TW201131873A - Catalyst for direct liquid fuel cell, and fuel cell using the catalyst - Google Patents

Abstract

Disclosed is a low-cost high-performance catalyst for a direct liquid fuel cell, which is capable of suppressing decrease in the cathode potential due to crossover of liquid fuel in a direct liquid fuel cell wherein liquid fuel such as methanol, ethanol, formic acid, 2-propanol or dimethyl ether is directly supplied. The catalyst for a direct liquid fuel cell is characterized by being composed of a metal oxycarbonitride that contains niobium and/or titanium. It is preferable that the catalyst for a direct liquid fuel cell is inert to oxidation of the liquid fuel.

Description

201131873 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a fuel cell using a direct liquid fuel medium. [Prior Art] The direct liquid fuel electric material using methanol, ethanol, formic acid, 2-propanol and dimethyl as a direct fuel is easy to handle, and therefore it is expected to be used for portable use and mobile moon. The direct liquid fuel cell has, for example, a structure in which a single electrolyte membrane is held by an anode (anode; fuel electrode) and an anode; j pole. By supplying oxygen to the anode directly from the anode, the liquid fuel is oxidized at the anode, and electric energy can be taken out outside the cathode. However, in the direct liquid fuel cell, the efficiency of the liquid drop conversion in the cathode is lowered, and the efficiency of the potential drop conversion in the cathode is remarkably lowered. The liquid fuel burns through the polymer electrolyte membrane, and the liquid fuel that moves from the anode to the cathode has a problem that the potential of the cathode is lowered at the surface of the cathode catalyst. In general, it is used as a direct liquid fuel for platinum or a platinum alloy catalyst. Platinum catalyst or platinum is also highly stable at the same time. However, the catalyst for platinum catalyst or platinum pool and the liquid fuel such as the catenyl ether are simple in structure or high in electrical conductivity of the power source and the dispersed power source. § (cathode; air liquid fuel, which is reduced at the cathode oxygen, The penetration of the fuel is low, and the penetration of the energy of the battery indicates the phenomenon of the liquid to the cathode. The cathode is oxidized, so the cathode catalyst is used, so that the catalyst is a highly active catalyst for the oxygen -5-201131873 Not only the high catalytic activity is exhibited, but also the oxidation reaction of the above liquid fuel exhibits high catalytic activity, so that the oxidation reaction of the liquid fuel which reaches the cathode by permeation is also promoted. As a result, the oxygen reduction potential and the liquid in the cathode Since the oxidation potential of the fuel forms a mixed potential, it is remarkably lowered. Further, since the direct liquid fuel cell suppresses the reaction in the anode and suppresses the potential drop in the cathode by the penetration of the fuel, it is used in comparison with a fuel cell using hydrogen. A large amount of platinum catalyst. However, platinum is expensive and resources are limited, so the development of catalysts for direct liquid fuel cells can be replaced. In order to suppress the penetration of the liquid fuel in the direct liquid fuel cell, an electrolyte membrane which does not cause permeation of a liquid fuel through a small electrolyte membrane or a liquid fuel has been developed (for example, refer to Patent Documents 1 to 3). In the electrolyte membranes described in Patent Documents 1 to 3, it is extremely difficult to greatly reduce the permeation system of the liquid fuel while maintaining high ion conductivity and stability. Further, even if an electrolyte membrane that suppresses the permeation of a certain amount of liquid fuel is used, In the electrolyte membrane, the penetration of the liquid and the penetration of the liquid fuel are small, but it still occurs, so the potential drop in the cathode cannot be avoided. On the other hand, the liquid fuel that reaches the cathode by permeation is not oxidized, and only the selection is made. The catalyst for the oxygen reduction is also disclosed (for example, refer to Patent Document 4 and Non-Patent Documents 1 to 4). However, the catalyst disclosed in Patent Document 4 and Non-Patent Documents 3 to 3 uses a large amount of expensive palladium. The precious metal of bismuth is economically disadvantageous. The catalyst disclosed in Non-Patent Document 4 is not economical but uses a catalyst as a catalyst. There is a problem in that the use of a catalyst for a direct liquid fuel cell which is cheaper and has a higher performance is strongly demanded. Patent Document 5 discloses that although the catalyst is disclosed in the patent document 5 An inexpensive chromium (Zr)-based oxide is used, but practically sufficient oxygen reduction energy cannot be obtained as a catalyst. Non-patent document 5 discloses that ZrOxNy compound having chromium as a base exhibits oxygen reduction energy. Patent Document 6 discloses The platinum substitute material contains an oxygen-reducing electrode material of a nitride selected from the group consisting of elements of Groups 4, 5, and 14 of the long-period table. However, these materials containing non-metals are practically unusable as a catalyst. A problem of sufficient oxygen reduction energy is obtained. Further, Patent Document 7 discloses a carbonitride oxide in which a mixed carbide, an oxide, or a nitride is heated at 500 to 150 CTC in a vacuum, inert or non-oxidizing atmosphere. However, the carbon oxynitride disclosed in Patent Document 7 is a thin film magnetic head ceramic substrate material, and there is no review on the use of the carbon oxynitride as a catalyst. Moreover, platinum is not only used as a catalyst for the fuel cell, but also It is useful as a catalyst for exhaust gas treatment or a catalyst for organic synthesis, but the price is high and the amount of resources is limited. Therefore, development of a catalyst that can be substituted for these uses is expected. [Patent Document 1] [Patent Document 1] JP-A-2002-257453 [Patent Document 2] JP-A-2002-257453 [Patent Document 2] JP-A-2003-257453 [Patent Document 5] International Publication No. 07-072665 [Patent Document 6] JP-A-2007-31781 (Patent Document 7) JP-A-2003-342058 Patent Literature] [Non-Patent Document 1] K. Lee, O. Savadogo, A. Ishihara, S. M it su sh ima, N. Kam iya, K. O ta, "Methanol-Tolerant Oxygen Reduction Electrocatalysts Based on Pd- 3 d Transition Metal Alloys for Direct Methanol Fuel Cells j , Journal of The Electrochemical Society, 2006, 153(1), A20-A24 [Non-Patent Document 2] K. Lee, L. Zhang, J. Zhang, "A novel Methanol-tolerant Ir-Sechalcogenide electrocatalyst for oxygen reduction", Journal of Power Sources, 2007, 165(1), 108-113 [Non-Patent Document 3] K. Lee, L. Zhang, J_Zhang, "IrxC 〇bX(x =0.3 -1.0)alloy electrocatalysts,catalytic activities, and m Ethanol tolerance in oxygen reduction reaction"

Journal of Power Sources ' 2007, 170(10), 2 9 1 -296 [Non-Patent Document 4] Y.Liu, A.Ishihara, S.Mitsushima, N.Kamiya, K.Ota, "Transition Metal Oxides as DMFC Cathodes

Without Platinum", Journal of The Electrochemical Society' 201131873 2007, 154(7), B664-B669 [Non-Patent Document 5] S. Doi, A. Ishihara, N. kamiya, and K. Ota, "Z irc ο Nium - B ased

Cathode of Polymer Electrolyte Fuel Cell The Electrochemical Society '2007, B369 【Explanation】 The object of the invention is as described above, platinum catalyst or uranium alloy catalyst promotes annual acid, 2-propanol and dimethyl ether It is very difficult to suppress the reduction of the liquid fuel by the oxidation of the liquid fuel. The present invention provides a direct liquid fuel cell for directly supplying a liquid fuel such as methanol, hexyl alcohol and dimethyl ether, and a cathode having a high potential for providing a high liquid crystal fuel. catalyst. The present inventors have attempted to solve the above problems of the prior art. When a direct liquid fuel cell using tantalum and/or a metal oxycarbonitride of titanium is used, it is possible to suppress a decrease in cathode potential caused by a liquid, and it is inexpensive to have Shoulder. The present invention is, for example, the following (1) to (14). j.Mitsushima, Compounds for ”, Journal of 154(3), B362- high performance of alcohol, ethanol, and ketone, cathode potential, formic acid, 2·C battery, which can be low, can be cheaply reviewed, detailed review The performance of the osmotic fuel of the catalyst is completed. -9- (1) 201131873 A catalyst for a direct liquid fuel cell made of a metal oxycarbonitride containing cerium and/or titanium. (2) The catalyst for direct liquid fuel cells (3) characterized by being inert to the oxidation of liquid fuel (3) is oxidized by a metal carbonitride containing at least one metal M1 other than cerium and lanthanum. The catalyst for direct liquid fuel cells described in (1) or (2) is characterized by the object. (4) The content is selected from the group consisting of tin, indium, giant, chromium, copper, iron, tungsten, chromium, molybdenum, nitrile, titanium, vanadium, cobalt, lanthanum, cerium, mercury, cerium, IZ, lanthanum, cerium, lanthanum,至少, 钹, 巨, 钐, 铕, 乱, 铽, 镝, 鈥, bait, surface, mirror, distillation and nickel are grouped by at least one metal Ml and yttrium metal oxycarbon oxides. The catalyst for a direct liquid fuel cell according to (1) or (2). (5) The composition formula of the above metal oxycarbonitride is NbaMlbCxNyOz (however, a, b, X, y, z are represented by atomic ratio, 〇〇1$a<1, 〇<b$〇99, 0.01 Helmets x$2, 0.01SyS2, 〇.01^zg3, a + b= 1 , and x + y + zS5.) The direct liquid fuel cell touch described in (3) or (4) Media. (6) When the metal carbonitride gas-10-201131873 compound was measured by a powder X-ray diffraction method (Cu-K line), a diffraction angle of 2 θ = 3 3 ° to 4 3 ° was observed, and 2 or more were observed. The catalyst for a direct liquid fuel cell according to any one of (3) to (5). (7) A catalyst for a direct liquid fuel cell according to (1) or (2), which is characterized by comprising a metal oxycarbonitride of at least one metal other than titanium. (8) consisting of at least one metal containing a group selected from the group consisting of calcium, strontium, barium, strontium, barium, strontium, strontium, strontium, barium, strontium, strontium, strontium, barium, strontium, bait, watch, mirror and distillate The catalyst for a direct liquid fuel cell according to (1) or (2) characterized by the metal oxycarbonitride of the titanium alloy (1) or (2), wherein the composition formula of the metal oxycarbonitride is TiaM2bCxNyOz ( However, a, b, X, y, and z are expressed in atomic ratios, 0.7$a$0.9999, 0.0001^b^0.3, 0.01^x^2, 0.01^2, 0.01^z^3, a + b=l, And the catalyst for direct liquid fuel cells described in (7) or (8) is characterized by the fact that x + y + z'5. (10) A catalyst layer for a direct liquid fuel cell characterized by containing the catalyst according to any one of (1) to (9). (11) A catalyst layer for a direct liquid fuel cell according to (1) which is further characterized by further containing electron conductive particles. -11 - (12) (12) 201131873 It is an electrode for a direct liquid fuel cell having a catalyst layer for a direct liquid fuel cell and a porous support layer, and the fuel cell catalyst layer is (10) or ( 11) An electrode for a direct liquid fuel cell characterized by a catalyst layer for a direct liquid fuel cell. (13) The membrane electrode assembly for a direct liquid fuel cell comprising a cathode, an anode, and an electrolyte membrane disposed between the cathode and the anode, wherein the cathode and/or the anode are as described in (12) A membrane electrode assembly for a direct liquid fuel cell characterized by an electrode for a direct liquid fuel cell. (14) A direct liquid fuel cell characterized by having the membrane electrode assembly for a direct liquid fuel cell according to (13). Advantageous Effects of Invention The present invention is capable of suppressing a decrease in cathode potential caused by permeation of a liquid fuel such as methanol, ethanol, formic acid, 2-propanol, and dimethyl ether, and is capable of obtaining an inexpensive and high-performance direct liquid fuel cell. . MODE FOR CARRYING OUT THE INVENTION <Catalyst for Direct Liquid Fuel Cell> The catalyst for direct liquid fuel cell of the present invention is characterized by a metal oxycarbonitride containing ruthenium and/or titanium. -12- 201131873 The direct liquid fuel cell using the catalyst of the present invention is such that the electrolyte is held by the cathode and the anode, the liquid fuel containing hydrogen is supplied to the anode, and the gas containing oxygen or oxygen (for example, air) is supplied to the cathode. After the hydrogen and oxygen are reacted, the electrical energy generation system is taken out. The liquid fuel used in the direct liquid fuel cell may, for example, be an alcohol, an ether or an acid equal to a carbon atom and a hydrogen atom in the chemical structure. Specific examples of the alcohol include methanol, ethanol, and 2-propanol. Moreover, as a specific example of the said ether, dimethyl ether is mentioned. Further, as a specific example of the above-mentioned acid, formic acid can be mentioned. Among them, methanol, ethanol and formic acid are preferred. The energy conversion efficiency of such liquid fuels in fuel cells tends to be higher. Examples of the electrolyte used in the direct liquid fuel cell include an acidic, neutral or alkaline electrolyte solution or a polymer membrane. When a cathode catalyst or a platinum alloy catalyst is used as the cathode catalyst in the direct liquid fuel cell configured as described above, a decrease in the cathode potential due to the permeation of the liquid fuel occurs. As a result, the performance of the direct liquid fuel cell can be significantly reduced. However, since the catalyst of the present invention is formed of a metal oxycarbonitride containing cerium and/or titanium, even if the liquid fuel is present at the cathode by permeation, the decrease in the cathode potential can be suppressed, which is excellent in oxygen reduction energy. And cheaper. The catalyst for a direct liquid fuel cell of the present invention is preferably inert to the oxidation of the liquid 'fuel. The catalyst for direct liquid fuel cells is inert to the liquid fuel, and even if the liquid fuel reaches the cathode by permeation, it does not cause oxidation reaction of the liquid fuel on the surface of the cathode catalyst, thereby suppressing the decrease of the cathode potential. . For example, when the liquid electrolyte is not contained in the acidic electrolyte solution, a current-potential curve such as L 图 in Fig. 1 is obtained for oxygen reduction. On the other hand, when the liquid electrolyte is contained in the acidic electrolyte solution, when the catalyst for the direct liquid fuel cell is active for the oxidation of the liquid fuel, the oxygen reduction reaction on the surface of the catalyst and the oxidation reaction of the fuel occur simultaneously. Combining the two reactions forms a mixed potential. As a result, the current-potential curve in Fig. 1 is from L 〇 to Lf, that is, to the low potential side. In general, the catalyst for direct liquid fuel cells is less active for oxidation of liquid fuels. The closer Lf and Lo are in Figure 1, the direct fluid fuel cell catalyst is completely inert to the oxidation of liquid fuel. In the case, Lf is consistent with Lo. In order to prevent a decrease in the cathode potential by the penetration of the liquid fuel, it is preferred that the catalyst for the direct liquid fuel cell is inert to the oxidation of the liquid fuel. In the present invention, the "catalyst for a direct liquid fuel cell is inert to the oxidation of a liquid fuel" means a potential at a current density of ΙΟΟμΑ/cm2 obtained by the following measurement method A1 (hereinafter also referred to as "EFue 丨 + 0xygen". Fig. 1 is a reference to Fig. 1 and the potential at a current density of ΙΟΟμΑ/cm2 (hereinafter also referred to as "E〇xygen". See Fig. 1) obtained by the following measurement method A2. For the current density - ΙΟΟμΑ/cm2, the oxygen reduction reaction is dispensable, so the oxygen reduction reaction can be appropriately evaluated in the mixed reaction of the fuel oxidation reaction and the oxygen reduction reaction at a current density of ΙΟΟμΑ/cm2. Selectivity. -14- 201131873 The lower the activity of the direct liquid fuel cell catalyst for the oxidation of liquid fuel, the closer the EFuel + 〇xygen to E0xygen, and the direct liquid fuel cell catalyst is completely inert to the oxidation of liquid fuel. When EF ue I + Ο X yge η and E 〇xygen. [Measurement Method Al: 0.095 g of a catalyst for a direct liquid fuel cell and 0.005 g of carbon (XC-72 manufactured by Cabot Co., Ltd.) were placed in a solution of a mass ratio of isopropyl alcohol: pure water = 2:1. 〇g, and then stirred with ultrasonic waves to obtain a suspension. 30 μί of the suspension was applied to a carbon glass rotating electrode (diameter: 5 mm manufactured by Hokuto Denko Co., Ltd.), and a catalyst layer for a fuel cell containing a catalyst for a direct liquid fuel cell was formed on carbon by drying in air. The glass is turned on the electrode. Further, NAFION (registered trademark) (Dupont 5% NAFION (registered trademark) solution (DE521)) was diluted to 10 times with pure water and applied to the above-mentioned catalyst layer by drying in air, which was obtained by drying in air. Electrode for fuel cells. Using the above fuel cell electrode, in a saturated oxygen atmosphere, a 0.5 mol/L liquid fuel in a mol.5 mol/L sulfuric acid aqueous solution, at a temperature of 30 ° C, a reversible hydrogen electrode in the same concentration of sulfuric acid aqueous solution As a reference electrode, it was made to be a polarization at a potential scanning speed of 5 mV/sec, and a current density by an oxygen reduction reaction when the current-potential curve was measured was -100 (electricity of IA / C Π 1 was taken as EFuei + 〇xygen.) The measurement current was measured in the same manner as in the measurement method A1 except that the 〇·5 mol/L sulfuric acid aqueous solution containing the liquid fuel of the measurement method A2: 0.5 mol/L was changed to a sulfuric acid aqueous solution containing no liquid fuel and 5 mol/L. In the case of the potential curve -15-201131873, the current density of the oxygen reduction reaction is -ΙΟΟμΑ/cm2 as E〇xygen]. In the catalyst for direct liquid fuel cells of the present invention, the above EFuel + 0xygen and E〇xygen are used. The relationship is preferably 〇.6S(EFuel + Oxygen/E〇xygen)Sl, and 0.8^(EFuel+Oxygen/E〇Xygen) ^ 1 is preferred '〇· 9 S (Ef:ue|+〇xygen) /E〇xygen) $ 1 is especially good. Use touches with such characteristics In the case of a direct liquid fuel cell, even if the liquid fuel is present in the cathode by permeation, there is no need to oxidize the liquid fuel, and there is a tendency to selectively reduce oxygen. Therefore, the catalyst for a direct liquid fuel cell of the present invention When EFue, + 0xygen/E0xygen is within the above range, the decrease in cathode potential can be suppressed, and it can be a very useful catalyst for an oxygen reduction catalyst in a direct liquid fuel cell. Moreover, for direct liquid fuel cells When the catalyst is active for the oxidation of the liquid fuel, the liquid fuel that has penetrated to the cathode is oxidized at a higher potential than the theoretical oxidation potential. For example, the theoretical oxidation potential of methanol is 〇·〇5 V, direct liquid fuel. When the catalyst for the battery is a platinum catalyst, the methanol which has penetrated to the cathode is oxidized at a potential of about 0.4 V or more. This can be confirmed by comparison between Fig. 2 and Fig. 3. Fig. 2 shows an electrode for using a platinum catalyst. Cyclic voltammetry in the presence of 0.5 mol/L of methanol in a sulfuric acid electrolyte of 5 mol/L in a saturated nitrogen atmosphere.

