartment and containing the same electrolyte but dihydrogen saturated, this compartment being connected in an electrolytic manner to the main compartment by a glass sinter, [0151] a potentiostat commercialized by the company Princeton Applied Research under the commercial name Versastat.

[0152] The experimental conditions of the device comprising the rotating disk electrode were as follows: [0153] ambient temperature, [0154] rotating speed of the electrode: 1600 rpm, [0155] 20 voltammetric cycles between 0.05 and 1.1 V relative to the HRE have been conducted in order to clean the rotating disk electrode.

[0156] Afterwards, the voltammetric cycles have been conducted between 0.2 and 1.0 VHRE at a scanning speed of 10 mV/s in the dinitrogen-saturated electrolyte, then in dioxygen, and the curves measured under dinitrogen have been subtracted from those measured under dioxygen, in order to eliminate the non-faradic currents (that is to say the currents not related to the dioxygen reduction, such as the capacitive current). In addition, the curves have been corrected for the ohmic drop in the electrolyte (a resistance of about 20 Ohms for this device).

[0157] In FIG. 1 are represented the polarization curves of the reduction of dioxygen obtained from a rotating disk electrode, and that with the tested catalysts A to F.

[0158] The curves of FIG. 1 indicate that the best catalyst for the reduction of dioxygen is the catalyst F. Indeed, the kinetics of the oxygen reduction reaction is shown around 0.9-1.0 V.sub.HRE.

[0159] At a lower potential, the curve of the catalyst F shows a plateau in current which is not related to the electrochemical kinetics of the dioxygen reduction, but defined by:

[0160] i) the maximum possible diffusion flow of the dioxygen dissolved in the electrolyte toward the electrode (this depends on the rotating speed of the electrode) and by

[0161] ii) the selectivity of the catalyst for the dioxygen reduction reaction (the reduction of dioxygen essentially into water, but also the reduction of a few percentages of dioxygen molecules into peroxide instead of water).

[0162] The catalyst A has a kinetic portion of its polarization curve for the oxygen reduction reaction which is shifted toward the more negative potentials, at about 150 mV. This means less rapid kinetics. Nonetheless, the diffusion limit current at low potential is close to that of the catalyst F thereby indicating that the product of the dioxygen reduction reaction on the catalyst A is essentially water.

[0163] The catalyst B corresponds to the catalyst A which has been subjected to a heat treatment; which has resulted in increasing its surface. The activity of the catalyst B is higher by about 50 mV than that of the catalyst A and lower by about 100 mV than that of the catalyst F. The kinetic regime of the curves is located between 0 and 2 mA/cm.sup.2. Its diffusion limit current is equal to that of the catalyst F thereby indicating a reduction of dioxygen into water essentially.

[0164] Considering the almost superimposition of the portions of the curves of the catalysts B to E between 0 and 2 mA/cm.sup.2 (namely the kinetic regime), the three hybrid catalysts C to E according to the invention have an activity for the dioxygen reduction reaction which is almost identical to that of the reference catalyst B.

[0165] This reflects that the dioxygen reduction reaction catalysis function of the catalysts C to E according to the invention lies only in the catalytic surface of the FeNC catalyst, obtained with the heat treatment, and not in the platinum salt that has been added before the implementation of the heat treatment.

[0166] Table 2 hereinbelow details for the catalysts A to E the activities per weight of catalyst at different potentials (namely at 0.8 V.sub.HRE, 0.85 V.sub.HRE and 0.9 V.sub.HRE).

TABLE-US-00002 TABLE 2 detailing the activities per weight of the catalysts at different potentials catalyst 0.8 V.sub.HRE 0.85 V.sub.HRE 0.9 V.sub.HRE A 2.3 0.5 0.1 B 6.5 1.3 0.3 C 9.2 1.8 0.3 D 6.6 1.9 0.4 E 7.7 1.5 0.3

[0167] As seen in Table 2, by comparing the activities of the catalyst A with those of the catalysts B to E, we note that the heat treatment has had the effect of increasing 3 to 4 times the activity of the catalyst. This increase of the activity of the catalyst is to be correlated with the increase of the surface of the catalyst subsequently to the heat treatment mentioned hereinabove with the results of Table 1.

