Metal supported catalyst, battery electrode, and battery
A metal-supported catalyst, battery electrode, and battery, each having excellent catalytic activity and durability. The metal-supported catalyst includes: a carbon carrier; and catalyst metal particles supported thereon, wherein, in a photoelectron spectrum obtained by X-ray photoelectron spectroscopy, the catalyst exhibits, as a peak derived from a is orbital of a nitrogen atom, a peak to be separated into peaks of first to sixth nitrogen atoms having peak tops in the following respective ranges: (1) 398.6±0.2 eV; (2) 399.5±0.3 eV; (3) 400.5±0.2 eV; (4) 401.3±0.3 eV; (5) 403.4±0.4 eV; and (6) 404.5±0.5 eV, wherein a ratio of a peak area of the second nitrogen atoms to a total peak area of the nitrogen atoms of the (1) to (6) is 0.03 or more, and wherein a ratio of a concentration of the second nitrogen atoms to a concentration of carbon atoms measured by the X-ray photoelectron spectroscopy is 0.0005 or more.
1. A metal-supported catalyst, comprising:
a carbon carrier; and
platinum particles supported on the carbon carrier, wherein, in a photoelectron spectrum obtained by X-ray photoelectron spectroscopy, the metal-supported catalyst exhibits a peak derived from a 1s orbital of a nitrogen atom, which is separated into the following peaks (1) to (6) of nitrogen atoms:
(1) a peak of first nitrogen atoms having a peak top in a range of a binding energy of 398.6±0.2 eV;
(2) a peak of second nitrogen atoms having a peak top in a range of a binding energy of 399.5±0.3 eV;
(3) a peak of third nitrogen atoms having a peak top in a range of a binding energy of 400.5±0.2 eV;
(4) a peak of fourth nitrogen atoms having a peak top in a range of a binding energy of 401.3±0.3 eV;
(5) a peak of fifth nitrogen atoms having a peak top in a range of a binding energy of 403.4±0.4 eV; and
(6) a peak of sixth nitrogen atoms having a peak top in a range of a binding energy of 404.5±0.5 eV,
wherein a ratio of a peak area of the second nitrogen atoms to a total peak area of the nitrogen atoms of the (1) to (6) measured by the X-ray photoelectron spectroscopy is 0.03 or more,
wherein a ratio of a concentration of the second nitrogen atoms to a concentration of carbon atoms measured by the X-ray photoelectron spectroscopy is 0.0005 or more,
wherein an electrochemical surface area (H 2 -ECSA) obtained by dividing a hydrogen adsorption electric quantity, measured in cyclic voltammetry using a rotating disc electrode containing the metal-supported catalyst, by a theoretical area-equivalent electric quantity of hydrogen adsorption to platinum and a weight of platinum supported on the metal-supported catalyst, is 20.0 m 2 /g-platinum or more, and
wherein an electrochemical surface area (CO-ECSA), obtained by dividing a carbon monoxide adsorption electric quantity measured in stripping voltammetry using the rotating disc electrode containing the metal-supported catalyst by a theoretical area-equivalent electric quantity of carbon monoxide adsorption to platinum and the weight of platinum supported on the metal-supported catalyst, is 20.0 m 2 /g-platinum or more.
2. The metal-supported catalyst according to claim 1 , wherein a ratio of a sum of a concentration of the first nitrogen atoms, a concentration of the third nitrogen atoms, and a concentration of the fourth nitrogen atoms to the concentration of the carbon atoms measured by the X-ray photoelectron spectroscopy is 0.004 or more.
3. The metal-supported catalyst according to claim 1 , wherein a ratio of the peak area of the second nitrogen atoms to a peak area of the first nitrogen atoms is 0.12 or more.
4. The metal-supported catalyst according to claim 1 , wherein a ratio of a peak area of the first nitrogen atoms to the total peak area of the nitrogen atoms of the (1) to (6) is 0.48 or less.
5. The metal-supported catalyst according to claim 1 , wherein a ratio of a peak area of the fourth nitrogen atoms to the total peak area of the nitrogen atoms of the (1) to (6) is 0.15 or more.
6. The metal-supported catalyst according to claim 1 , wherein an average crystallite diameter of the platinum particles calculated by Scherrer equation through use of a diffraction angle and a full width at half maximum of one or more diffraction peaks obtained by separating a diffraction line having a diffraction angle 2θ in a vicinity of 40° in a powder X-ray diffraction pattern by a CuKα ray is 5.40 nm or less.
7. The metal-supported catalyst according to claim 1 , wherein the metal-supported catalyst has a carbon structure that exhibits a full width at half maximum of 160 cm −1 or less of a D band having a peak top in a vicinity of 1,360 cm −1 in a Raman spectrum obtained by Raman spectroscopy.
8. The metal-supported catalyst according to claim 1 , wherein the metal-supported catalyst has a carbon structure that exhibits a full width at half maximum of 80 cm −1 or less of a G band having a peak top in a vicinity of 1,600 cm −1 in a Raman spectrum obtained by Raman spectroscopy.
9. The metal-supported catalyst according to claim 1 , wherein the metal-supported catalyst has a carbon structure that exhibits a ratio of 0.25 or more and 0.40 or less of a minimum intensity between a G band having a peak top in a vicinity of 1,600 cm −1 and a D band having a peak top in a vicinity of 1,360 cm −1 to an intensity of the G band in a Raman spectrum obtained by Raman spectroscopy.
10. The metal-supported catalyst according to claim 1 , wherein the metal-supported catalyst has a carbon structure that exhibits a nitrogen desorption amount of 1.20×10 −5 (mol/g-carrier) or more from 600° C. to 1,000° C. per unit weight of the carbon carrier in a temperature programmed desorption method.
11. The metal-supported catalyst according to claim 1 , wherein the metal-supported catalyst has a carbon structure that exhibits a nitrogen desorption amount of 0.75×10 −5 (mol/g-carrier) or more from 800° C. to 1,000° C. per unit weight of the carbon carrier in a temperature programmed desorption method.
12. A battery electrode, comprising the metal-supported catalyst of claim 1 .
13. A battery, comprising the battery electrode of claim 12 .