Fig. 3 shows a cyclic voltammetry in the absence of methanol in a sulfuric acid electrolyte of 55 mol/L in a saturated nitrogen atmosphere for an electrode using a uranium catalyst. Figure 2 shows that a large oxidation current (ANODEIKKU -16 - 201131873 current) can be observed from about 4.4V (vs RHE). That is, it was found that methanol was oxidized by about 0.4 V on the platinum catalyst. Figure 4 is a graph showing the current-potential curve of oxygen reduction energy in the absence of methanol in a 0.5 mol/L sulfuric acid electrolyte in a saturated oxygen atmosphere for an electrode using a uranium catalyst, and 0.5 mol/L in a saturated oxygen atmosphere. A comparison chart of the current-potential curves of the oxygen reduction energy in the presence of 0.5 mol/L of methanol in the sulfuric acid electrolyte. When methanol is not present in the sulfuric acid electrolyte, 'E0xygen is 0.96V (vs RHE), and when 〇·5 mol/L of methanol is present in the sulfuric acid electrolyte, EFuel + 〇xygen is reduced to 0.58V (vsRHE). For the electrode using a platinum catalyst, the reason why EFuel + 〇xygen is greatly reduced by E0xygen is that the activity of the platinum catalyst is large for the methanol oxidation reaction. That is, in the case of using a platinum catalyst electrode, when a liquid fuel such as methanol is present in the electrolyte, the oxygen reduction energy is remarkably lowered. Therefore, in the direct liquid fuel cell which causes the liquid fuel permeation, * as the cathode catalyst, it is preferable that EFuei + 〇Xygen and E〇Xygen are close to the catalyst. The electrical characteristics of the catalyst of the present invention for the oxidation of liquid fuels, for example, inert to methanol oxidation, are described in detail below using Figures 5 to 7. Figure 5 shows the electrodes used in the catalyst of the present invention in a saturated nitrogen atmosphere. An example of cyclic voltammetry in the presence of mol.5 mol/L of methanol in a 5 mol/L sulfuric acid electrolyte. Fig. 6 shows an example of a cyclic voltammetry in the absence of methanol in a sulfuric acid electrolyte of 5 mol/L in a saturated nitrogen atmosphere for an electrode using the catalyst of the present invention. -17- 201131873 The cyclic voltammetry of the uranium catalyst active with methanol oxidation described above (the relationship between Fig. 2 and Fig. 3) is different, and the cyclic voltammetry in Fig. 5 is almost identical to the cyclic voltammetry in Fig. 6. . Namely, when the catalyst of the present invention is inert to the oxidation of a liquid fuel such as methanol, an oxidation current by oxidation of methanol cannot be observed by cyclic voltammetry. Figure 7 is a graph showing the current-potential curve of oxygen reduction energy evaluated in the presence of 〇.5 mol/L of methanol in a sulfuric acid electrolyte of 55 mol/L in a saturated oxygen atmosphere for an electrode using the catalyst of the present invention. An example of a comparison of the current-potential curves of oxygen reduction energy in the absence of methanol in a sulfuric acid electrolyte of 5 mol/L in a saturated oxygen atmosphere. From the above, it can be seen from FIGS. 5 to 7 that when the catalyst of the present invention is inert to the oxidation of a liquid fuel such as methanol, the mixed potential of the oxygen reduction potential and the methanol oxidation potential is not formed, and EFuel + 0xygen is almost identical to E0xygen. The catalyst having such characteristics has a tendency to selectively reduce oxygen in the direct liquid fuel cell 'inhibiting the oxidation reaction of the liquid fuel, so that the performance of the direct liquid fuel cell can be improved. The cathodic catalyst in a direct liquid fuel cell is generally exposed to an acidic or basic polymer electrolyte to reduce the supplied oxygen. In the present invention, the electrolyte is mainly used as a sulfuric acid electrolyte, the electrolyte is brought into contact with the catalyst, and the state of the cathode catalyst in the direct liquid fuel cell is reproduced in an analog manner, thereby evaluating the oxygen reduction catalyst energy. The catalyst layer for a direct liquid fuel cell of the present invention formed using the above catalyst is preferably used in an acidic electrolyte at a potential of 〇.4 V (vs. RHE) or higher, and the upper limit of the potential depends on the electrode. The stability can be used to generate an oxygen potential to about 1.23V (vs. RHE). When the potential is less than 44. 4V (vs. RHE), there is no problem in the stability of the compound, but oxygen cannot be favorably reduced, and it is used as a membrane electrode assembly included in a direct liquid fuel cell. The usefulness of the catalyst layer is lacking. [Metal Carbon Nitride Oxide Containing Bismuth] The catalyst for a direct liquid fuel cell of the present invention is a metal oxycarbonitride containing at least one metal M1 other than cerium and lanthanum (hereinafter also referred to as "metal carbon oxynitride" The object 1") is better. The metal M1 is selected from the group consisting of tin, indium, giant, zirconium, copper, iron, tungsten, chromium, molybdenum, titanium, vanadium, cobalt, manganese, cerium, mercury, cerium, lanthanum, cerium, lanthanum, cerium, At least one metal of the group consisting of 鐯, hinge, giant, 钐, 铕', 铽, 镝, 鈥, bait, 铥, mirror, distillation, and nickel is preferred. Among them, at least one metal composed of iron, tin, indium, giant, manganese, lanthanum, chromium and cobalt is particularly preferred. When a catalyst composed of a metal oxycarbonitride containing such a metal is used in a liquid fuel cell, the decrease in the cathode potential by permeation can be suppressed, which is excellent in oxidation-reduction energy. The composition formula of the above metal oxycarbonitride 1 is NbaMlbCxNyOz (however, a, b, X, y, z are represented by atomic ratio, 0.01 Sa < l, 0 < bS 0.99 , 0.01 , 0.01 1 ^ y ^ 2 0.0 1 ^ z ^ 3, a + b = 1 , and x + y + z$5.) is preferred. -19· 201131873 The a and b of the above composition formula NbaMlbCxNyOz are 0.05SaS0.99, 0.01SbS0.95, and a+b=1 is preferred, 0.50SaS0.99, 0.01SbS0.50, and a + b=l More preferably, 0.80Sa 0.99, 0.01 SbS 0.20, and a + b = 1 is particularly good. The x, y and z in the above composition formula NbaMlbCxNyOz are 0.01Sx$2, 0.01, 0.05, and 0.07 S x + y + z S 5 is preferred. When the ratio of the number of atoms is in the above range, the catalyst formed of the metal oxycarbonitride 1 can improve the effect of suppressing the decrease in the cathode potential and has a tendency to increase the oxygen reduction energy. The catalyst composed of the metal oxycarbonitride 1 of the present invention is a single compound or a mixture of at least bismuth, metal M1, carbon, nitrogen and oxygen when elemental analysis of the catalyst is performed. . That is, the catalyst formed by the metal oxycarbonitride 1 of the present invention is a compound represented by NbaMlbCxNyOz or an oxide containing a metal M1, a carbide of a metal M1, a nitride of a metal M1, or a metal M1. Carbonitride, carbon oxide of metal M1, nitrogen oxide of metal Ml, oxide of silver, carbide of niobium, niobium of tantalum, niobium carbonitride, niobium oxycarbide, niobium oxynitride An oxide containing a metal M1 and lanthanum, a carbide containing a metal M1 and lanthanum, a nitride containing a metal M1 and lanthanum, a carbonitride containing a metal M1 and lanthanum, a carbon oxide containing a metal M1 and lanthanum, and a metal containing Ml and bismuth oxynitride, etc., have a compositional formula as a whole mixture of NbaMlbCxNyOz (but may or may not contain a compound represented by NbaMlbCxNyOz), or both. Among them, when an oxide such as Nb12029 having an oxygen deficiency is contained, the oxygen reduction energy of the catalyst of -20-201131873 tends to be high, which is preferable. Further, when the metal oxycarbonitride 1 was measured by a powder X-ray diffraction method (Cu-K line), two or more diffraction lines were observed at a diffraction angle of 2 Θ = 3 3 ° to 4 3 °. The peak is better. When two or more diffraction line peaks are observed, the oxygen reduction potential of the obtained catalyst tends to be high, which is preferable. The diffraction line peak is a peak at a specific diffraction angle and diffraction intensity when the sample (crystal) is irradiated to the X-ray at various angles. In the present invention, a signal in which the ratio (S/N) of the signal (S) to (N) is 2 or more is detected as one diffraction line peak. The noise (N) is the width of the bottom line. As a measuring apparatus of the X-ray diffraction method, for example, a powder X-ray analysis apparatus: Rigaku RAD-RX can be used, and the measurement conditions are X-ray output (Cu-K line): 50 kV, 180 mA, scanning axis: Θ/2 Θ, Measuring range (2Θ): 10°~89.98 °, Measurement mode: FT, reading amplitude: 〇.〇2°, sampling time: 0.70 sec, DS, SS, RS: 0.5°, 0.5. , 0.1 5 m m, goniometer radius: 1 8 5 m m. Further, the metal oxycarbonitride 1 is a mixture of several phases, and when the metal oxycarbonitride i is measured by a powder X-ray diffraction method (Cu-K line), a peak derived from Nb12029 is preferably observed. Other peaks from oxides such as NbO 'Nb02, Nb205, Nb25〇62, Nb4701, 6, Nb22〇54 can also be observed. Although the structure of the metal oxycarbonitride 1 is not known, the inventors have estimated that it is considered that the metal oxycarbonitride 1 has a phase such as an oxide such as Nb12029 which has an oxygen deficiency. Generally, Nbl2〇29 alone cannot exhibit high oxygen reduction energy, but the above-mentioned metal oxycarbonitride 1 has a phase formed by an oxide such as NbI2029 having oxygen deficiency of from 21 to 201131873, so that the finally obtained catalyst has a high oxygen reduction. can. In the above-mentioned metal oxycarbonitride 1, when Nb12029 having oxygen deficiency is used as one unit, it is considered that oxygen is a bridged ligand (Nb-0-O-Nb) between Nb and Nb of each unit. Although the expression mechanism of oxygen reduction energy is not known, it is presumed that the above-mentioned bridge ligand (Nb-0-O-Nb) makes Nb an active point and exhibits oxygen reduction energy. When the oxygen-deficient >^1) 12029 overlaps each unit, the bonding distance between Nb and Nb between the units becomes short. The more the shorter the bonding distance, the higher the oxygen reduction energy. Further, it is stacked in the unit to increase the catalytic activity by changing the electron density around Nb via carbon or nitrogen. Further, the deposition of carbon and nitrogen can also improve the electron conductivity, but the reason for the improvement in performance has not been determined. When the metal oxycarbonitride 1 is used as a catalyst for a direct liquid fuel cell, an additive which imparts conductivity may be added. Specifically, electron conductive particles such as carbon black represented by Vulcan XC72 and Ketjen Black may be added. However, even if conductive particles such as carbon black are not added to the catalyst formed of the metal oxycarbonitride 1 of the present invention, carbon is detected during elemental analysis. [Metal oxycarbonitride containing titanium] The catalyst for a direct liquid fuel cell of the present invention is a metal oxycarbonitride containing at least one metal M2 other than titanium and titanium (hereinafter also referred to as "metal carbon oxynitride" The object 2") is better. As the metal M2, at least one metal of calcium, lanthanum, cerium, lanthanum, cerium, lanthanum, lanthanum-22-201131873, giant, cerium, lanthanum, lanthanum, cerium, lanthanum, cerium, bait, surface, mirror and distillation It is better. Among them, at least one metal selected from the group consisting of strontium, barium, ammonium, strontium, bait calcium and strontium is particularly preferred. In the case of a direct-liquid type fuel cell composed of a metal oxycarbonitride containing such a metal, it is possible to suppress the cathode electric charge by permeation, which is excellent in oxidation-reduction energy and inexpensive. The composition formula of the above metal oxycarbonitride 2 is TiaMZbCd, and a, b, X, y, z are represented by atomic ratio, 0.7Sa$0. 0.0001 ^ b ^ 0.3, 0.01 ^ X ^ 2, 0.01 ^ 2, 0.01 ^ a + b= l, and x + y + z$5. The one shown is better. The a and b in the above composition formula TiaM2bCxNyOz are 0.8$a each of 0.001^0.2, and a + b = 1 is preferable, 0.9$a$0 O.OOlSbSO.l, and a + b = 1 is more preferable. In the above composition formula TiaM2bCxNyOz, X, y and 0.01^x^2' 0.01^y^2' 0.01^z^3> and x + y + z helmet 5 ο the ratio of the respective atoms is in the above range, by the foregoing The catalyst formed by the metal carbon 2 can improve the reduction of the cathode potential, and the reduction energy tends to be higher. When the catalyst composed of the metal oxycarbonitride 2 of the present invention is subjected to elemental analysis of the catalyst, at least titanium, metal M2 nitrogen and oxygen are detected, and there is also a possibility of a single compound or a mixture. In the metal oxycarbonitride 2 used in the present invention, the crystal fraction is at least a crystal structure of an oxide. That is, it has a rutile type group, 缌, suitable for the position to be reduced by 4y0Z (but 9999, z ^ 3, 0.999 '.999, z is preferred nitrogen oxidation, and oxygen is, carbon, sex Oxidization-23- 201131873 The possibility of a compound (1) in which one part of oxygen is replaced by carbon or nitrogen | An oxide formed from titanium and oxygen (sometimes an oxidized crystalline compound containing oxygen deficiency) And the possibility of an amorphous compound (2) made of carbon and nitrogen. It has the possibility of mixing the compound (1) with the mixture (2), but it is technically necessary to separate and identify these. When the metal oxycarbonitride 2 is used as a direct liquid fuel, when a catalyst is used, an additive material for imparting conductivity may be added. In some cases, Vulcan XC72, Ketjen Black, etc. may be added as a representative; However, the catalyst formed by the metal carbonitride oxyfluorene f of the present invention does not contain such conductive particles such as carbon black, and carbon is detected in the analysis of each element" <catalyst for direct liquid fuel cell Manufacturing method > The above direct liquid fuel Although the method for producing a battery catalyst is limited, for example, a metal carbon containing ruthenium and/or titanium is contained, and heating is carried out in an inert gas containing oxygen to obtain a metal oxycarbonitride containing titanium or titanium. The manufacturing method of the step. When the angle formed by the metal oxycarbonitride obtained by the manufacturing method is used for a direct liquid fuel cell, the reduction of the ruthenium by the penetration can be suppressed, and the redox energy is excellent and inexpensive. The method for producing a catalyst formed by the carbon oxynitride 1 is particularly limited to the production of a catalyst made of the metal oxycarbonitride 1 described above. However, for example, the content of the catalyst is selected from tin, indium, or a substance. ): Mixing • I use the pool. 