[0168] FIG. 2 represents the kinetic portion of the curves represented in FIG. 1, after correction of the curves so as to correct the limitation due to the diffusion of dioxygen, and that using the Koutecky-Levich equation.

[0169] The kinetics of the dioxygen reaction are determined by an exponential law between the current and the electrochemical potential, that is to say a line in on a semi-logarithmic scale E.sub.HRE vs log(i).

[0170] FIG. 2 shows that: [0171] the slopes of the curves are similar: which means that the mechanism of the dioxygen reduction reaction is similar for the different catalysts, but [0172] the kinetics are different: the activity of the dioxygen reduction reaction can be quantified by collecting the current density at a given electrochemical potential, for example at 0.9 V vs HRE: about 6 mA/cm.sup.2 for the catalyst F, 0.2 mA/cm.sup.2 for the catalyst B and between 0.2 and 0.3 mA/cm.sup.2 for the catalysts C to E.

[0173] This accurate quantification of the activity of the dioxygen reduction reaction allows demonstrating that platinum in the catalysts C to E according to the invention is not active for the dioxygen reduction reaction. Indeed, there is no significant increase of the activity of the catalyst C to E according to the invention with respect to that of the reference catalyst B.

[0174] Yet, despite the low weight content of platinum (namely: 0.5, 1 or 2%) in the catalysts C to E according to the invention, if the structure of the platinum particles in the catalysts according to the invention C to E was the same as that in the catalyst F (namely metallic platinum nanoparticles with a zero oxidation state), an increase of the activity of the catalysts C to E according to the invention with respect to that of said catalyst B would have been observed.

[0175] Indeed, the electrode comprising the catalyst F contains 20 g of platinum per cm.sup.2 and the electrode comprising the catalyst E contains an almost equivalent content of platinum, namely 16 g/cm.sup.2, and this considering that the size of the platinum nanoparticles in these two catalysts is similar, a similar activity of the dioxygen reduction reaction would have been observed between these two catalysts E and F. Yet, this has not been the case.

[0176] This reflects that the platinum contained in the hybrid catalysts C to E according to the invention is not therefore active for the dioxygen reduction reaction. Its structure is different from that of the metallic platinum contained in the catalyst F.

[0177] With this same experimental technique of the rotating disk electrode implementing the catalysts detailed hereinabove, the kinetics of the hydrogen peroxide reduction reaction have been studied.

[0178] FIG. 3 represents the polarization curves of the hydrogen peroxide reduction at the rotating disk electrode.

[0179] In these experimentations, the experimental conditions of the device comprising the rotating disk electrode were as follows: [0180] pH 1 acid electrolyte containing HClO4 at a concentration of 0.1 mol/L dinitrogen-saturated and with a concentration of 3 mmol/L of hydrogen peroxide, [0181] ambient temperature, [0182] rotating speed of the electrode: 1600 rpm.

[0183] As seen in the curves of FIG. 3, it is observed that the catalyst F is very active: [0184] for the electrochemical reduction reaction of hydrogen peroxide into water, and this considering the negative currents, as well as [0185] for the electrochemical oxidation of the hydrogen peroxide into dioxygen, and this considering the positive currents,

[0186] with a zero-current potential of 0.9-0.95 V vs HRE, which is characteristic of a reduced platinum surface.

[0187] Conversely, the catalysts A, B and D are barely active for the hydrogen peroxide reduction and oxidation reactions. This is characteristic of the catalysts whose active sites are iron-based.

[0188] Thus, the curves of FIG. 3 also clearly reflect that the platinum structures that the catalysts according to the invention comprise do not consist of metallic platinum as that of the catalyst F. The platinum present in the catalysts according to the invention does not contribute to the electrochemical reduction of small amounts of hydrogen peroxide produced during the dioxygen reduction reaction.

[0189] Afterwards, a 3.sup.rd catalytic function of the platinum present in the catalysts according to the invention has been studied, namely the electrochemical oxidation of dihydrogen. Indeed, in a PEMFC, a low flow of dihydrogen passes through the fine polymer membrane separating the anode and the cathode. Dihydrogen that has diffused through the membrane may chemically react with the dioxygen of the cathode so as to form extremely oxidant radical species such as .sup.OH and .sup.OOH. These radical species may attack the membrane or the catalyst.

[0190] This is why, using the same rotating disk electrode experimental technique, the kinetics of oxidation of dihydrogen into protons H.sup.+, and of reduction of protons H.sup.+ into dihydrogen has been studied.

[0191] FIG. 4 represents the polarization curves of the protons reduction and dihydrogen oxidation at the rotating disk electrode.

[0192] The experimental conditions of the device comprising the rotating disk electrode were as follows: [0193] a pH 1 dihydrogen-saturated acid electrolyte containing HClO.sub.4 at a concentration of 0.1 mol/L, [0194] ambient temperature, [0195] rotating speed of the electrode: 1600 rpm.

[0196] As seen in the curves of FIG. 4, we note that: [0197] when using a catalyst F at the cathode, the small amount of dihydrogen that arrives from the anode to the cathode by diffusion through the membrane is immediately electro-oxidized into protons; [0198] the catalyst A is completely inactive for this reaction (cf. the curve A in FIG. 4). This catalyst rather promotes a chemical reaction between dihydrogen and dioxygen for forming free radicals.

[0199] In FIG. 4, we note that the curve of the catalyst E according to the invention is almost superimposed with the theoretical curve (cf. the calculated curve) corresponding to infinite kinetics of the dihydrogen oxidation, meaning that the sole experimentally observable loss is due to the diffusion of the dihydrogen dissolved in the electrolyte toward the electrode, the kinetics being much faster than the diffusion that the kinetics cannot therefore be quantified by this experimental method.

[0200] The curves of FIG. 4 reflect that the platinum structures in the hybrid catalysts according to the invention are active for the dihydrogen oxidation reaction, and this considering the positive currents of FIG. 4, but also for the reduction of the protons into dihydrogen, and this considering the negative currents of FIG. 4.

[0201] As seen in FIG. 4, the catalyst A is completely inactive for the dihydrogen reduction and protons oxidation reactions. This inactivity toward dihydrogen and protons is a known property for the family of FeNC and CoNC type catalysts.

[0202] The hybrid catalysts C to E according to the invention show a proportional increase of their catalytic activity for dihydrogen and protons H.sup.+ with the increase of the platinum content. This may be related to the better stabilization observed in PEFMC of the catalysts D and E according to the invention whose weight content of platinum is 1% and 2% respectively. Indeed, the catalysts A to E have also been tested in PEMFCs. This better stabilization is detailed hereinafter.

[0203] The initial polarization curves in PEMFC of the anode-membrane-cathode assemblies in which only the catalyst of the cathode (namely the tested catalysts A to E) vary are represented in FIG. 5.

[0204] The curves show the electric potential difference cathode less anode of the PEMFC as a function of the current density, and this after correction in order to take into account the ohmic resistance of the membrane.

[0205] Cathode catalytic inks have been prepared by mixing 20 mg of the concerned catalyst, 652 L of a solution of 5 weight % of Nafion containing 15-20 weight % of water, 326 L of ethanol and 272 L of deionized water. The inks have been homogenized by subjecting them alternately to ultrasounds and to a mechanical stirring in a vortex stirrer every 15 minutes, and this for a total time period of one hour.

[0206] Afterwards, 405 L of catalyst ink have been successively deposited over a microporous later of a carbon tissue with a surface of 4.84 cm.sup.2 commercialized by the company SGL Group The Carbon Company under the commercial name SIGRACET S10-BC so as to obtain a cathode comprising a catalyst load of 4 mg/cm.sup.2.

[0207] The cathode has been disposed in a vacuum oven at 90 C. for one hour in order to be dried.

[0208] The anode contained a Pt/C type commercial catalyst whose platinum load was 0.5 mg/cm.sup.2, pre-deposited over a microporous layer of the same carbon tissue, namely Sigracet S10-BC.

[0209] The anode-membrane-cathode assembly has been prepared by hot pressing at 135 C. for 2 minutes 4.48 cm.sup.2 of the anode and of the cathode on either side of a membrane commercialized by the company DuPont under the commercial name Nafion NRE-211.