〖In terms: carbon black: material 2; row element from special, material 铌 and / ΐ 丨 丨 、 、 销 销 销 销 销 - - - - - - - - - - - - - - - - - - - - - - - - - , group, feed, titanium, vanadium, cobalt, manganese, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, ammonium, giant, cerium, lanthanum, cerium, lanthanum, bait, surface, mirror, distillation and nickel At least one metal and carbonitride of gold and rhodium (hereinafter also referred to as "metal carbon nitrogen" 1 By heating in an inert gas containing oxygen, it is obtained to contain indium, bismuth, pin, copper, iron, tungsten, lanthanum, molybdenum, niobium, tantalum, yttrium, yttrium, mercury, lanthanum, cerium, lanthanum, cerium, lanthanum, The process of the steps of the steps of obtaining the metal M1 and the metal oxycarbonitride 1 of the group of yttrium, ammonium, giant, lanthanum, cerium, lanthanum, lanthanum, cerium, lanthanum, lanthanum, lanthanum, cerium, lanthanum, bait, surface, mirror, yttrium and nickel Metal Carbonitride 1 A method of producing a product 1 by heating an oxide of the above metal M1, a mixture of cerium oxide and carbon, or an inert gas containing nitrogen, (i), an oxide of the metal M1, and lanthanum carbide The mixture is produced by heating the carbonitride 1 (i) in an inert gas such as nitrogen or by heating the mixture of the yttrium oxide yttrium nitride and the yttrium oxide of the metal M1 by inert gas such as nitrogen. The method (iii) of extracting the metal carbonitride 1, the compound of the metal M1 (for example, an organic acid salt, a chloride, a nitride, a dislocation, etc.), the niobium carbide, and the tantalum nitride are mixed with an inert gas such as nitrogen. Heating to produce metal carbon nitrogen Method (iv) and the like are cited. Also, if a metal carbonitride is available! The material is not particularly limited, and for example, the above-mentioned production method (i) ^ raw material and other raw materials can be used in combination. The mixture thus combined can be heated by an inert gas to produce a metal lanthanum carbonitride, a mercury, a test, a ruthenium ruthenium 1 to a ruthenium 1") selected from the group consisting of tin, cobalt, manganese ruthenium, osmium, At least 1 method. a method for producing a metalloide, a carbonaceous gas, or a compound, a carbon compound by the compound 1 by nitrogen metal lanthanum carbonitride and nitrogen, as a raw material in the original u (iv) -25-201131873 Method (V) » [Manufacturing method (i)] The manufacturing method (i) is by using the above-mentioned metal M1 oxide, oxidation & carbon mixture in a nitrogen atmosphere or an inert gas containing nitrogen. A method of producing metal carbonitride 1 by heating. The heating temperature at the time of producing the metal carbonitride 1 is in the range of 600 to 1 800 ° C, preferably in the range of 800 to 1600 °C. When the heating temperature is within the above range, it is preferable from the viewpoint of good crystallinity and uniformity. When the heating temperature is less than 600t, the crystallinity is deteriorated and the uniformity is deteriorated. When it is 1880 °C or more, it tends to be easily sintered. The oxide of the metal M1 of the raw material may be tin oxide, indium oxide, antimony oxide, chromium oxide, copper oxide, iron oxide, tungsten oxide, chromium oxide, molybdenum oxide, oxide bell, titanium oxide, vanadium oxide, cobalt oxide, or oxidation. Manganese, cerium oxide, oxidized mercury, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, oxidized giant, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, Oxidation baits, oxidation tables, oxidizing mirrors, cerium oxide and nickel oxide. One type or more of the oxide of the metal M1 can be used. Examples of the cerium oxide as a raw material include carbon as a raw material such as NbO, NbO 2 or Nb 205, and examples thereof include carbon, carbon black, graphite, black lead, activated carbon, carbon nanotubes, nano carbon fibers, and carbon nanohorns. , Fullerene. When the particle size of the carbon powder is small, the specific surface area becomes large, and it is preferable to easily react with the oxide. For example, carbon black (specific surface area -26-201131873: 100 to 300 m2/g, for example, XC-72 manufactured by Cabot Co., Ltd.) or the like can be used. The catalyst of the metal carbonitride 1 obtained by heating the oxide of the metal M1, cerium oxide and carbon by the metal oxycarbonitride 1 obtained by heating in an inert gas containing oxygen, even if any of the above materials is used. When used in a direct liquid fuel cell, it is possible to suppress a decrease in cathode potential by permeation, and its redox energy is excellent and inexpensive. When the amount of the oxide, cerium oxide, and carbon added (molar ratio) of the metal ruthenium is controlled, a suitable metal carbonitride 1 can be obtained. The above-mentioned addition amount (mole ratio) is generally for cerium oxide 1 mol, the oxide of the aforementioned metal M1 is 〇.〇1~1〇mol, carbon is 1 to 10 mol, preferably for cerium oxide 1 In the case of Mohr, the aforementioned metal M1 has an oxide of 0.01 to 4 moles and a carbon of 2 to 6 moles. When the metal carbonitride 1 produced by the combination of the molar ratios in the above range is used, the metal carbonitride 1 which is excellent in oxygen reduction energy and high in activity can be suppressed by suppressing the decrease in the cathode potential by the permeation. [Production Method (ii)] The production method (ii) is a method in which a mixture of an oxide of the metal M1, a mixture of niobium carbide and niobium nitride is heated in an inert gas such as nitrogen to produce a metal carbonitride 1. The heating temperature at the time of producing the metal carbonitride 1 is in the range of 600 to 1800 ° C, preferably 800 to 1600. When the heating temperature is within the above range, the crystallinity and uniformity are good. When the heating temperature is less than 600 ° C, the crystallinity is deteriorated, and the uniformity is deteriorated. - 201131873, when it is 18 ° C or higher, it tends to be easily sintered. As the raw material, the oxide of the metal M1, tantalum carbide and tantalum nitride are used. The oxide of the metal M1 of the raw material may be tin oxide or oxidation. Indium, molybdenum oxide, chromium oxide, copper oxide, iron oxide, tungsten oxide, chromium oxide, molybdenum oxide, oxidation, titanium oxide, vanadium oxide, cobalt oxide, manganese oxide, antimony oxide, mercury oxide, antimony oxide, antimony oxide, Cerium oxide, cerium oxide, cerium oxide, cerium oxide, ammonium oxide, oxidized giant, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, oxidized bait, cerium oxide, oxidizing mirror, oxidizing distillation and nickel oxide NbC or the like can be used as the raw material of the metal hydride. Examples of the niobium nitride as a raw material include NbN, etc. Even if any of the above raw materials is used, the oxygen of the metal M1 described above is used. The metal carbonitride 1 obtained by the compound, the tantalum carbide and the tantalum nitride is used in a direct liquid fuel cell by using a catalyst formed by heating the metal carbonitride oxide 1 obtained by heating in an inert gas containing oxygen. It is possible to suppress the reduction of the cathode potential by permeation, and the redox energy is excellent and inexpensive. When the amount of the oxide of the metal M1, the amount of niobium carbide and the tantalum nitride (mol ratio) is controlled, a suitable metal carbonitride can be obtained. The aforementioned addition amount (mole ratio) is generally 0.01 to 500 m for niobium nitride (NbN), the niobium carbide (NbC) is 0.01 to 500 m, and the oxide of the aforementioned metal M1 is 〇.〇1 to 50 m'. Preferably, for niobium nitride (NbN) l Mo, the niobium carbide (NbC) is 0.1 to 3 〇 0 mol. The oxide of the aforementioned metal M1 is 〇1 to 3 〇 Mo. Use to satisfy the above range. In the case of the metal carbonitride i-28-201131873 produced by Moerby, it is possible to suppress the decrease in the cathode potential by permeation, and it is preferable to obtain the metal nitron oxide 1 which is excellent in activity and high in activity. [Manufacturing method (m)] The manufacturing method (Hi) is an oxide of the aforementioned metal M1, nitrogen A method of producing a metal carbonitride 1 by heating an inert gas such as nitrogen gas with a mixture of cerium oxide and cerium oxide. The heating temperature at the time of producing the metal carbonitride 1 is 600 to a range, preferably 800 to 160. In the range of 0 ° C. When the above heating temperature range is good, the crystallinity and uniformity are good. When the hot temperature is less than 60 ° C, the crystallinity is deteriorated, and the uniformity is changed. If it is at 1 800 ° When it is C or more, it tends to be easily sintered. As the raw material, the oxide of the metal M1, lanthanum carbide and lanthanum oxide are used. The oxide of the metal M1 of the raw material may be indium oxide ruthenium oxide, chromium oxide, copper oxide or iron oxide. Chromium oxide's molybdenum oxide, oxidized, titanium oxide, vanadium oxide, cobalt oxide, cerium oxide, oxidized mercury, cerium oxide, cerium oxide, oxidized nail, cerium oxide, cerium oxide, ammonium oxide, oxidized giant, cerium oxide, cerium oxide , cerium oxide, cerium oxide, cerium oxide, oxidized bait, oxidizing mirror, oxidation distillation and nickel oxide. The oxide of the metal M1 can be made above. Examples of the niobium carbide as a raw material include NbC and the like. Examples of the tantalum nitride as a raw material include NbN and the like. The cerium oxide as a raw material may be a NbO 'Nb02 or Nb2 oxygen reducing energy cerium carbide, and a degree of adding 180 ton is the above. The above-mentioned tendency to add 铌, tin nitride, oxygen crane, oxidation, manganese oxide ruthenium oxide, ruthenium oxide, osmium oxide, oxidation type 1 〇5, and the like. • 29-201131873 The use of any of the above-mentioned raw materials 'the metal carbon nitrogen obtained by heating the metal carbonitride obtained by the aforementioned metal M1, niobium carbide, tantalum nitride and niobium oxide in an inert gas containing oxygen In the case of a direct liquid fuel cell, the cathode potential which can be suppressed is lowered, and its redox energy is excellent and inexpensive. When the amount of the oxide of the metal ruthenium 1, the amount of ruthenium carbide, and the amount of ruthenium nitride (the molar ratio) are controlled, the amount of the appropriate metal carbonitride added (mol ratio) is generally obtained for the niobium nitride (NbN) Mob (NbC). ) is 0. 01~5 〇〇 耳 , , , , , 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 倂 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属The combined metallization and cerium oxide are 0.1 to 30 moles. When the metal carbonitride 1 produced by the above molar ratio is used, it is possible to suppress a decrease in the cathode potential, and it is preferred to have an excellent oxygen reduction energy and a high activity of the nitrogen oxide 1. [Production Method (iv)] The production method (iv) is a method of producing a metal carbonitride 1 by using a mixture of niobium carbide and niobium nitride containing the metal M1 in an inert gas such as nitrogen. The heating temperature at the time of producing the metal carbonitride 1 is 600 to a range ', preferably in the range of 800 to 1600 °C. In the case of heating the temperature 匮I, the crystallinity and uniformity are good, and the crystallinity is deteriorated when the hot temperature is less than 600 ° C, and the oxide 1 having uniformity is reduced by the oxide 1 By percolation and oxidation 1. In the foregoing, in the case of the carbide and the oxygen, the oxygen in the range of M1 is added by the infiltrated metal carbon compound, and is heated to 1 800 〇. . The degree is as described above. The tendency to add the difference -30-201131873 has a tendency to be easily sintered if it is above 1 800 00. As the raw material, a compound containing the above metal M1, ruthenium carbide and ruthenium nitride are used. Examples of the compound containing the metal M1 of the raw material include tin, indium, molybdenum, zirconium, copper, iron, tungsten, chromium, pin, niobium, vanadium, vanadium, methane, lanthanum, yttrium, yttrium, yttrium, yttrium, yttrium Organic acid salts, carbonates, chlorides, organic compounds, carbides, nitrogen, such as lanthanum, cerium, lanthanum, sharp, giant, shirt, scorpion, chaos, cockroach, cockroach, cockroach, bait, cockroach, mirror, distillation or nickel Compounds, etc. As the raw material of the metal containing M1, one type or more can be used, and NbC or the like can be mentioned. Examples of the tantalum nitride as a raw material include NbN and the like. Even if any of the above materials is used, the metal carbonitride 1 obtained by the compound containing the metal M1, the tantalum carbide and the tantalum nitride is formed by the metal carbonitride oxide 1 obtained by heating in an inert gas containing oxygen. When the medium is used in a direct liquid fuel cell, the decrease in the cathode potential by permeation can be suppressed, and the redox energy is excellent and inexpensive. When the amount of the compound containing the metal M1, the amount of lanthanum carbide and the amount of tantalum nitride (mol ratio) is controlled, a suitable metal carbonitride 1 can be obtained. The amount of addition (mole ratio) is usually 0.01 to 500 moles for lanthanum nitride (NbN), and the compound containing the metal M1 is o.ooi to 5 〇m. For niobium nitride (NbN) 1 Mo, the niobium carbide (Nbc) is 0.1 to 300 m, and the compound containing the aforementioned metal M1 is o. oi to 30 mol. When the metal carbonitride 1 produced by adding the molar ratio in the above range is used, it is possible to suppress the decrease in the cathode potential by permeation, and it is preferable to obtain the metal oxycarbonitride 1 which is excellent in oxygen reduction energy and high in activity. -31 - 201131873 [Manufacturing method (V)] The metal carbonitride 1 ' is not particularly limited as long as it can be used as the raw material. The raw materials and other raw materials in the above production methods (1) to (iv) can be seeded. Use in combination. The production method (V) is a method of producing a metal carbonitride 1 by heating a raw material mixture other than the combination of the raw materials in the above production methods (i) to (iv) with an inert gas such as nitrogen. The heating temperature at the time of producing the metal carbonitride 1 is 600 to 1800. The range of (: is preferably in the range of 800 to 16 00 ° C. When the heating temperature is within the above range, the crystallinity and uniformity are good. The heating temperature is less than 600 ° C and there is crystallization. When the properties are deteriorated and the uniformity is deteriorated, it tends to be easily sintered if it is at a temperature of 1 800 ° C or higher. As the raw material, for example, a compound containing the metal ruthenium 1 , ruthenium carbide, ruthenium nitride, ruthenium oxide, or the like may be used. A combination of a precursor of ruthenium or carbon is used as a raw material mixture. Compounds containing a metal M1 of a raw material include tin 'indium, giant, pin, copper, iron, tungsten, chromium, molybdenum, bell, chin, vanadium, and Meng, 铈, 录, 钸, 钇, 钌, 镧, 钸, 鐯, 钹, 鈪, 钐, 铕, 铽 '铽, 镝, 鈥, bait, 铥, mirror, distillation or nickel and other organic acid salts, carbonates , a chloride, an organic compound, a carbide, a nitride, a precursor, etc. The compound containing the metal M1 can be used in an amount of one or more. Examples of the niobium carbide as a raw material include NbC and the like. Etc. -32- 201131873 As a raw material, cerium oxide can be cited as N B0, Nb〇2 or Ο As the ruthenium precursor, an organic acid salt, a carbonate, an organic dysfunction, a carbide, a nitride, an alkoxide, etc. of ruthenium may be mentioned. Examples of carbon as a raw material include carbon and carbon black. , graphite, black lead, carbon nanotubes, carbon nanotubes, carbon nanohorns, fullerenes. When the particle size is small, the specific surface area becomes large, and it is easy to carry out the oxide. For example, carbon black (specific surface area) can be used. : 100 to 300 m2, XC-72, manufactured by Cabot Co., Ltd., etc. Even if any of the above materials is used, the obtained metal carbon nitrogen is used as a catalyst for the metal carbon 1 obtained by heating in an inert gas containing oxygen, and is used in a direct liquid type. In the case of a fuel cell, the cathode potential which can be suppressed is lowered, and the redox energy is excellent and inexpensive. For example, when the amount of the compound containing the metal ruthenium 1 and the amount of lanthanum carbide (molar ratio) is controlled, a suitable metal carbon nitrogen can be obtained. The amount of addition (mole ratio) is usually 0.01 to 500 moles for NbN, and 0.001 to 50 moles of the aforementioned metal M1 is preferred for NbN. Ear and silver (NbC) is 0 · 1~3 00 m' before containing 0.01 to 30 moles of the metal μ 1 . When the metal carbonitride 1 to which the molar is added in the above range is used, it is possible to suppress oxidation of the metal carbon nitrogen which is excellent in oxygen reduction energy and high in activity by the cathodic electricity which is infiltrated. to.