[0210] The experimentations with the PEMFCs have been carried out in a commercial single-cell fuel cell comprising gas distribution channels in the form of a serpentine (the Fuel Cell Technologies company), using a PEMFC test bench within the laboratory, and by controlling the electric potential of the cell and the current produced with a commercial potentiostat of the company Biologic, coupled to a 50 A amplifier of the same company.

[0211] The experimental conditions were as follows: [0212] cell temperature: 80 C., [0213] gas: dihydrogen and dioxygen humidified to 100% at a temperature of 85 C., [0214] relative pressure of the gases of 1 bar at the inlet of the anode and of the cathode, [0215] gas flow of 50-70 cm.sup.3/minute for the humidified dioxygen and dihydrogen, [0216] the polarization curves have been recorded at a scanning speed of 0.5 mV.Math.s.sup.1.

[0217] As seen in FIG. 5, we note that the initial polarization curves for the catalysts B to E are almost identical. Indeed, the small differences are due to the reproducibility error in the synthesis of the catalysts and/or in the preparation of the anode-membrane-cathode assembly.

[0218] Initially, the catalysts B to E are more performant than the catalyst A, the initial current density at 0.5 V of the catalysts B to E being higher than that of the catalyst A by about 150 mA/cm.sup.2. This is explained by the fact that the catalysts B to E have undergone a heat treatment. Thus, this reflects the effect of the heat treatment on the Metal-NC type catalysts.

[0219] In order to test the mid-term stability of the hybrid catalysts C to E according to the invention for the dioxygen reduction reaction at the cathode, the potential difference of the PEMFC has been set to 0.5 V an the current density has been measured over 50 hours. This time period is sufficient to observe a decrease of the performances of the reference FeNC catalyst, that is to say the catalyst B.

[0220] FIG. 6 represents the current density as a function of time for a PEMFC potential set to 0.5 V for 50 hours.

[0221] As seen in FIG. 6, we note that, in a reproducible manner, the FeNC catalysts (catalysts A and B), are active during the first hours of operation of the PEFMC, and then exhibit a continuous degradation of the performances over time (about 20-25% of current loss with respect to the maximum observed after 3-6 hours).

[0222] The addition of platinum does not increase the initial performance at 0.5 V but stabilizes the hybrid catalysts (slighter slope for the hybrid catalyst C and no slope observable over 50 hours with the hybrid catalysts D and E according to the invention).

[0223] This shows that the platinum particles in the hybrid catalysts according to the invention should be advantageously present at a content high enough to effectively stabilize the Metal-NC catalyst. The hybrid catalyst C according to the invention is not completely stable because of the low platinum content (namely 0.5%). This may be related to a much large average distance between any iron-based catalytic site and the closest platinum particle in this hybrid catalyst.

[0224] FIG. 7 represents the polarization curves corrected by taking into account the ohmic resistance of the membrane, measured after 50 hours of operation at 0.5 V of the PEMFC.

[0225] As seen in FIG. 7, we note that at a low electric potential, the polarization curves corresponding to the catalysts D and E are better after the 50 hour test than before the 50 hour test. This is due to an improvement of the transport properties of the species (dioxygen, water, protons) in the cathode, whereas the catalytic activity at 0.8 V is not or is barely modified as reflected by FIG. 8 described hereinafter.

[0226] FIG. 8a represents the activity for the dioxygen reduction reaction at 0.8 V in PEMFC, before and after the 50 hour test.

[0227] Considering the reproducibility error in the measurements, the initial activities of the dioxygen reduction reaction for the catalysts B to E are almost identical.

[0228] In addition, we note that, for each catalyst, the final activity of the dioxygen reduction reaction is more and more close to the initial activity as the platinum content of the hybrid catalysts C to E increases. This reflects that the low platinum content that the hybrid catalysts according to the invention comprise has the effect of stabilizing their non-precious transition metal based active sites.

[0229] FIG. 8b represents the current density (i) as a function of time (expressed in hours) with a PEMFC potential set to 0.5 V for the catalyst E tested over a time period of 200 hours. FIG. 8b shows that the stabilization observed over 50 hours (FIG. 6) is also effective over longer time periods such as 200 hours. As seen in the curve of FIG. 8b and the curve E of FIG. 6, we note that the final performance at 0.5 V is also similar to that observed after the 50 hour test.