The powder of salt, chlorinated or activated carbon such as Nb205 reacts with /g, for example, the compound 1 is made by nitriding ruthenium and nitrogen. In the case of a ruthenium carbide compound, the carbonization compound is lower than the position to be produced, and the tilt of the material 1 is -33 to 201131873 (manufacturing step of the metal oxycarbonitride 1). Next, the metal obtained by the above production methods (i) to (v) The carbonitride 1 is described by the step of obtaining the metal carbonitride oxide 1 by heating in an inert gas containing oxygen. Examples of the inert gas include nitrogen gas, helium gas, neon gas, argon gas, helium gas, neon gas or helium gas. Nitrogen, argon or helium are particularly easy to start with. The concentration of oxygen in the inert gas depends on the heating time and the heating temperature, preferably from 0.1 to 10% by volume, particularly preferably from 0.5 to 5% by volume. When the concentration of oxygen described above is within the above range, a uniform carbon oxynitride can be formed, which is preferable. Further, when the concentration of the oxygen gas is less than 0.1% by volume, the oxidation state tends to be unoxidized, and when it exceeds 1% by volume, the oxidation tends to be excessive. In the above inert gas, hydrogen is preferably contained in a range of 5% by volume or less. The hydrogen content is preferably 0.01 to 4% by volume, more preferably 0.1 to 4% by volume. Further, the gas concentration (% by volume) in the present invention is in the standard state. The heating temperature in this step is usually in the range of 400 to 1400 ° C, preferably in the range of 600 to 1 200 ° C. When the heating temperature is within the above range, a uniform metal oxycarbonitride 1 can be formed, which is preferable. When the heating temperature is less than 400 ° C, oxidation tends not to occur, and if it is 1400 ° C or more, it is excessively oxidized, and crystal growth tends to occur. Examples of the heating method include a standing method, a stirring method, a dropping method, and a powder capturing method. -34- 201131873 The so-called static method is a method in which metal carbonitride 1 is placed in a stationary electric furnace or the like. Further, there is also a method in which an alumina disk, a quartz disk, etc., which are used for weighing metal carbon nitrogen 1, are placed and heated. The standstill method is preferable from the viewpoint of heating a large amount of metal carbonitride 1. The stirring method is a method in which metal carbonitride is placed in an electric furnace such as a rotary furnace, and the mixture is heated while stirring. In the case of the stirring method, a large amount of metal carbonitride 1 is thermally, and it is preferable to suppress aggregation and growth of the metal carbonitride 1 . <=> When the tubular furnace is subjected to a standing method of a stirring method or the like, the heating time of the metal carbonitriding is 〇 1 to 10 hours, preferably 0.5 to 5 hours. When the preheating time is within the above range, there is a tendency that a uniform metal carbonitride 1 is formed. When the heating time is less than 1 hour, the metal oxycarbonitride 1 tends to form in a divided manner, and when it exceeds 10 hours, the tendency to oxidize excessively. The drop method is a method in which a furnace containing a trace amount of oxygen inert gas is introduced into a furnace to heat the furnace to a predetermined heating temperature, and after the temperature is thermally equilibrated, the metal carbonitride is dropped in the crucible of the heating zone of the furnace to be heated. In the case of the dropping method, it is preferable to suppress the aggregation and growth of the metal carbonitride particles to a minimum. In the case of the dropping method, the heating time of the metal carbonitride 1 is 0.5 to 10 minutes, preferably 0.5 to 3 minutes. When the heating time is within the range, there is a tendency to form a uniform metal carbonitride oxide 1. The above heating time is less than 〇. 5 minutes, there is a tendency to form gold oxynitride 1 partially, and when it is more than 1 minute, there is an oxidized over-evolutionary compound state as a compound which can be added. The holder 1 is generally preferred to the above-mentioned preferred carbon line -35-201131873. The powder capture method is a method in which a metal carbonitride 1 is sputtered and floated in an inert gas atmosphere containing a trace amount of oxygen, and a metal carbonitride 1 is captured and heated in a vertical tubular furnace maintained at a predetermined heating temperature. In the case of the powder capture method, the heating time of the metal carbonitride 1 is 0.2 seconds to 1 minute, preferably 0.2 to 10 seconds. When the heating time is within the above range, there is a tendency to form a uniform metal carbonitride oxide 1 Therefore, it is better. When the heating time is less than 0.2 second, the metal oxycarbonitride 1 tends to be partially formed, and excessive oxidation tends to occur over one minute. As the catalyst of the present invention, the metal oxycarbonitride 1 obtained by the above production method or the like can be used as it is, but a finer powder of the metal oxycarbonitride 1 obtained by further pulverization can be used. Examples of the method of pulverizing the metal oxycarbonitride 1 include a method of rotating a honing machine, a ball honing machine, a medium agitating honing machine, a jet mill, a mortar, a trough, etc. by a roll, etc. From the viewpoint of the finer particles of the metal oxycarbonitride 1 , it is preferable that the method by the jet mill is preferable, and the method of using a mortar is preferable from the viewpoint of a small amount of processing. [Method for Producing Catalyst Made of Metal Carbonitride OX 2] The method for producing the catalyst formed of the metal oxycarbonitride 2 is not particularly limited, and examples thereof include calcium, strontium, and barium. , 钌, 镧, 鐯, 铰, 巨, 钐, 铕, 乱, 铽, 镝, 饵, bait, table, mirror, and distillate group of at least one metal M2 and titanium metal carbonitride (the following also - 36- 201131873, described as "metal carbonitride 2") is heated in an inert gas containing oxygen to obtain calcium, strontium, barium, strontium, barium, strontium, strontium, strontium, barium, strontium, strontium, strontium, barium A method for producing a step of at least one metal M2 and titanium metal oxycarbonitride 2 in a group of sputum, bait, watch, mirror, and ruthenium. The method of obtaining the metal carbonitride 2 used in the above step includes, for example, a mixture containing a compound containing the metal M2, a compound containing titanium, and carbon, and heating in a nitrogen atmosphere or an inert gas containing nitrogen. A method of producing metal carbonitride 2 (vi). Further, a method of producing a metal carbonitride 2 by heating the mixture of the oxide of the metal M2, titanium oxide and carbon in a nitrogen atmosphere or an inert gas containing nitrogen is preferred. [Manufacturing Method (vi)] The production method (vi), comprising a mixture of a compound containing the metal M2, a compound containing titanium, and carbon, and heating in a nitrogen atmosphere or an inert gas containing nitrogen to produce a metal carbonitride 2 The heating temperature at the time of producing the metal carbonitride 2 is in the range of 500 to 220 CTC, preferably in the range of 800 to 2 000 ° C. When the heating temperature is within the above range, the crystallinity and uniformity are good. When the heating temperature is less than 500 ° C, the crystallinity tends to be deteriorated and the uniformity tends to be deteriorated. When the temperature is 2200 ° C or higher, sintering may occur and the crystal tends to be large. a nitrogen or nitrogen compound mixed gas can be supplied to the nitrogen source in the synthesized carbonitride. The compound containing the metal M2 of the raw material can be exemplified by an oxide, a carbide-37-201131873, a nitride, a carbonate, a nitrate, and an acetic acid. a carboxylate such as a salt, an oxalate or a citrate, a phosphate, etc. Examples of the oxide include calcium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, and oxidation. , cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, oxidized bait, oxidation table, oxidized shovel, cerium oxide, etc. As the carbide, calcium carbide, strontium carbide, strontium carbide, strontium carbide , cerium carbide, cerium carbide, cerium carbide, carbonized cerium, cerium carbide, cerium carbide, cerium carbide, cerium carbide, cerium carbide, cerium carbide, carbonized bait, carbonization table, carbonation mirror or carbonized distillation, etc. Calcium nitride, tantalum nitride, tantalum nitride, tantalum nitride, tantalum nitride, tantalum nitride, tantalum nitride, tantalum nitride, tantalum nitride, tantalum nitride, tantalum nitride, tantalum nitride, nitrogen Hydrazine, tantalum nitride, nitriding bait, nitriding meter, nitriding mirror or nitriding, etc. Examples of the carbonate include calcium carbonate, cerium carbonate, cerium carbonate, cerium carbonate, cerium carbonate, cerium carbonate, and carbonic acid.钹, 碳酸 carbonate, cesium carbonate, cesium carbonate, cesium carbonate, cesium carbonate, cesium carbonate, cesium carbonate, cesium carbonate, cesium carbonate, carbonic acid mirror, cesium carbonate, etc. The compound containing metal M2 may be used in one type or more, and is not particularly limited. As a compound containing titanium as a raw material, oxygen can be mentioned. a substance, a carbide, a nitride, a carbonate, a nitrate, an acetate, an oxalate, a citrate, a carboxylate, a phosphate, an oxychloride, etc. Examples thereof include Ti304, TiO2, and TinOzn (but, η It is an integer of 1 to 20, preferably an integer of 1 to 10, TiC, TiN, TiCl2, TiCl4, etc. Examples of carbon as a raw material include carbon, carbon black, graphite, black lead, activated carbon, and nanometer. Carbon tube, nano carbon fiber, carbon nano angle, and fullerene-38-201131873 (Fullerene). When the particle size of carbon powder is small, the specific surface area becomes large, and it is preferable to react easily with an oxide. Carbon black (specific surface area: 100 to 300 m2/g, such as XC-72 manufactured by Cabot Co., Ltd.). Even if any of the above-mentioned raw materials is used, the obtained metal carbonitride 2 can be inhibited from being used in a direct liquid fuel cell by using a catalyst formed by heating the metal carbonitride oxide 2 obtained by heating in an inert gas containing oxygen. The cathode potential of the permeation is lowered, and its redox energy is excellent and inexpensive. When the amount of the compound containing the metal M2 and the compound containing titanium (molar ratio) is controlled, the appropriate metal carbonitride 2 can be obtained. When the metal carbonitride 2 produced by the optimum molar ratio is used in the above-mentioned addition amount (mole ratio), the decrease in the cathode potential by the permeation can be suppressed, and the oxygen-based energy can be excellent. The tendency of the object 2. [Using method] The method (via) is a method of producing a metal carbonitride 2 by heating an oxide of the metal M2, a mixture of titanium oxide and carbon in a nitrogen atmosphere or an inert gas containing nitrogen. The metal carbonitride 2 obtained by the production method (vi a) is preferably made of a metal carbonitride 2 obtained by heating in an inert gas containing oxygen because the redox energy is excellent. The heating temperature in the case of the nitride 2 is in the range of 600 to 2200 ° C, preferably in the range of 800 to 2000 ° C. More preferably from 1000 to 1900. The scope of 匚. When the heating temperature is within the above range, it is preferable from the viewpoint of good crystallinity and uniformity. The heating temperature is less than 60 (the crystallization has a characteristic of deterioration of the crystal of the structure of 39 to 201131873, and the tendency of the uniformity to deteriorate '22〇〇°c or more' has a tendency to be sintered and the crystal becomes large. As a manufacturing method (via) Examples of the oxide of the raw material metal M2 include oxidation loss, cerium oxide, oxidized particles, cerium oxide, cerium oxide, cerium oxide, cerium oxide, oxidized giant, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, The cerium oxide, the oxidized bait, the oxidized surface, the oxidizing mirror, or the oxidized distillation. These oxides may be used in one type or more. Examples of the titanium oxide as a raw material in the production method include Ti304, TiO2, and TinOh. η is an integer of 1 to 20, preferably an integer of 1 to 10.) The carbon of the raw material in the production method (via) includes carbon, carbon black, graphite, black lead, activated carbon, and nanometer. Carbon tube, nano carbon fiber, carbon nano angle, fullerene (Fullerene), among which carbon black is particularly preferable. When the particle size of carbon powder is small, the specific surface area becomes large, and it is preferable to react easily with oxide. For example, using carbon black (specific surface area: 100~300m2/g, for example It is preferable to use XC-72) manufactured by Cabot Co., Ltd., etc. Even if the metal carbonitride 2 obtained by using any of the above raw materials is used as a catalyst formed by heating the metal carbonitride 2 obtained by heating in an inert gas containing oxygen. In the case of a direct liquid fuel cell, it is possible to suppress a decrease in the cathode potential by permeation, and the redox energy is excellent and inexpensive. When the amount of the oxide, titanium oxide and carbon (molar ratio) of the metal M2 is controlled, it is obtained. Suitable for metal carbonitrides 2. The amount of addition (molar ratio) is generally 1 mole for titanium oxide, and the oxide of the above metal M2 is 〇.〇〇〇!~:!mol, carbon is 1~1〇 Ear, more than -40-201131873 Preferably, for the titanium oxide 1 mole, the oxide of the aforementioned metal M2 is 0.001 to 0.4 moles of carbon is 2 to 6 moles. More preferably for the titanium oxide 1 mole The oxide of the aforementioned metal M2 is o.ooi~〇.1 mole, and the carbon is 2 to 3 moles. The metal M2 is calcium, strontium, barium, strontium, barium, strontium, giant, cockroach, cockroach, chaos, cockroach When 镝, 鈥, 饵, bait, watch, mirror, 铿, for the titanium oxide 1 mole, the oxide of the metal M2 is 0. 001 〇 〇 〇 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. A tendency to obtain a metal oxycarbonitride 2 having excellent oxygen reduction energy and high activity (manufacturing step of metal oxycarbonitride 2) Next, a metal carbonitride obtained by the production method (vi) such as the above-described production method (via) (2) The step of heating the oxygen-containing inert gas to obtain the metal carbonitride oxide 2 will be described. Examples of the inert gas include nitrogen gas, helium gas, neon gas, hydrogen gas, helium gas, neon gas or helium gas. Nitrogen or argon is preferred because it is easier to get started. The oxygen concentration in the above inert gas depends on the heating time and the heating temperature, preferably 0.1 to 10% by volume, and particularly preferably 0.5 to 5% by volume. When the above oxygen concentration is within the above range, a uniform metal carbonitride oxide 2 can be formed, which is preferable. Further, when the oxygen concentration is less than 0.1% by volume, the oxidation state tends to be unoxidized, and when it exceeds 10% by volume, it tends to be excessively oxidized. -41 - 201131873 In the above inert gas, 'hydrogen is preferably contained in a range of 1% by volume or less. The hydrogen content is preferably from 0.01 to 10% by volume, more preferably from 0.1 to 5% by volume. Further, the gas concentration (% by volume) in the present invention is the standard state. When hydrogen is contained in the above range, a uniform carbon oxynitride can be formed, which is preferable. When there is more than 1 〇 capacity %, there is a tendency to excessively reduce. 加热 The heating temperature in this step is generally in the range of 400 to 1400 ° C, preferably in the range of 600 to 1 200 ° C. When the heating temperature is within the above range, a uniform metal oxycarbonitride 2 can be formed, which is preferable. When the heating temperature is less than 400 ° C, the oxidation tends not to be performed. When the temperature exceeds 140 (the rc or more is oxidized, the crystal tends to grow. The heating method includes a standing method, a stirring method, and The dropping method, the powder trapping method, etc. The standing method is a method in which a metal carbonitride 2 is placed and heated in a stationary electric furnace, etc. Further, an alumina disk and quartz in which a metal carbonitride 2 is weighed are placed. A method of heating by a disk or the like. In the case of the standing method, it is preferable to heat a large amount of the metal carbonitride 2. The stirring method is to stir the metal carbonitride 2' in an electric furnace such as a rotary furnace. In the case of the stirring method, a large amount of the metal carbonitride 2 can be heated, and aggregation and growth of the particles of the metal carbonitride 2 can be suppressed, and it is preferable to carry out the tubular furnace by a standing method, a stirring method, or the like. The heating time of the metal carbonitride 2 is 0.1 to 10 hours, preferably 0.5 to 5 hours. When the heating time is within the above range, the metal salt can be formed to form a uniform metal-carbon oxide-42-201131873 It is preferable to hold the two substances as the tendency of the oxygen temperature to be 2, and the heating time is less than 〇. When 1 hour, the tendency of the metal carbon oxynitride 2 is partially formed. When it exceeds 10 hours, there is a tendency to excessively oxidize. The so-called drop method is to heat the furnace to a predetermined heating temperature while flowing into a furnace containing a trace amount of oxygen inert gas, and to maintain the heat balance at the temperature, in the heating zone of the furnace. The metal carbonitride is dropped in the crucible and heated. The dropping method is preferable because the aggregation and growth of the metal carbonitride 2 particles can be suppressed to a minimum. In the case of the falling method, the metal carbonitride 2 The heating time is generally 0.5 to 10 minutes, preferably 0.5 to 3 minutes. When the heating time is within the former range, the tendency to obtain a uniform metal carbonitride 2 is preferred. When the heating time is less than 0.5 minutes, the heating time is The tendency to partially form gold oxycarbonitride 2 tends to over-progress over 1 minute. The so-called powder capture method is inert in containing trace amounts of oxygen. The metal carbonitride 2 is made to float and float in the body ring, and the metal carbonitride 2 is captured and