[0230] FIG. 8c represents the catalytic activity with a PEMFC potential set to 0.8 V (current density divided by the total load of the P/Metal-NC type catalyst E) for the tested catalyst E, before and after 200 hours of operation of the PEMFC. Given the uncertainty of the electrochemical activity measurement (in the range of more or less 20%), we note that the initial activity and the final activity are very similar. This demonstrates that the partially oxidized platinum in the catalyst according to the invention can stabilize the FeNC catalyst in the long run, and also demonstrates that the platinum has not been reduced (activated) during the test at 0.5 V. On the contrary, a significant increase of the activity would have been observed after 200 hours, which is not the case.

[0231] FIG. 9 represents X-ray absorption spectra around the absorption threshold L.sub.3 of platinum at 11562 eV (known as XANES, standing for X-ray Absorption Near Edge Structure) of the platinum atoms of the hybrid catalysts C and E according to the invention in comparison with the XANES spectrum around the absorption threshold L.sub.3 of the platinum of a platinum metallic sheet in which the platinum atoms are in a metallic form. FIG. 9 represents the XANES spectra a few eV below the threshold L.sub.3 of platinum up to 50 eV above this threshold.

[0232] In the platinum metallic sheet, the platinum atoms have a zero oxidation state and have a face-centered cubic crystalline structure (namely each platinum atom has 12 neighboring platinum atoms). The XANES spectrum of the metallic platinum nanoparticles of a platinum structure present in the platinum-based non-hybrid catalysts or in the Pt/Metal-NC type hybrid catalysts of the related art is very similar to that of a platinum metallic sheet.

[0233] FIG. 10 represents an enlargement of the spectra of FIG. 9 at the absorption threshold L.sub.3 of platinum, namely at 11562 eV.

[0234] The XANES portion of the absorption spectrum is characteristic of the local order around the X-ray absorber atom, herein platinum. Hence, according to FIGS. 9 and 10, the atom type and the number of atoms around the platinum atoms are fundamentally different between the hybrid catalyst according to the invention and the catalysts of the related art.

[0235] Considering the differences in the spectra of platinum between the catalysts according to the invention and the platinum metallic sheet, we note that the platinum that the catalysts according to the invention comprise has not a platinum structure in a metallic form (namely a face-centered cubic structure). In particular, between 11562 and 11565 eV, we note that the spectra of the catalysts according to the invention are positively shifted by 0.5-1.0 eV relative to the spectrum of the platinum metallic sheet. This positive shift by 0.5-1.0 eV relative to the platinum metallic sheet corresponds to an average oxidation state between 1.1 and 2.3 of the platinum atoms located in the Pt/FeNC type hybrid catalysts according to the invention.

[0236] Thus, the average oxidation state of the platinum atoms of the hybrid catalysts according to the invention is not equal to zero as is the case for the platinum of the platinum metallic sheet. Hence, the platinum salt precursor has not been completely reduced during the manufacture of the catalyst according to the invention, that is to say during the heat treatment under a dihydrogen and dinitrogen gaseous mixture.

[0237] FIG. 11 is a graph of the Fourier transform of the X-ray absorption spectroscopy experimentations in fine structure (namely experimentations abbreviated hereinafter as EXAFS, standing for Extended X-ray Absorption Fine Structure) of the platinum of the hybrid catalysts C and E according to the invention in comparison with the Fourier transform of the EXAFS signal for the platinum of the platinum metallic sheet.

[0238] This analysis allows plotting the amplitude of the EXAFS signal (k.sup.2.sub.(R)), which depends on the average number of neighboring atoms around each platinum atom, as a function of the distance between the absorber platinum atom and the neighboring atoms.

[0239] FIG. 11 shows that the structure at a long distance around the platinum atoms of the hybrid catalysts of the invention is also very different from that of the platinum atoms in a metallic face-centered cubic structure.

[0240] Indeed, as seen in FIG. 11, we note that the coordination number of the platinum of the catalysts according to the invention is lower than that of the platinum of the platinum metallic sheet.

[0241] The EXAFS signal observed at a radial distance of 2.5 Angstrom, a distance corresponding to the platinum atoms the closest to a given platinum atom, is actually lower for the platinum of the catalysts according to the invention than for the metallic platinum with a face-centered cubic structure of the platinum metallic sheet. This shows that the coordination number of the platinum by other platinum atoms is much smaller in the catalysts of the invention than in the platinum face-centered cubic structure whose coordination number is 12.