heated in a vertical tubular furnace at a predetermined heating degree. The powder capture method is the heating of the metal carbonitride 2 The time is 0.2 seconds to 1 minute', preferably 0.2 to 10 seconds. When the heating time is within the range, the tendency to form a uniform metal carbonitride 2 is preferred. If the heating time is less than 0.2 seconds, There is a tendency to form a carbon oxynitride 2 in a partial manner, and there is a tendency to excessively carry out oxygen in excess of one minute. As a catalyst of the present invention, a metal oxycarbonitride 2 can be obtained by the above-mentioned production method or the like -43-201131873 It can be used as it is, but the obtained metal oxycarbonitride 2 can be further pulverized to make it a finer powder. As a method of pulverizing the metal oxycarbonitride 2, for example, a method of rotating a honing machine, a ball honing machine, a medium agitating honing machine, a jet mill, a mortar, a trough, etc. by a roll may be used, and further fine particles may be used. From the viewpoint of the metal oxycarbonitride 2, the method by the jet mill is preferred, and the method of nipple is preferred from the viewpoint of being easily handled in a small amount. <Use> The catalyst of the present invention can be effectively used as a catalyst in a direct liquid fuel cell, and can be effectively used as a substitute catalyst for a platinum catalyst in a direct liquid fuel cell. Further, the catalyst of the present invention is particularly useful as an oxygen reduction catalyst in a direct liquid fuel cell using a liquid fuel such as methanol, ethanol or formic acid. When a platinum catalyst is used as a cathode catalyst in a direct liquid fuel cell, a decrease in cathode potential due to penetration of the aforementioned liquid fuel occurs. As a result, the performance of the direct liquid fuel cell is remarkably lowered. However, when the catalyst of the present invention is used as a cathode catalyst in a direct liquid fuel cell, as described above, even if the liquid fuel is present in the cathode by permeation, the decrease in the cathode potential can be suppressed, and the oxygen reduction energy is excellent and inexpensive. The catalyst layer for a direct liquid fuel cell of the present invention is characterized by containing the aforementioned catalyst. The catalyst layer for a direct liquid fuel cell has an anode catalyst layer and a cathode catalyst layer. In particular, the above-mentioned catalyst is excellent in durability and has a large oxygen reduction energy, and it is possible to suppress the cathode potential of the liquid fuel from permeating from -44 to 201131873, so that it is preferably used for the cathode catalyst layer. In the catalyst layer for a direct liquid fuel cell of the present invention, it is preferred to further contain electron conductive particles. When the catalyst layer for a direct liquid fuel cell containing the above catalyst further contains electron conductive particles, the reduction current can be further increased. Since the electron conductive particles generate an electrical contact capable of inducing an electrochemical reaction due to the above-mentioned catalyst, it is considered to increase the reduction current. The above electron conductive particles are generally used as a carrier for a catalyst. Examples of the material constituting the electron conductive particles include carbon, a conductive polymer, a conductive ceramic material, a metal, or a conductive inorganic oxide such as tungsten oxide or cerium oxide. These may be used singly or in combination. In particular, a carbon particle having a large specific surface area alone or a mixture of carbon particles having a large specific surface area and other electron conductive particles is preferred. In other words, the catalyst layer for a direct liquid fuel cell preferably contains the above-mentioned catalyst and carbon particles having a large specific surface area. As the carbon, carbon black 'graphite, black lead, activated carbon, carbon nanotubes, nano carbon fiber, carbon nanohorn, Fullerene, and the like can be used. If the particle size of carbon is too small, it is not easy to form an electron conduction path. If it is too large, the gas diffusion property of the fuel cell catalyst layer is lowered, and the utilization rate of the catalyst tends to decrease. Therefore, the range of 10 to 100 nm is preferable. It is preferably in the range of 10 to 100 nm. Further, in the present invention, the particle diameter of carbon is measured by a transmission electron microscope (TEM). In the case where the material constituting the electron conductive particles is carbon, the mass ratio of the medium to the carbon of the touch-45-201131873 (catalyst: electron conductive particles) is preferably 0.5:1 to 1 〇〇〇:1. Good for 1: 1 to 100: 1, better for 4: 1 to 10: 1. The conductive polymer is not particularly limited, and examples thereof include polyacetylene, poly-P-phenylene, polyaniline, polyalkylaniline, polypyrrole, polythiophene, polyfluorene, poly-1,5-di. Aminoguanidine, polyaminodiphenyl, poly(anthracene-phenylenediamine)' poly(quinoline key) salt, polyazole, polyquinoxaline, polyphenylhydrazine, and the like. Among them, polypyrrole, polyaniline and polythiophene are preferred, and polypyrryl D is preferred. The polymer electrolyte is not particularly limited as long as it is generally used as a catalyst layer for a direct liquid fuel cell. Specifically, a perfluorocarbon polymer having a sulfonic acid group (for example, NAFION (registered trademark) (DUp〇nt Corporation 5% NAFION (registered trademark) solution (DE521)), etc.), a hydrocarbon having a sulfonic acid group A polymer compound, a polymer compound in which a mineral acid such as phosphoric acid is doped, an organic/inorganic hybrid polymer partially substituted with a proton conductive functional group, a proton conductor in which a polymer matrix is impregnated with a phosphoric acid solution or an aqueous sulfuric acid solution, or the like. Among them, NAFION (registered trademark) (Dupont 5% NAFION (registered trademark) solution (DE521)) is preferred. As a method of dispersing the above-mentioned catalyst on the electron conductive particles of the carrier, methods such as gas flow dispersion and liquid dispersion are exemplified. The dispersion in the liquid is such that the catalyst and the electron conductive particles are dispersed in the solvent, and the catalyst layer forming step for the direct liquid fuel cell can be preferably carried out. Examples of the dispersion in the liquid include a method of shrinking a flow by a hole, a method of breaking a flow by a rotary line, or a method by ultrasonic. The solvent which can be used in the dispersion in the liquid does not erode the catalyst or the electron conductive particles can be dispersed without any particular limitation. -46- 201131873 A volatile liquid organic solvent or water is used. Further, when the catalyst is dispersed on the electron conductive particles, the electrolyte and the dispersant can be dispersed at the same time. The method of forming the catalyst layer for the direct liquid fuel cell is not particularly limited, and for example, a suspension containing the catalyst and the electron conductive particles and the electrolyte is applied to an electrolyte membrane or a gas diffusion layer to be described later. method. Examples of the coating method include a dipping method, a screen printing method, a roll coating method, and a spray method. In addition, a catalyst layer for a direct liquid fuel cell is formed on a substrate by a coating method or a filtration method, and a suspension liquid containing the catalyst and the electron conductive particles and the electrolyte is applied to the electrolyte membrane by a transfer method. A method of forming a catalyst layer for a direct liquid fuel cell. The electrode for a direct liquid fuel cell of the present invention is characterized by having the above-described catalyst layer for a direct liquid fuel cell and a porous support layer. The porous support layer is a layer of a diffusion gas (hereinafter also referred to as a "gas diffusion layer"). As the gas diffusion layer, if it has electron conductivity, the gas diffusion property is high and the corrosion resistance is high. Generally, a carbon-based porous material such as carbon paper or carbon cloth, or a stainless steel or a coated corrosion-resistant material to be lightweight can be used. Aluminum foil. The membrane electrode assembly of the present invention is a membrane electrode assembly for a direct liquid fuel cell comprising an electrolyte membrane disposed between a cathode and an anode and between the cathode and the anode, wherein the cathode and/or the anode are the direct liquid An electrode for a fuel cell is characterized. The direct liquid fuel cell of the present invention is characterized by comprising the membrane electrode assembly for a direct liquid fuel cell. [47] [Embodiment] [Embodiment] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these embodiments. Further, various measurements in the examples and comparative examples can be carried out by the following methods. [Analytical method] 1. Powder X-ray diffraction Powder X-ray diffraction of a sample was carried out using Roterflex manufactured by Rigaku Corporation and X'Pert Pro manufactured by PANalytical. The number of diffraction line peaks in the powder X-ray diffraction of each sample is calculated by using a signal whose signal (S) and noise (N) ratio (S/N) is 2 or more as one peak. Moreover, the noise (N) is the width of the bottom line. 2. Elemental analysis Carbon: The sample was taken for approximately O.lg and was measured by a carbon analyzer (EMIA-1 1〇). Nitrogen and oxygen: The sample was weighed in approximately 0.3 g. After the Ni-Cup was sealed, it was measured by an ON analyzer (manufactured by Leco Co., Ltd., Model TC600).铌, titanium and other metals: Weigh the sample about 〇. lg in the uranium dish, add acid for thermal decomposition. The heated decomposition product was diluted to a constant volume and quantified by ICP-MS (ICP-OESVISTA-PRO type manufactured by SII Corporation). -48 - 201131873 [Example 1] (NbaFebCxNyOz) 1. Catalyst preparation: 5.8 8g (5 6mmol) of niobium carbide (NbC, manufactured by Tatsukawa Chemical Co., Ltd.) and second iron oxide (Fe203, Co., Ltd.)纯度.4(^(2.5111111〇1) and tantalum nitride (>^^[, manufactured by High Purity Chemical Research Institute Co., Ltd.) 5.14g (1 2 38mm〇l) fully The mixture was pulverized and mixed, and the mixed powder was subjected to a tubular furnace at 1,600 ° C for 3 hours, and heated in a nitrogen atmosphere to obtain 11.19 g of a metal carbonitride (1) containing iron and lanthanum. The nitride (1) is pulverized by a ball honing machine. The pulverized metal carbonitride (1) 1. 〇〇g is flowed under nitrogen containing 1% by volume of oxygen and 0.8% by volume of hydrogen. The furnace was heated at 9000 ° C for 6 hours to obtain 1.24 g of metal oxycarbonitride containing iron and cerium (hereinafter also referred to as "catalyst (!)"). Elemental analysis of the obtained catalyst (1) The results are shown in Table 1. The X-ray diffraction spectrum of the catalyst (1) was as shown in Fig. 8. The diffraction angle was 2Θ = 33° to 43°. Four diffraction line peaks were observed. -49-1 Manufacturing of fuel cell electrodes 2 The oxygen reduction energy was measured as follows. Catalyst (l) 〇.〇95g and carbon (XC-72 manufactured by Cabot) 0.005 g is placed in a solution of isopropyl alcohol: pure water = 2: 3 1 in a mass ratio of 1 〇g in a mixture of ultrasonic waves to obtain a suspension. The suspension is applied to a carbon glass rotating electrode (Beidou) The diameter of the electrician company: 5mm) 'The amount of the catalyst is 2mg' is fully dried in the air 201131873. Further coating will be NAFION (registered trademark) (Dupont 5% NAFION (registered trademark) solution (DE521) ) 10 μί diluted to 1 × times with pure water, and sufficiently dried in air to obtain an electrode (1-1) for a fuel cell. 3. Evaluation of oxygen reduction energy in the absence of methanol in an aqueous sulfuric acid solution in an aqueous sulfuric acid solution The catalyst energy (oxygen reduction energy) of the fuel cell electrode (1-1) in the absence of methanol was evaluated by the following method. First, the fuel cell electrode (1-1) was fabricated in a saturated oxygen atmosphere at 0.5. In a molar solution of mol/L sulfuric acid, a potential sweep of 3 (TC, 5 mV/sec) The scanning speed is subjected to polarization, and the current-potential curve is measured. At this time, a reversible hydrogen electrode (RHE) in the same concentration of sulfuric acid aqueous solution is used as a reference electrode. In this embodiment, the measurement (liquid fuel such as no methanol) is at the oxygen reduction current. The potential of the density - ΙΟΟμΑ/cm2 was used as "E0xygen". The catalytic energy (oxygen reduction energy) of the fuel cell electrode (1-1) produced was evaluated by "E0xygen". In other words, the higher the "E0xygen" is, the higher the catalyst energy (oxygen reduction energy) of the fuel cell electrode (1-1) is displayed. Fig. 9 shows a current-potential curve obtained by the above measurement. It is known that the fuel cell electrode (1-1) has an ugly ~^^ of 0.83 V (vs. RHE) and has high oxygen reduction energy. 4. Evaluation of oxygen reduction energy in the presence of methanol in a sulfuric acid aqueous solution, changing a 0.5 mol/L aqueous sulfuric acid solution to a 0.5 m ο 1 / L sulfuric acid aqueous solution containing 0.5 mol/L of a-50-50 201131873 alcohol, 3 The current-potential curve was measured in the same manner, and the oxygen reduction energy of the fuel cell electrode (1-1) in the presence of methanol in the sulfuric acid aqueous solution was evaluated. In the present embodiment, the measurement (having a liquid fuel such as methanol) is referred to as "EFuel + 0xygen" at a potential of an oxygen reduction current density of ΙΟΟμΑ/cm2. Fig. 10 shows a graph comparing the current-potential curve obtained by the measurement (with methanol) and the current-potential curve obtained by the measurement in the above 3 (without methanol). When the fuel cell electrode (1 -1) was present in methanol in an aqueous sulfuric acid solution, EFuel + 0xygen was 0.80 V (vs_RHE), and EOxygen (0.83 V (vs. RHE)) obtained by measuring (without methanol) in the above 3 was obtained. Has almost the same high oxygen reduction energy. The oxygen reduction potential ratio (EFUei + 〇xygen/E0xygen) was 0.96. In other words, when the electrode (1 -1) of the catalyst for a fuel cell produced in the first embodiment is used, even when a direct methanol fuel cell (DMFC) using methanol as a liquid fuel is used, methanol can be suppressed by methanol. The cathodic potential of the infiltration is lowered, indicating excellent oxygen reduction energy. 5. Evaluation of oxygen reduction energy in the absence of ethanol in an aqueous sulfuric acid solution A new fuel cell electrode (1-2) was produced in the same manner as in the above. The catalyst energy (oxygen reduction energy) of the fuel cell electrode (1-2) in the absence of ethanol in the aqueous sulfuric acid solution was evaluated by the following method. First, the produced fuel cell electrode (I·2) ' was subjected to polarization at a potential scanning rate of 30 ° C ' 5 mV / sec in a saturated oxygen atmosphere in a 0.5 mol / L sulfuric acid aqueous solution, and the current-potential curve was measured. At this time, a reversible hydrogen electrode (RHE) in the same concentration of -51 - 201131873 sulfuric acid aqueous solution was used as a reference electrode. It is known that the fuel cell electrode (1-2) has a high oxygen reduction energy of 0.78 V (vs. RHE). 6. Evaluation of oxygen reduction energy in the presence of ethanol in a sulfuric acid aqueous solution The current-potential was measured in the same manner as in the above except that a 0.5 mol/L sulfuric acid aqueous solution was changed to a 0.5 mol/L sulfuric acid aqueous solution containing 0 to 5 mol/L of ethanol. The curve was evaluated for the oxygen reduction energy of the fuel cell electrode (1-2) in the presence of ethanol in an aqueous sulfuric acid solution. Fig. 11 is a graph showing a comparison of a current-potential curve ' obtained by the measurement (with ethanol) and a current-potential curve obtained by the above measurement (without ethanol). When the fuel cell electrode (1-2) produced in Example 1 was found to have ethanol in an aqueous sulfuric acid solution, EFuel + 0xygen was 0.78 V (vs. RHE), which was measured in the above 5 (no ethanol). EOxygen (0_78V (vs. RHE)) has the same local oxygen reduction energy). The oxygen reduction potential ratio (EFuel + Oxygen / E 〇 xygen) was 1 · 0 0. In other words, when the electrode (1-2) of the fuel cell catalyst produced in Example 1 is a direct Ethanol fuel cell (DEFC) using ethanol as a liquid fuel, it is possible to suppress the use of ethanol. The cathodic potential of the permeation is lowered, indicating excellent oxygen reduction energy. 7. Evaluation of oxygen reduction energy in the absence of formic acid in an aqueous sulfuric acid solution A new fuel cell electrode (1-3) was produced in the same manner as in the above 2. -52- 201131873 The catalyst energy (oxygen reduction energy) of the fuel cell electrode (丨·3) in the absence of formic acid in an aqueous sulfuric acid solution was evaluated by the following method. First, the produced fuel cell electrode (1-3) was subjected to a polarization-measurement current-potential curve at a potential scanning rate of 30 ° C and 5 mV / sec in a saturated oxygen atmosphere in a 0.5 mol/L sulfuric acid aqueous solution. At this time, a reversible hydrogen electrode (RHE) in the same concentration of sulfuric acid aqueous solution was used as a reference electrode. It is known that the fuel cell electrode (1-3) has a high oxygen reduction energy of 0.78 V (vs. RHE). 8. Evaluation of oxygen reduction energy in the presence of formic acid in a sulfuric acid aqueous solution The current-potential was measured in the same manner as in the above 7 except that a 0.5 mol/L sulfuric acid aqueous solution was changed to a 0.5 mol/L sulfuric acid aqueous solution containing 0.5 mol/L of formic acid. The curve was used to evaluate the oxygen reduction energy of the fuel cell electrode (1-3) in the presence of formic acid in an aqueous sulfuric acid solution. Fig. 12 is a graph showing a comparison of a current-potential curve obtained by the measurement (with formic acid) and a current-potential curve obtained by measuring (without formic acid) in the above 7. It is known that the electrode for fuel cell (1-3) has EF. ) (0.78 ¥ ^ 3.1 ^ £)) Almost has the same high oxygen reduction target to ° oxygen source potential ratio (EFue 丨 + 0xygen / E 〇 xygen) is 0.99. That is, the electrode (!-3) of the fuel cell catalyst produced in Example 1 is a direct Fotmie Acid Fuel Cell (DFAFC) using formic acid as a fuel, and the penetration by formic acid can be suppressed. -53- 201131873 The cathode potential is lowered, showing excellent oxygen reduction energy. [Example 2] (TiaLabCxNyOz) 1. Preparation of catalyst: 3.53 g (44.12 mmol) of titanium oxide (Ti02, manufactured by Showa Denko, SUPER-TITANIAF6), and lanthanum oxide (La203, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.144 g (0.44 mmol) And carbon (manufactured by Cabot Co., Ltd., Vulcan 72) 1.33 g (110 mmmol) was sufficiently pulverized and mixed. The mixed powder was heated in a nitrogen atmosphere at a temperature of 1 800 ° C for 3 hours to obtain a metal carbonitride (2) containing 2.52 g of titanium and niobium (about 2 mol% for titanium). . This will be broken by the mortar. 1.0 g of the obtained metal carbonitride (2) was introduced into a nitrogen gas containing 2% by volume of oxygen and 4% by volume of hydrogen, and heated in a tubular furnace at 1 000 ° C for 3 hours to obtain a metal containing niobium and titanium. Carbonitride (hereinafter also referred to as "catalyst (2)"). 1.2 7g. The elemental analysis results of the obtained catalyst (2) are shown in Table 1. Further, the powder X-ray diffraction spectrum of the catalyst (2) is as shown in Fig. 13. 2. The fuel cell electrode was produced in the same manner as in the second embodiment except that the catalyst (2) was used. Electrode (2-1). 3. Evaluation of oxygen reduction energy in the absence of methanol in the aqueous sulfuric acid solution The use of the fuel cell electrode (2-1) was carried out in the same manner as in Example 1 and the same as -54 to 201131873, and methanol was not present in the aqueous sulfuric acid solution. The evaluation of the oxygen reduction energy of the fuel cell electrode (2 -1 ). Figure 14 shows the current-potential curve obtained by this measurement. It is known that the fuel cell electrode (2-1) has an ugly value of 0.83 V (vs. RHE) and has high oxygen reduction energy. 4. Evaluation of oxygen reduction energy in the presence of methanol in an aqueous sulfuric acid solution using the aforementioned fuel The evaluation of the oxygen reduction energy of the fuel cell electrode (2-1) in the presence of methanol in a sulfuric acid aqueous solution was carried out in the same manner as in the fourth embodiment of the battery electrode (2-1). Fig. 15 shows the comparison by A graph of the current-potential curve obtained by the measurement (with methanol) and the current-potential curve obtained by the measurement of the above 3 (without methanol). It is known that the fuel cell electrode (2-1) exists even in an aqueous sulfuric acid solution. In the case of methanol, 0.83 V (vs. RHE) has the same high oxygen reduction energy as EOxygen (0.83 V (vs. RHE)) obtained by the above measurement (without methanol). Oxygen reduction potential ratio (EFuel + Oxygen/E〇) The xygen) is 1.00. That is, the electrode (2-1) using the fuel cell catalyst produced in the second embodiment is a direct methanol fuel cell (Direct Methanol Fuel Cell, D MFC) used for using methanol as a liquid fuel. ), can suppress the decrease of the cathode potential by the permeation of methanol, showing excellent oxygen 5. Reduction of oxygen reduction energy in the absence of ethanol in the aqueous sulfuric acid solution The electrode for new fuel cell (2-2) was produced in the same manner as in the above 2. -55- 201131873 The electrode for the fuel cell described above was used (2- 2) The evaluation of the oxygen reduction energy of the fuel cell electrode (2-2) in the absence of ethanol in the sulfuric acid aqueous solution was carried out in the same manner as in Example 5, except that the fuel cell electrode (2-2) was known. E0xygen is 〇.85V (vs. RHE) and has high oxygen reduction energy. 6. Evaluation of oxygen reduction energy in the presence of ethanol in an aqueous sulfuric acid solution using the fuel cell electrode (2-2) and the sixth embodiment Similarly, the evaluation of the oxygen reduction energy of the fuel cell electrode (2-2) in the presence of ethanol in an aqueous sulfuric acid solution was carried out. Fig. 16 shows a comparison of the current-potential curve obtained by the measurement (with ethanol), and by A graph of the current-potential curve obtained by the measurement of the above 5 (without ethanol). It is known that the fuel cell electrode (2-2) is 0.84 V (vs. RHE) even when ethanol is present in the sulfuric acid aqueous solution, and the above 5 The EOxygen (0.85V (vs. RHE)) obtained by measuring (without ethanol) is almost There is an equivalent high oxygen reduction energy. The oxygen reduction potential ratio (Ej?ue| + 〇Xygen/E〇Xygen) is 0.99. That is, even if the fuel cell catalyst electrode (2-2) produced in Example 2 is used, In the case of Direct Ethanol Fuel Cell (DEFC) using ethanol as a liquid fuel, the decrease in cathode potential by permeation of ethanol can be suppressed, and excellent oxygen reduction energy can be exhibited. 7. Evaluation of oxygen reduction energy in the absence of formic acid in an aqueous sulfuric acid solution A new fuel cell electrode (2-3) was produced in the same manner as in the above. -56-201131873 The evaluation of the oxygen reduction energy of the fuel cell electrode (2-3) in the absence of formic acid in a sulfuric acid aqueous solution was carried out in the same manner as in the seventh embodiment except for the fuel cell electrode (2-3). . It is known that the fuel cell electrode (2-3) has a high oxygen reduction energy of 〇.85V (vs. RHE). 8. Evaluation of oxygen reduction energy in the presence of formic acid in the aqueous sulfuric acid solution The electrode for a fuel cell in the presence of formic acid in a sulfuric acid aqueous solution was used in the same manner as in the eighth embodiment of the fuel cell (2-3). 2-3) Evaluation of oxygen reduction energy. Fig. 17 is a graph showing a comparison of a current-potential curve obtained by the measurement (with formic acid) and a current-potential curve obtained by the above-mentioned 7 (without formic acid). It is known that the fuel cell electrode (2-3) has a formic acid in an aqueous sulfuric acid solution, and £!^1 + 0)^611 is 〇.83V (vs. RHE), and is determined by the above 7 (without formic acid). The resulting EOxygen (0.85 V (vs. RHE)) has almost the same high oxygen reduction energy. The oxygen reduction potential ratio (EFuel + 0xygen / E0xygen) was 0.98. In other words, the electrode (2-3) using the fuel cell catalyst produced in the second embodiment can be inhibited by formic acid even if it is used in a direct formic acid fuel cell (DFAFC) using formic acid as a fuel. The cathodic potential of the infiltration is lowered, indicating excellent oxygen reduction energy. [Comparative Example 1] (Pt/C) 1. Modulation of a catalyst -57- 201131873 A uranium-supported carbon catalyst (manufactured by E-TEK, 20.0% by weight) was used as a catalyst (Cl). 2. Production of electrode for fuel cell The measurement of oxygen reduction energy was carried out as follows. The catalyst (C 1) 1 Omg was placed in pure water 5. OmL, stirred by ultrasonic waves, and the county was turbid. The turbid liquid of the county was applied to a carbon glass rotating electrode (manufactured by Hokuto Denko Co., Ltd., diameter: 5.0 mm), and sufficiently dried in the air. Further, NAFION (registered trademark) (Dupont 5% NAFION (registered trademark) solution (DE521)) was diluted with pure water to a 10-fold ratio of 1 μμί, and dried sufficiently in air to obtain an electrode for a fuel cell ( C 1-1). 3. Evaluation of oxygen reduction energy in the absence of methanol in the aqueous sulfuric acid solution The fuel cell in the absence of methanol in the sulfuric acid aqueous solution was used in the same manner as in the third embodiment except for the fuel cell electrode (C 1-1). Evaluation of the oxygen reduction energy of the electrode (C1-1). Fuel cell electrode (C1-1) £〇"8 <:11 is 0.96 V (vs. RHE). 4. Evaluation of oxygen reduction energy in the presence of methanol in the sulfuric acid aqueous solution The fuel cell electrode in the presence of methanol in the sulfuric acid aqueous solution was used in the same manner as in the fourth embodiment except for the fuel cell electrode (C 1-1). Evaluation of the oxygen reduction energy of (Cl-ι). Fig. 18 is a graph showing a comparison of a current-potential curve obtained by the measurement (with methanol) and a current-potential curve obtained by the above measurement (without methanol) -58-201131873. When the fuel cell electrode (c丨_丨) was present in the presence of methanol in the aqueous sulfuric acid solution, EFuel + 0xygen was 〇.58V (vs. RHE), which was higher than that of the above 3 (no methanol) E〇xygen (0.96). V(vs.RHE)) decreases more 'and reduces oxygen reduction energy. The oxygen reduction potential ratio (EFuel + 0xygen / E0xygen) was 0.60. That is, the electrode (C1-1) using the platinum-carrying carbon catalyst of Comparative Example 1 was used for direct methanol fuel cell (DMFC) using methanol as a liquid fuel, and it was shown to be infiltrated by methanol. The cathode potential is lowered. 5. Evaluation of oxygen reduction energy in the absence of ethanol in an aqueous sulfuric acid solution A new fuel cell electrode (C1-2) was produced in the same manner as in the above. The fuel cell electrode (C1-2) is evaluated for the oxygen reduction energy of the fuel cell electrode (C1-2) in the absence of ethanol in the sulfuric acid aqueous solution, except for the fuel cell electrode (C1-2). The ugly ^(1) of the electrode (C1-2) was 0.94 V (vs. RHE). 6. Evaluation of oxygen reduction energy in the presence of ethanol in the sulfuric acid aqueous solution The fuel cell power in the presence of ethanol in the sulfuric acid aqueous solution was carried out in the same manner as in the sixth embodiment except that the fuel cell electrode (C1-2) was used. Evaluation of the oxygen reduction energy of the pole (C 1 - 2). Fig. 19 is a view showing a comparison of a current-potential curve ' obtained by the measurement (with ethanol) and a current-potential curve obtained by the above 5 (without ethanol) -59 - 201131873. When the fuel cell electrode (Cl-2) was present in ethanol in an aqueous sulfuric acid solution, EFuel + 0xygen was 0.5 3 V (vs. RHE), which was EOxygen (0.94 V (vs. RHE) obtained by the above 5 measurement (no ethanol). )) more greatly reduces 'and reduces oxygen reduction energy. The oxygen reduction potential ratio (EFuel + 0xygen/E0xygen) was 0.56 〇, that is, the platinum-carrying carbon catalyst electrode (C1_2) in Comparative Example 1 was used for a direct ethanol fuel cell using ethanol as a liquid fuel (Direct Ethanol Fuel). Cell, DEFC) shows a decrease in cathodic potential by permeation of ethanol. 7. Evaluation of oxygen reduction energy in the absence of formic acid in an aqueous sulfuric acid solution A new fuel cell electrode (C1-3) was produced in the same manner as in the above. The evaluation of the oxygen reduction energy of the fuel cell electrode (C1-3) in the absence of formic acid in the sulfuric acid aqueous solution was carried out in the same manner as in the seventh embodiment except that the fuel cell electrode (C1-3) was used. E0xygeng 〇.94V (vs. RHE) of the fuel cell electrode (C1-3). Figure 60-201131873. When the fuel cell electrode (Cl-3) was present in the sulfuric acid aqueous solution, the EFue dike xygen became 0.32 V (vs. RHE), which was EOxygen (0.94 (vs. RHE) obtained from the above 7 measurement (without formic acid). )) is more greatly reduced, and reduces oxygen reduction energy. The oxygen reduction potential ratio (EFuei + 0xygen/E0xygen) was 0.34. That is, the electrode (C 1-3) using the platinum-supporting carbon catalyst in Comparative Example 1 was used for the direct formic acid fuel cell (DFAFC) using formic acid as a fuel, and it was shown by formic acid. The cathodic potential of the permeation is reduced. [Example 3] (TiaCxNyOz) 1. Preparation of a catalyst Titanium oxide (Ti02, SUPER-TITANIAF6, manufactured by Showa Denko) 3.53 g (44.12 mmol) and carbon (Vu 1 c an 7 2 manufactured by Cabot Co., Ltd.) 1 3 3 g (llOmmmol) was thoroughly pulverized and mixed. The mixed powder was placed in a tubular furnace and heated in a nitrogen atmosphere at 1,800 °C for 3 hours to obtain 2.50 g of a metal carbonitride (3) containing titanium. This will be broken by the mortar. 1.0 g of the broken metal carbonitride (3) was introduced into a nitrogen gas containing 2% by volume of oxygen and 4% by volume of hydrogen, and heated in a tubular furnace at 1000 ° C for 3 hours to obtain a metal-nitrogen oxide containing titanium. (hereinafter also referred to as "catalyst (3)"). 1.24g. The elemental analysis results of the obtained catalyst (3) are shown in Table 1. Further, the powder X-ray diffraction spectrum of the catalyst (3) is shown in Fig. 21. 2. Manufacture of fuel cell electrode -61 - 201131873 A fuel cell electrode (3-1) was obtained in the same manner as in the first embodiment except that the catalyst (3) was used. 3. Evaluation of oxygen reduction energy in the absence of methanol in the aqueous sulfuric acid solution The fuel cell was used in the absence of methanol in the sulfuric acid aqueous solution, except for the fuel cell electrode (3-1). Evaluation of the oxygen reduction energy of the electrode (3-1). Fig. 22 shows a current-potential curve obtained by the measurement. It is known that the ugly 0)^611 of the fuel cell electrode (3-1) is 〇.73V (vs. RHE) and has high oxygen reduction energy. 4. Evaluation of oxygen reduction energy in the presence of methanol in the sulfuric acid aqueous solution The fuel cell electrode in the presence of methanol in the sulfuric acid aqueous solution was used in the same manner as in the fourth embodiment except for the fuel cell electrode (3-1). 3-1) Evaluation of oxygen reduction energy. Fig. 23 is a graph showing a comparison of a current-potential curve obtained by the measurement (with methanol) and a current-potential curve obtained by the above measurement (without methanol). When the fuel cell electrode (3 -1) was present in methanol in an aqueous sulfuric acid solution, EFuel + 0xygen was 0.73 V (vs. RHE), and EOxygen (0.73 V (vs.) obtained from the above measurement (without methanol). RHE)) has the same high oxygen reduction energy. The oxygen reduction potential ratio (Efuei + Oxygen / Eoxygen) was 1.00. In other words, when the electrode (3-1) for the fuel cell catalyst produced in Example 3 is used for a direct methanol fuel cell-62-201131873 (Direct Methanol Fuel Cell, DMFC) using methanol as a liquid fuel, it can be suppressed. The cathode potential is lowered by the permeation of methanol, showing excellent oxygen reduction energy. 5. Evaluation of oxygen reduction energy in the absence of ethanol in an aqueous sulfuric acid solution A new fuel cell electrode (3-2) was produced in the same manner as in the above. The evaluation of the oxygen reduction energy of the fuel cell electrode (3-2) in the absence of ethanol in the sulfuric acid aqueous solution was carried out in the same manner as in the fifth embodiment of the fuel cell electrode (3-2). The fuel cell electrode (3-2) is £0) [^11 is 〇.73V (vs. RHE) and has high oxygen reduction energy. 6. Evaluation of oxygen reduction energy in the presence of ethanol in the sulfuric acid aqueous solution The fuel cell electrode in the presence of ethanol in the sulfuric acid aqueous solution was used in the same manner as in the sixth embodiment except for the fuel cell electrode (3-2). 3 - 2) Evaluation of oxygen reduction energy. Fig. 24 is a graph showing a comparison of a current-potential curve obtained by the measurement (with ethanol) and a current-potential curve obtained by the above measurement (without ethanol). It was found that the fuel cell electrode (3-2) had an EFuel + 0xygen of 0.73 V (vs. RHE) even in the presence of ethanol in an aqueous sulfuric acid solution, and EOxygen (0.73 V (vs.) obtained by the above measurement (without ethanol). RHE)) has the same high oxygen reduction energy. The oxygen S original potential ratio (EFuel + 〇xygen/E〇xygen) is 1 · 0 0. That is, the electrode (3 _ 2) using the fuel cell catalyst produced in Example 3 can be suppressed even when used in a direct ethanol fuel cell-63-201131873 (Direct Ethanol Fuel Cell, DEFC) using ethanol as a liquid fuel. The cathode potential was lowered by the permeation of ethanol, showing excellent oxygen reduction energy. 7. Evaluation of oxygen reduction energy in the absence of formic acid in an aqueous sulfuric acid solution A new fuel cell electrode (3-3) was produced in the same manner as in the above. The evaluation of the oxygen reduction energy of the fuel cell electrode (3_3) in the absence of formic acid in the sulfuric acid aqueous solution was carried out in the same manner as in the seventh embodiment except that the fuel cell electrode (3-3) was used. The E0xygen of the fuel cell electrode (3-3) has a high oxygen reduction energy of 0.73 V (vs. RHE). 8. Evaluation of oxygen reduction energy in the presence of formic acid in the sulfuric acid aqueous solution The fuel cell electrode in the presence of formic acid in the sulfuric acid aqueous solution was carried out in the same manner as in the eighth embodiment except the fuel cell electrode (3-3). 3-3) Evaluation of oxygen reduction energy. Fig. 25 is a graph showing a comparison of a current-potential curve obtained by the measurement (with formic acid) and a current-potential curve obtained by the above measurement (without formic acid). It is known that the fuel cell electrode (3-3) has an EFue 丨 + 0xygen of 0.73 V (vs. RHE) even when sulfuric acid is present in the sulfuric acid aqueous solution, and is ugly with the above 7 measurement (without formic acid) [^ <: 11 (0.73 乂 ^ 8.11 ^)) has the same high oxygen reduction energy. The oxygen reduction potential ratio (Efuel + Oxygen/Eoxygen) is 1.〇〇. In other words, the electrode (3-3) of the catalyst for a fuel cell produced in the third embodiment can be used even when it is used in a direct formic acid fuel cell (DFAFC) of 64-201131873 (DFAFC). The decrease in the cathode potential by the penetration of formic acid is suppressed, showing excellent oxygen reduction energy. [Example 4] (NbCxNyOz) 1. Catalyst preparation: 4.96 g (81 mmol) of niobium carbide (NbC, manufactured by Tatsukawa Chemical Co., Ltd.) and niobium oxide (Nb〇2, Co., Ltd. High Purity Chemical Research Institute) 1.58 (1〇111111〇1) and tantalum nitride (>^>1, manufactured by High Purity Chemical Research Laboratory Co., Ltd.) 54.54g (10mmol) were sufficiently pulverized and mixed. The mixed powder was heated in a tubular furnace at 600 ° C for 3 hours in a nitrogen atmosphere to obtain 2.70 g of a metal carbonitride (4) containing cerium. The sintered metal carbonitride (4) was pulverized in a ball honing machine. The pulverized metal carbonitride (4)1.