[0242] In addition, the EXAFS signal observed at 1.5 for the Pt/FeNC type hybrid catalysts according to the invention may be attributed to platinum-carbon platinum-nitrogen bonds, namely bonds which are absent in the face-centered cubic structure of the platinum of the platinum metallic sheet.

[0243] FIG. 12 represents curves of an electrochemical detection test of carbon monoxide. The carbon monoxide is a molecule known for characterizing metallic platinum particles (platinum atoms having a zero oxidation state inside the particle). Conventionally, carbon monoxide is used in the electrochemical field in order to quantify the surface of reduced platinum based catalysts.

[0244] The carbon monoxide is first injected in the cell system in the form of gas at the cathode. The carbon monoxide molecule adsorbs strongly onto the reduced platinum surface, thereby covering its entire surface with one layer. Afterwards, the excess non-adsorbed carbon monoxide gas is purged away from the cathode with an inert gas which is dinitrogen. Only this one later of carbon monoxide adsorbed onto the reduced platinum remains present in the cathode (the potential of the cathode is controlled around 0 V during this time, in order to avoid any premature oxidation of the carbon monoxide).

[0245] Afterwards, the amount of adsorbed carbon monoxide is quantified by electrochemically desorbing the carbon monoxide (electrochemical oxidation of the carbon monoxide which then desorbs in an oxidized form), by progressively increasing the electrochemical potential of the cathode from 0 to 1 V.

[0246] The electric charge corresponding to the surface area below the carbon monoxide oxidation peak in the voltammogram is directly proportional to the amount of adsorbed carbon monoxide, and therefore to the surface area of the reduced platinum in the catalyst. The position of this carbon monoxide oxidation peak is at about 0.8 V vs. a hydrogen reference electrode.

[0247] FIG. 12 shows the comparison of the curves before and after a 50 hour test in PEMFC at 0.5 V carried out with the catalyst D.

[0248] More specifically, in FIG. 12: [0249] the curve entitled initial represents the voltammogram determined after injection of carbon monoxide, and then dinitrogen at the cathode; [0250] the curve entitled blank represents the voltammogram determined after injection of dinitrogen alone (and therefore without any injection of carbon monoxide); [0251] the curve entitled after 50 hours represents the voltammogram determined after injection of carbon monoxide, dinitrogen at the cathode, and then the performance of a 50 hour functional test in PEMFC at 0.5 V.

[0252] FIG. 12 shows no signal corresponding to the electrochemical oxidation of carbon monoxide for the catalyst D, neither before nor after the 50 hour test in the cell. Indeed, the curve entitled initial is totally superimposes with the curve entitled blank. This demonstrates that no carbon monoxide molecule has adsorbed onto the platinum of the hybrid catalyst according to the invention. This is unexpected and is explained by the different structure of the platinum particles and by the different condition of their surface in the catalyst according to the invention. This is also correlated with the inactivity of platinum for the dioxygen reduction.

[0253] FIG. 12 shows the absence of carbon monoxide adsorption onto the platinum present in the catalyst D. The absence of any oxidation peak (that is to say the oxidation of the carbon monoxide potentially adsorbed onto platinum, which is reflected by a positive current peak during the increase of the electrochemical potential from 0 to 1 V) demonstrates that the platinum is initially incapable of adsorbing the carbon monoxide. This is explained by the partially oxidized state of the platinum in the catalyst according to the invention. After 50 hours of operation in the cell at 0.5 V, the platinum is still incapable of adsorbing the carbon monoxide, thereby demonstrating that the platinum has not been reduced during the test in the cell.

[0254] FIG. 13 represents X-ray absorption spectra around the absorption threshold L.sub.3 of platinum at 11562 eV of the platinum atoms of the catalyst D (that is to say the XANES spectra), before and after a test in the cell at 0.5 V for 50 hours. The superimposition of the spectra shows that the coordination and the average oxidation state of the platinum in the catalyst D has not changed during the test in the cell. Hence, the platinum is inactive for the oxygen reduction reaction throughout the test, but it stabilizes the catalytic sites of the FeNxCy type iron.