〇g- flows into a nitrogen gas containing 2% by volume of oxygen and 4% by volume of hydrogen, and is heated in a tubular furnace at 1000 ° C for 3 hours to obtain a metal carbon containing ruthenium. Nitrogen oxide (hereinafter also referred to as "catalyst (4)"). 1. 3 4g. The elemental analysis results of the obtained catalyst (4) are shown in Table 1. Further, the powder X-ray diffraction spectrum of the catalyst (4) is shown in Fig. 26. 2. Production of fuel cell electrode The fuel cell electrode (2-1) was obtained in the same manner as in Example 1 (2) except for the above-mentioned catalyst (1 2). -65- 1 Evaluation of oxygen reduction energy in the absence of methanol in a sulfuric acid aqueous solution 2 Except that the fuel cell electrode (2-1) was used, and in the same manner as in Example 1 3 and 201131873, methanol was not present in the sulfuric acid aqueous solution. Evaluation of the oxygen reduction energy of the fuel cell electrode (4-1). Fig. 27 shows a current-potential curve obtained by the measurement. It was found that the fuel cell electrode (4-1) had an E0xygen of 0.72 V (vs. RHE) 1 and had high oxygen reduction energy. 4. Evaluation of oxygen reduction energy in the presence of methanol in the sulfuric acid aqueous solution The fuel cell electrode in the presence of methanol in the sulfuric acid aqueous solution was used in the same manner as in the fourth embodiment except for the fuel cell electrode (4-1). 4-1) Evaluation of oxygen reduction energy. Fig. 28 is a graph showing a comparison of a current-potential curve obtained by the measurement (with methanol) and a current-potential curve obtained by the above measurement (without methanol). It was found that the fuel cell electrode (4-1) had EFuel + 0xygen of 0.72 V (vs. RHE) even when methanol was present in the sulfuric acid aqueous solution, and EOxygen (0.72 V (vs.) obtained by the above measurement (without methanol). RHE)) has the same high oxygen reduction energy. The oxygen reduction potential ratio (EFuei + 〇xygen/E〇xygen) was 1.00. In other words, when the electrode (4-1) of the fuel cell catalyst produced in the fourth embodiment is used, even when a direct methanol fuel cell (DMFC) using methanol as a liquid fuel is used, methanol can be suppressed. The cathode potential of the permeation is lowered, indicating excellent oxygen reduction energy. 5. Evaluation of oxygen reduction energy in the absence of ethanol in an aqueous sulfuric acid solution. The electrode for a new fuel cell is produced in the same manner as the above 2 (4-2) » -66- 201131873 The evaluation of the oxygen reduction energy of the fuel cell electrode (4-2) in the absence of ethanol in the sulfuric acid aqueous solution was carried out in the same manner as in the fifth embodiment of the fuel cell electrode (4-2). It is known that the fuel cell electrode (4-2) has a high oxygen reduction energy of 0.72 V (vs. RHE). 6. Evaluation of oxygen reduction energy in the presence of ethanol in the sulfuric acid aqueous solution The fuel cell electrode in the presence of ethanol in the sulfuric acid aqueous solution was used in the same manner as in the sixth embodiment except for the fuel cell electrode (4-2). 4-2) Evaluation of oxygen reduction energy. Fig. 29 is a graph showing a comparison of a current-potential curve obtained by the measurement (with ethanol) and a current-potential curve obtained by the above measurement (without ethanol). It was found that the fuel cell electrode (4-2) had an EFuel + 0xygen of 0.72 V (vs. RHE) even when ethanol was present in the sulfuric acid aqueous solution, and EOxygen (0.72 V (vs.) obtained by the above measurement (without ethanol). RHE)) has the same high oxygen reduction energy. The oxygen reduction potential ratio (EFuel + Oxygen / E 〇 Xygen) was 1.00. In other words, the electrode (4-2) using the fuel cell catalyst produced in the fourth embodiment can be suppressed by using the direct Ethanol fuel cell (DEFC) using ethanol as a liquid fuel. The cathode potential of the penetration of ethanol is lowered, showing excellent oxygen reduction energy. 7. Evaluation of oxygen reduction energy in the absence of formic acid in an aqueous sulfuric acid solution A new fuel cell electrode (4-3) was produced in the same manner as in the above. -67-201131873 The oxygen reduction energy of the fuel cell electrode (4_3) in the absence of formic acid in a sulfuric acid aqueous solution was carried out in the same manner as in the seventh embodiment except for the fuel cell electrode (4-3). . It was found that the E0xygen of the fuel cell electrode (4-3) was 0.72 V (vs. RHE) and had high oxygen reduction energy. 8. Evaluation of oxygen reduction energy in the presence of formic acid in the aqueous sulfuric acid solution The fuel cell electrode in the presence of formic acid in the sulfuric acid aqueous solution was carried out in the same manner as in the eighth embodiment except the fuel cell electrode (4-3). 4-3) Evaluation of oxygen reduction energy. Fig. 30 is a graph showing a comparison of a current-potential curve obtained by the measurement (with formic acid) and a current-potential curve obtained by the above measurement (without formic acid). The electrode for fuel cell (4-3) has EFuel + 0xygen of 0.72 V (vs. RHE) even in the presence of formic acid in an aqueous sulfuric acid solution, and EOxygen (0.72 V (vs. RHE) obtained by the measurement of the above 7 (without formic acid). ) has the same high oxygen reduction energy. The oxygen reduction potential ratio (EFuel + 0xygen / E0xygen) was 1.00. In other words, the electrode (4-3) using the fuel cell catalyst produced in the fourth embodiment can be suppressed by using the direct formic acid fuel cell (DFAFC) using formic acid as a fuel. The cathodic potential of the infiltration of formic acid is lowered, showing excellent oxygen reduction energy. [Example 5] (TiaSmbCxNyOz) 1. Preparation of Catalyst-68- 201131873 Titanium oxide (Ti〇2, SUPER-TITANIAF6 by Showa Denko) 3.53 g (44.12 mmol), yttrium oxide (Sm203 manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.077 g (0.5 mmol) and carbon (Vulcan 72 manufactured by Cabot Co., Ltd.) 1.3 3 g (110 mmmol) were sufficiently pulverized and mixed. The mixed powder was heated in a nitrogen atmosphere at 1,800 ° C for 3 hours in a nitrogen atmosphere to obtain 2.48 g of a metal carbonitride (5) containing titanium and lanthanum. This will be broken by the mortar. 1.0 g of the crushed metal carbonitride (5) was introduced into a nitrogen gas containing 2% by volume of oxygen and 4% by volume of hydrogen, and heated in a tubular furnace at 100 ° C for 3 hours to obtain titanium and niobium. The metal oxycarbonitride (hereinafter also referred to as "catalyst (5)") was 1.22 g. The elemental analysis results of the obtained catalyst (5) are shown in Table 1. Further, the powder X-ray diffraction spectrum of the catalyst (5) is as shown in Fig. 31. 2. The electrode for a fuel cell is produced in the same manner as in the second embodiment except that the catalyst (5) is used. -1 ). (3) Evaluation of oxygen reduction energy in the absence of methanol in the aqueous sulfuric acid solution The fuel cell is used in the absence of methanol in the sulfuric acid aqueous solution in the same manner as in the third embodiment of the fuel cell electrode (5-1). Evaluation of the oxygen reduction energy of the electrode (5-1). Fig. 32 shows a current-potential curve obtained by the measurement. It is known that the electrode for fuel cell (5-1) has a high oxygen reduction energy of .84V (vs. RHE). -69 - 201131873 4. Oxygen reduction energy in the presence of methanol in aqueous sulfuric acid Evaluation of the oxygen reduction energy of the fuel cell electrode (5-1) in the presence of methanol in a sulfuric acid aqueous solution was carried out in the same manner as in the fourth embodiment of the present invention, except for the fuel cell electrode (5-1). The graph of the current-potential curve obtained by the measurement (with methanol) and the current-potential curve obtained by the above measurement (without methanol) is shown. It is known that the fuel cell electrode (5-1) is When methanol is present in the aqueous sulfuric acid solution, EFuel + 0xygen is 0.84 V (vs. RHE), which has the same high oxygen reduction energy as EOxygen (0.84 V (vs. RHE)) obtained by the above measurement (without methanol). The ratio (EFuel + 〇xygen/E0xygen) is 1·〇〇. That is, the electrode (5-1) using the fuel cell catalyst produced in Example 5 is used even for direct methanol fuel using methanol as a liquid fuel. When the battery (Direct Methanol Fuel Cell, DMFC) can inhibit the infiltration by methanol When the cathode potential is lowered, the oxygen reduction energy is excellent. 5. Evaluation of oxygen reduction energy in the absence of ethanol in the aqueous sulfuric acid solution The electrode for the new fuel cell (5-2) is produced in the same manner as in the above 2. The fuel cell is used. The evaluation of the oxygen reduction energy of the fuel cell electrode (5-2) in the absence of ethanol in the sulfuric acid aqueous solution was carried out in the same manner as in the fifth example of the first embodiment except for the electrode (5-2). 5-2) The ugly 0)^6„ is 0.83V (vs.RHE) with high oxygen reduction energy. -70-201131873 6. Evaluation of oxygen reduction energy in the presence of ethanol in an aqueous solution of sulfuric acid The fuel in the presence of ethanol in an aqueous sulfuric acid solution was used in the same manner as in the sixth embodiment of the fuel cell electrode (5-2). Evaluation of the oxygen reduction energy of the battery electrode (5-2). Fig. 34 is a graph showing a comparison of a current-potential curve obtained by the measurement (with ethanol) and a current-potential curve obtained by the above measurement (without ethanol). When the fuel cell electrode (5-2) was present in ethanol in an aqueous sulfuric acid solution, EFuel + 0xygen was 0.83 V (vs. RHE) ' and EOxygen (0.84 V (vs.) obtained by the above 5 measurement (without ethanol). RHE)) has almost the same high oxygen reduction energy. The oxygen reduction potential ratio (EFuei + 〇Xygen/E〇Xygen) was 0.99. In other words, the electrode (5-2) using the fuel cell catalyst produced in the fifth embodiment can be suppressed by using the direct Ethanol fuel cell (DEFC) using ethanol as a liquid fuel. The cathode potential of the penetration of ethanol is lowered, showing excellent oxygen reduction energy. 7. Evaluation of oxygen reduction energy in the absence of formic acid in an aqueous sulfuric acid solution A new fuel cell electrode (5-3) was produced in the same manner as in the above. The evaluation of the oxygen reduction energy of the fuel cell electrode (5-3) in the absence of formic acid in the sulfuric acid aqueous solution was carried out in the same manner as in the seventh embodiment except that the fuel cell electrode (5-3) was used. It is known that the E〇xygen of the fuel cell electrode (5-3) is 〇.83V (vs. RHE) and has high oxygen reduction energy. -71 - 201131873 8. Evaluation of oxygen reduction energy in the presence of formic acid in a sulfuric acid aqueous solution The fuel in the presence of formic acid in an aqueous sulfuric acid solution was used in the same manner as in the eighth embodiment except the fuel cell electrode (5-3). Evaluation of the oxygen reduction energy of the battery electrode (5-3). Fig. 35 is a graph showing a comparison of a current-potential curve obtained by the measurement (with formic acid) and a current-potential curve obtained by the above measurement (without formic acid). It was found that the fuel cell electrode (5-3) had EFue丨+ 〇xygen of 0.83 V (vs. RHE) even when formic acid was present in the sulfuric acid aqueous solution, and EOxygen (0.84 V (obtained from the above-mentioned 7 measurement (without formic acid)). Vs. RHE)) has almost the same high oxygen reduction energy. The oxygen reduction potential ratio (EFuel + 0xygen/E〇xygen) was 0.99. In other words, the electrode (5-3) using the fuel cell catalyst produced in the fifth embodiment can be suppressed by using the direct formic acid fuel cell (DFAFC) using formic acid as a fuel. The cathodic potential of the infiltration of formic acid is lowered, showing excellent oxygen reduction energy. [Example 6] (NbaTabCxNyOz) 1. Preparation of a catalyst: 4.96 g (42.5 mol) of lanthanum carbide (NbC, manufactured by Tatsukawa Chemical Co., Ltd.) and molybdenum oxide (Ta205, manufactured by Takatsu Chemical Co., Ltd.) 1.1 lg (2.5 mmol) and cerium nitride (NbN, manufactured by High Purity Chemical Research Laboratory Co., Ltd.) 0.27 g (2.5 mm 〇l) were sufficiently pulverized and mixed. The mixed powder was heated in a tubular furnace at 150 (TC for 3 hours in a nitrogen atmosphere - 72-201131873 to obtain 5.94 g of niobium and giant metal carbonitride (6). The sintered metal carbonitride (6) The pulverization was carried out by a ball honing machine. The pulverized metal carbonitride (6) 1.0 g was introduced into a nitrogen gas containing 2% by volume of oxygen and 4% by volume of hydrogen gas at a tubular furnace at 1,000. ^ The metal oxycarbonitride containing ruthenium and osmium (hereinafter also referred to as "catalyst (6)") l.llg was obtained by heating for 3 hours. The elemental analysis results of the obtained catalyst (6) are shown in Table 1. In addition, the powder X-ray diffraction spectrum of the catalyst (6) is shown in Fig. 36. 2. The fuel cell electrode is produced in the same manner as in the second embodiment except that the catalyst (6) is used. Electrode (6 -1) 3. Evaluation of oxygen reduction energy in the absence of methanol in the aqueous sulfuric acid solution The same as the third embodiment of the fuel cell electrode (6-1), the sulfuric acid aqueous solution was not used. Evaluation of the oxygen reduction energy of the fuel cell electrode (6-1) in the presence of methanol. The obtained current-potential curve was measured. It was found that the ugly electrode of the fuel cell electrode (6-1) was 〇.76V (vs. RHE) 'having high oxygen reduction energy. -73- 201131873 (6-1) Evaluation of oxygen reduction energy Figure 3 8 shows a graph comparing the current-potential curve obtained by the measurement (with methanol) and the current-potential curve obtained by the above measurement (without methanol). Battery Electrode (6-1) E00xygen (0.76 V (vs. RHE) obtained from EF.76V (vs. RHE) even when methanol is present in aqueous sulfuric acid solution, and the above 3 (no methanol). The oxygen reduction electric energy ratio (Ej:ue| + 〇Xygen/E〇xygen) is 1 · 〇〇. That is, the electrode of the fuel cell catalyst produced in Example 6 is used ( 6-1) Even when it is used in a direct methanol fuel cell (DMFC) using methanol as a liquid fuel, it is possible to suppress a decrease in cathode potential by methanol permeation, and exhibit excellent oxygen reduction energy. The evaluation of the oxygen reduction energy in the absence of ethanol in the aqueous solution is the same as in the above 2 In the same manner as in the fifth embodiment, the fuel cell electrode (6-2) in the absence of ethanol in the sulfuric acid aqueous solution is used in the same manner as in the fifth embodiment of the fuel cell electrode (6-2). Evaluation of oxygen reduction energy. It is known that the fuel cell electrode (6-2) has a high oxygen reduction energy of 0.75 V (vs. RHE). 6. Oxygen in the presence of ethanol in an aqueous sulfuric acid solution The evaluation of the reduction energy is carried out in the same manner as in the first embodiment, except that the fuel cell electrode (6-2) is used, and the oxygen reduction of the fuel cell electrode-74-201131873 (6-2) in the presence of ethanol in the sulfuric acid aqueous solution is performed. Can evaluate. Fig. 3.9 is a graph showing a comparison of a current-potential curve obtained by the measurement (with ethanol) and a current-potential curve obtained by the above measurement (without ethanol). It is known that the electrode for fuel cell (6-2) is EO.75V (vs. RHE) even when ethanol is present in the aqueous sulfuric acid solution, and EOxygen (0.76V (vs. RHE)) obtained by the above measurement (without ethanol). Almost the same high oxygen reduction energy. The oxygen reduction potential ratio (EFuel + 0xygen / E0xygen) was 0.99. In other words, the electrode (6-2) using the fuel cell catalyst produced in the sixth embodiment can be suppressed by using the direct Ethanol fuel cell (DEFC) using ethanol as a liquid fuel. The cathode potential of the penetration of ethanol is lowered, showing excellent oxygen reduction energy. 7. Evaluation of oxygen reduction energy in the absence of formic acid in an aqueous sulfuric acid solution A new fuel cell electrode (6-3) was produced in the same manner as in the above. The evaluation of the oxygen reduction energy of the fuel cell electrode (6-3) in the absence of formic acid in the sulfuric acid aqueous solution was carried out in the same manner as in the seventh embodiment except that the fuel cell electrode (6-3) was used. It was found that the E0xygen of the fuel cell electrode (6-3) was 〇.76V (vs. RHE) and had high oxygen reduction energy. 8. Evaluation of oxygen reduction energy in the presence of formic acid in the aqueous sulfuric acid solution The fuel cell electrode in the presence of formic acid in the sulfuric acid aqueous solution was carried out in the same manner as in the eighth embodiment except the fuel cell electrode (6-3). 75- 201131873 (6-3) Evaluation of oxygen reduction energy. Fig. 40 is a graph showing a comparison of a current-potential curve obtained by the measurement (with formic acid) and a current-potential curve obtained by the above measurement (without formic acid). It was found that the fuel cell electrode (6-3) had EFue丨+ 〇xygen of 0.76 V (vs. RHE) even in the presence of formic acid in an aqueous sulfuric acid solution, and EOxygen (0.76 V (obtained from the above-mentioned 7 measurement (without formic acid)). Vs. RHE)) has the same high oxygen reduction energy. The oxygen reduction potential ratio (Epuei + 〇xygen/E〇Xygen) was 1.00. In other words, the electrode (6-3) using the fuel cell catalyst produced in the sixth embodiment can be suppressed by using the direct formic acid fuel cell (DFAFC) using formic acid as a fuel. The cathodic potential of the infiltration of formic acid is lowered, showing excellent oxygen reduction energy. [Example 7] (NbaSnbCxNyOz) 1. Catalyst was prepared in cerium oxide (IV) (Nb02, manufactured by High Purity Chemical Research Laboratory Co., Ltd.) 4.00 g (32 mmol), tin oxide (IV) (Sn02, limited stock) 1.21 g (8 mmol) of the company's high-purity chemical research institute was fully pulverized and mixed with carbon (Vulcan 72 manufactured by Cabot Co., Ltd.) 1.2 g (100 mmol)» The mixed powder was placed in a tubular furnace at 1 400 ° C for 3 hours. Heat treatment in a nitrogen atmosphere gave 4.23 g of a metal carbonitride (7) containing bismuth and tin. The sintered metal carbonitride (7) was pulverized in a ball honing machine. 1.0 g of the pulverized metal carbonitride (7) was introduced into a nitrogen gas containing 2% by volume of oxygen and 4% by volume of hydrogen, and heated in a tubular furnace at 1〇〇〇-76-201131873 for 3 hours to obtain Metal and nitrogen oxides of antimony and tin (hereinafter also referred to as "catalyst (7)")) 1.09 g. The elemental analysis results of the obtained catalyst (7) are shown in Table 1. Further, the powder X-ray diffraction spectrum of the catalyst (7) is shown in Fig. 41. 2. Production of fuel cell electrode The fuel cell electrode (7-1) was obtained in the same manner as in Example 1 (2) except for the above-mentioned catalyst (7). (3) Evaluation of oxygen reduction energy in the absence of methanol in the aqueous sulfuric acid solution The fuel cell was used in the absence of methanol in the sulfuric acid aqueous solution, except for the fuel cell electrode (7-1). Evaluation of the oxygen reduction energy of the electrode (7-1). Fig. 42 shows a current-potential curve obtained by the measurement. It is known that the fuel cell electrode (7-1) is ugly 0; (^611 is 0.68 V (vs. RHE), and has oxygen-reducing energy. 4. Evaluation of oxygen reduction energy in the presence of methanol in an aqueous sulfuric acid solution. The evaluation of the oxygen reduction energy of the fuel cell electrode (7-1) in the presence of methanol in a sulfuric acid aqueous solution was carried out in the same manner as in the fourth embodiment of the fuel cell electrode (7-1). Fig. 43 shows the comparison by A graph of the current-potential curve obtained by the measurement (with methanol) and the current-potential curve obtained by the measurement of the above 3 (without methanol). -77- 201131873 It is known that the fuel cell electrode (7-1) is ' &^| + 0"8 in the presence of methanol in aqueous sulfuric acid <:11 is 〇.68V (vs. RHE), which has the same high oxygen reduction energy as E0xygen (0.68 V (vs. RHE)) obtained by the above measurement (without methanol). The oxygen reduction potential ratio (EFuel + 0xygen / E0xygen) was 1.00. That is, the electrode (7-1) using the fuel cell catalyst produced in the seventh embodiment can be suppressed by using the direct Methanol fuel cell (DMFC) using methanol as a liquid fuel. The cathode potential of methanol permeation is lowered, showing excellent oxygen reduction energy. 5. Evaluation of oxygen reduction energy in the absence of ethanol in an aqueous sulfuric acid solution A new fuel cell electrode (7-2) was produced in the same manner as in the above. The evaluation of the oxygen reduction energy of the fuel cell electrode (7-2) in the absence of ethanol in the sulfuric acid aqueous solution was carried out in the same manner as in Example 5, except that the fuel cell electrode (7-2) was used. It is known that the electrode for fuel cell (7-2) (^«:11 is 0.68V (vs.RHE)' has high oxygen reduction energy. 6. Evaluation of oxygen reduction energy in the presence of ethanol in aqueous sulfuric acid The evaluation of the oxygen reduction energy of the fuel cell electrode (7-2) in the presence of ethanol in the sulfuric acid aqueous solution was carried out in the same manner as in the sixth embodiment of the fuel cell electrode (7-2). A graph comparing the current-potential curve obtained by the measurement (with ethanol) and the current-potential curve obtained by the above measurement (without ethanol) -78-201131873, the electrode for the fuel cell (7-2) Even if ethanol is present in the aqueous solution of sulfuric acid, 'EFuel + 0xygen is 〇.68V (vs. RHE), and E0xygen (〇.68V(vs.RHE)) obtained by the above 5 (no ethanol) has the same high oxygen reduction. The oxygen reduction potential ratio (EFuel + 0xygen / E0xygen) is 1.00. That is, the electrode (7-2) using the fuel cell catalyst produced in Example 7 is used even in the direct ethanol form using ethanol as a liquid fuel. In the case of a fuel cell (Direct Ethanol Fuel Cell, DEFC), it inhibits the penetration of ethanol. When the cathode potential is lowered, the oxygen reduction energy is excellent. 7. Evaluation of the oxygen reduction energy in the absence of formic acid in the aqueous sulfuric acid solution The electrode for the new fuel cell (7-3) is produced in the same manner as in the above 2. The fuel cell electrode is used. (7-3) In the same manner as in the seventh embodiment, the oxygen reduction energy of the fuel cell electrode (7-3) in the absence of formic acid in the sulfuric acid aqueous solution was evaluated. 3) 〇)) [) ^11 is 0.68V (vs. RHE) with high oxygen reduction energy. 8. Evaluation of oxygen reduction energy in the presence of formic acid in the sulfuric acid aqueous solution The fuel cell electrode in the presence of formic acid in the sulfuric acid aqueous solution was carried out in the same manner as in the eighth embodiment except the fuel cell electrode (7-3). 7-3) Evaluation of oxygen reduction energy. Fig. 4 is a graph showing a comparison of a current-potential curve obtained by the measurement (with formic acid) and a current-potential curve obtained by the above measurement (without formic acid). -79- 201131873 It is known that the fuel cell electrode (7-3) has EFuel + 0xygen of 0.68 V (vs. RHE) even in the presence of formic acid in an aqueous sulfuric acid solution, and EOxygen (0_68 V) obtained by the above 7 measurement (without formic acid). (vs.RHE)) has the same high oxygen reduction energy. The oxygen reduction potential ratio (EFuel + Oxygen / E 〇 xygen) was 1.00. In other words, the electrode (7-3) using the fuel cell catalyst produced in the seventh embodiment can be suppressed by using the direct formic acid fuel cell (DFAFC) using formic acid as a fuel. The cathodic potential of the infiltration of formic acid is lowered, showing excellent oxygen reduction energy. <Comparison of oxygen reduction onset potential> The oxygen reduction potential ratio (EFuel + 0xygen/E0xygen) at -ΙΟΟμΑ/cm2 obtained from the current-potential curves in the above examples and comparative examples is shown in Table 1. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] Fig. 1 shows an electrode using a catalyst active for oxidation of a liquid fuel, a case where a liquid fuel (Lf) exists in an electrolyte, and a current in a case where a liquid fuel does not exist (Lo) An example of a comparison of a potential curve. [Fig. 2] Fig. 2 shows Cyclic Voltammetry (CV) in the presence of methanol in a sulfuric acid electrolyte for an electrode using a platinum catalyst [Fig. 3] Fig. 3 shows an electrode for using a platinum catalyst in sulfuric acid Cyclic voltammetry in the absence of methanol in the electrolyte. Fig. 4 is a graph showing the comparison of the oxygen reduction energy in the presence of methanol in the sulfuric acid electrolysis -80-201131873 and the oxygen reduction in the absence of methanol for the electrode using uranium catalyst. Fig. 5 shows an example of cyclic voltammetry in the presence of methanol in a sulfuric acid electrolyte for an electrode using the catalyst of the present invention. Fig. 6 is a view showing an example of cyclic voltammetry in the absence of methanol in a sulfuric acid electrolyte for an electrode using the catalyst of the present invention. Fig. 7 is a view showing an example of a graph for evaluating the oxygen reduction energy of the electrode of the catalyst of the present invention in the presence of methanol in the sulfuric acid electrolyte and the absence of methanol. Fig. 8 shows a powder X-ray diffraction spectrum of the catalyst (1) of Example 1. Fig. 9 is a graph showing the evaluation of the oxygen reduction energy of the electrode (1-1) for a fuel cell of Example 1. [Fig. 10] Fig. 10 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where methanol is present in the aqueous sulfuric acid solution and the oxygen in the absence of methanol, for the electrode electrode for fuel cell of the first embodiment. [Fig. 11] Fig. 11 is a graph showing the comparison of the oxygen reduction energy in the case where the presence of ethanol in the aqueous sulfuric acid solution and the absence of ethanol were carried out for the fuel cell electrode 〇-2) of Example 1. Fig. 12 is a graph showing the comparison of the oxygen reduction energy in the presence of formic acid in the aqueous sulfuric acid solution and the oxygen reduction in the absence of formic acid in the fuel cell electrode (1-3) of Example 1. Fig. 13 shows a powder X-ray diffraction spectrum of a catalyst (2) of Example 2. -81 - 201131873 [Fig. 14] Fig. 14 is a view showing the evaluation of the oxygen reduction energy of the fuel cell electrode (2-1) of Example 2. [Fig. 15] Fig. 15 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where methanol is present in the aqueous sulfuric acid solution and the oxygen reduction in the absence of methanol, for the fuel cell electrode (2-1) of Example 2. [Fig. 16] Fig. 16 is a graph showing the comparison of the oxygen reduction energy in the case where ethanol is present in the aqueous sulfuric acid solution and the oxygen reduction energy in the absence of ethanol, for the fuel cell electrode (2-2) of Example 2. Fig. 17 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where the formic acid is present in the aqueous sulfuric acid solution and the oxygen reduction in the absence of formic acid in the fuel cell electrode (2-3) of Example 2. [Fig. 18] Fig. 18 is a graph showing the comparison of the oxygen reduction energy in the case where methanol is present in the sulfuric acid aqueous solution and the oxygen reduction energy in the absence of methanol, for the fuel cell electrode (C1-1) of Comparative Example 1. Fig. 19 is a graph showing the comparison of the oxygen reduction energy in the case where ethanol is present in the sulfuric acid aqueous solution and the oxygen reduction energy in the absence of ethanol, for the fuel cell electrode (C 1 _2) of Comparative Example 1. [Fig. 20] Fig. 20 is a graph showing the comparison of the oxygen reduction energy in the case where formic acid is present in the aqueous sulfuric acid solution and the oxygen reduction energy in the absence of formic acid in the fuel cell electrode (C1-3) of Comparative Example 1. Fig. 21 shows a powder X-ray diffraction spectrum of a catalyst (3) of Example 3. [Fig. 22] Fig. 22 is a view showing the evaluation of the oxygen reduction energy of the fuel cell electrode (3-1) of Example 3. -82- 201131873 [Fig. 23] Fig. 23 is a graph showing the comparison of the oxygen reduction energy in the case where methanol is present in the aqueous sulfuric acid solution and the oxygen reduction energy in the absence of methanol for the fuel cell electrode ρ-ΐ) of Example 3. Fig. 24] Fig. 24 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where ethanol is present in the aqueous sulfuric acid solution and the oxygen reduction in the absence of ethanol, for the fuel cell electrode (3-2) of Example 3. [Fig. 25] Fig. 25 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where the formic acid is present in the aqueous sulfuric acid solution and the oxygen reduction in the absence of formic acid in the fuel cell electrode (3-3) of Example 3. Fig. 26 shows a powder X-ray diffraction spectrum of the catalyst (4) of Example 4. Fig. 27 is a graph showing the evaluation of the oxygen reduction energy of the fuel cell electrode (4-1) of Example 4. [Fig. 28] Fig. 28 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where methanol is present in the aqueous sulfuric acid solution and the oxygen reduction in the absence of methanol, for the fuel cell electrode (4-1) of Example 4. [Fig. 29] Fig. 29 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where ethanol is present in the sulfuric acid aqueous solution and the oxygen reduction energy in the absence of ethanol, for the fuel cell electrode (4- 2) of Example 4. Fig. 30 is a graph showing the evaluation of the oxygen reduction energy in the presence of formic acid in an aqueous sulfuric acid solution and the absence of formic acid in the electrode for fuel cell of Example 4 (4-.3). Fig. 31 shows a powder X-ray diffraction spectrum of a catalyst (5) of Example 5. [83] Fig. 32 is a graph showing the evaluation of the oxygen reduction energy of the fuel cell electrode (5-1) of Example 5. [Fig. 33] Fig. 33 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where methanol is present in the aqueous sulfuric acid solution and the oxygen reduction energy in the absence of methanol, for the electrode for fuel cell of Example 5, Ο-ΐ). [Fig. 34] Fig. 34 is a graph showing the comparison of the oxygen reduction energy in the case where ethanol is present in the sulfuric acid aqueous solution and the oxygen reduction energy in the absence of ethanol, with respect to the fuel cell electrode (5-2) of Example 5. [Fig. 35] Fig. 35 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where the formic acid is present in the aqueous sulfuric acid solution and the oxygen reduction in the absence of formic acid in the fuel cell electrode (5-3) of Example 5. Fig. 36 shows a powder X-ray diffraction spectrum of a catalyst (6) of Example 6. [Fig. 37] Fig. 37 is a view showing the evaluation of the oxygen reduction energy of the fuel cell electrode (6-1) of Example 6. [Fig. 38] Fig. 38 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where methanol is present in the sulfuric acid aqueous solution and the oxygen reduction energy in the absence of methanol, for the fuel cell electrode (6-1) of Example 6. [Fig. 39] Fig. 39 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where the fuel electrode (6-2) of the fuel cell of Example 6 is present in the sulfuric acid aqueous solution and the case where the ethanol is absent. Fig. 40 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where the formic acid is present in the aqueous sulfuric acid solution and the oxygen reduction in the absence of formic acid in the electrode for fuel cell (6-3) of Example 6. -84 - 201131873 [Fig. 41] Fig. 41 shows a powder X-ray diffraction spectrum of the catalyst (7) of Example 7. Fig. 42 is a graph showing the evaluation of the oxygen reduction energy of the fuel cell electrode (7-1) of Example 7. [Fig. 43] Fig. 43 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where methanol is present in the sulfuric acid aqueous solution and the oxygen reduction energy in the absence of methanol, for the fuel cell electrode (7-1) of Example 7. [Fig. 44] Fig. 44 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where ethanol is present in the aqueous sulfuric acid solution and the oxygen reduction in the absence of ethanol, for the fuel cell electrode (7-2) of Example 7. [Fig. 45] Fig. 45 is a graph showing the comparative evaluation of the oxygen reduction energy in the case where the formic acid is present in the aqueous sulfuric acid solution and the oxygen reduction in the absence of formic acid in the electrode for fuel cell (7-3) of Example 7. -85- 201131873 Brewing s Secret 5 • N^ CJ S OT u > 〇0 rH 1 ^Fu· 1+0* jrgen/^)yxe〇n Formic acid 0.99 0. 98 0.34 1.00 1.00 0. 99 1.00 1.00 ^ Fue) *Qxyc*«/^Oyie〇n Ethanol o rH 03⁄4 CT> o CD LO 〇oo fH <Ti <Ji 〇0.99 o ^uel-*O)〇reer»/^0yicen Methanol 0. 96 o 0.60 oo rH o rH oo Composition of the catalyst 96^e0.04^0.33^a 07^2.18 T i〇. 9aL3 ^. 02^0. wN〇〇Q〇i. 69 Pt/C TiCy HN0 ^ M He 0)·3βΝ〇. i〇].9 Ti0 9aSm〇0lCa 12N0”0]59 90^3⁄4 04^0.31^0.1 ^1.5 Nb〇. 9eSn〇WC0 36〇0 69 j 1 Embodiment 1 Embodiment 2 Comparative Example 1 Example 3 Example 4 i 1 J Example 5 Example 6 Example 7 -86-

Claims (1)

201131873 VII. Patent application scope: 1. A catalyst for direct liquid fuel cells, characterized by being composed of metal oxycarbonitride containing cerium and/or titanium. 2. The catalyst for direct liquid fuel cells according to claim 1 of the patent scope, which is inert to the oxidation of liquid fuel. .3. The catalyst for a direct liquid fuel cell according to the first or second aspect of the patent application is a metal oxycarbon oxide containing at least one metal M1 other than cerium and lanthanum. 4. The catalyst for direct liquid fuel cells according to item 1 or 2 of the patent application, which is selected from the group consisting of tin, indium, giant, zirconium, copper, iron, tungsten, chromium, molybdenum, niobium, niobium , vanadium, Ming, Meng, 钸, 众, 钸, 纪, 钉, 镧, 铈, 鐯, 钹, 钐, 钐, 铕, I, 铽, 镝, 鈥, bait, table, mirror, distillation and nickel A group of at least one metal ruthenium 1 and a ruthenium metal oxycarbonitride. 5. The catalyst for a direct liquid fuel cell according to claim 3 or 4, wherein the composition of the metal oxycarbonitride is NbaMlbCxNyOz (however, a, b, X, y, ζ are in atomic number) The ratio is expressed as 0.01 ^ a < l ' 0< bS0.99, 0.01 ^ 2 > 0.01 ' 0.01^2^3 , a + b = 1, and x + y + z$5). 6. The catalyst for a direct liquid fuel cell according to any one of claims 3 to 5, wherein the metal oxycarbon oxide is determined by a powder X-ray diffraction method (Cu-K line) The diffraction angle is 2 Θ = 3 3 ° ~ 4 3 . Two or more diffraction line peaks were observed between. 7 · For direct liquid fuels as claimed in item 1 or 2 of the patent scope -87- 201131873 Catalysts for batteries are made of metal oxycarbon oxides containing titanium and at least one metal M2 other than titanium. By. 8. The catalyst for direct liquid fuel cells according to item 1 or 2 of the patent application, which is selected from the group consisting of calcium, strontium, barium, strontium, strontium, strontium, barium, giant 钐, 铕, 釓钺, 镝, 镝, 鈥, bait, watch, mirror and 镏 group of at least one metal M2 and titanium metal oxycarbon oxide. 9. The catalyst for direct liquid fuel cells according to claim 7 or 8, wherein the metal oxycarbonitride has a composition formula of TiaM2bCxNyOz (however, a, b, x, y, z are atoms) The numerical ratio is expressed as 0.7 ^ a ^ 0.9999 ' 0.0001 ^ 0.3 ' 0.0 1 ^ x ^ 2 ' 0.01$y$2, 0.01 S z $ 3, a + b = 1, and x + y + z$5). A catalyst layer for a direct liquid fuel cell, which is characterized by containing a catalyst as in any one of claims 1 to 9. 11. The catalyst layer for a direct liquid fuel cell according to the first aspect of the invention, further comprising electron conductive particles. An electrode for a direct liquid fuel cell, which is a direct liquid fuel cell electrode having a catalyst layer for a direct liquid fuel cell and a porous support layer, which is characterized by the catalyst for a direct liquid fuel cell. The layer is a catalyst layer for a direct liquid fuel cell as described in claim 10 or item 11. A membrane electrode assembly for a direct liquid fuel cell, which is a membrane electrode assembly for a direct liquid fuel cell having a cathode, an anode, and an electrolyte membrane disposed between the cathode and the anode, and is characterized in that The foregoing cathode and/or the foregoing anode is an electrode for a liquid type fuel cell as described in claim 12, Direct-88-201131873. 1 . A direct liquid fuel cell characterized by having a membrane electrode assembly for a direct liquid fuel cell according to claim 13 of the patent application.