Composite oxide, metal-supported material, and ammonia synthesis catalyst

1. A ternary composite oxide a metal element expressed by a composition of General Formula (1-2):

A n X y M m   (1-2)

wherein,

A represents a lanthanoid, wherein a ratio (A 3+ /A total ) of a number of moles of the element in a trivalent state (A 3+ ) to a total number of moles of the A (A total ) satisfies 0.1≤A 3+ /A total ≤1.0,

X represents an element that is a Group-2 element in the periodic table selected from the group consisting of Ca, Sr, and Ba, or a lanthanoid that is different from A,

M represents an element that is a Group-1 element in the periodic table, a Group-2 element selected from the group consisting of Ca, Sr, and Ba, or a lanthanoid that is different from A and X,

n satisfies 0<n<1,

y satisfies 0<y<1,

m satisfies 0≤m<1, and

n+y+m= 1), and

the ternary composite oxide is in a mixed state in which:

(1) a solid solution of A and an oxide of one of X and M; and

(2) an oxide of the other of X and M are mixed.

2. The ternary composite oxide according to claim 1 , wherein the ratio (A 3+ /A total ) satisfies 0.2≤A 3+ /A total ≤1.0.

3. The ternary composite oxide according to claim 1 , wherein the ternary composite oxide includes a solid solution that is a tetragonal crystal or a cubic crystal.

4. The ternary composite oxide according to claim 1 , wherein at least one of the elements A, X, and M in the ternary composite oxide is an element with strong basicity in which a value of a partial negative charge (−δ O ) of oxygen in an oxide state is 0.50 or more.

5. The ternary composite oxide according to claim 1 , wherein when a composition ratio of each element (i) in the ternary composite oxide is ni, a Sanderson electronegativity of each element is χi and a value of a partial negative charge (−δ O ) of oxygen expressed by the following Formula (A):

((Π(χ i ni )){circumflex over ( )}(1/Σ ni )−5.21)/−4.75  Formula (A)

is 0.52 or more.

6. The ternary composite oxide according to claim 1 , wherein

A is an element selected from Ce and La,

X is Ba.

7. The ternary composite oxide according to claim 1 , wherein X in General Formula (1) is Ba and a quantity of carbonate ions included in the ternary composite oxide is 10 mol % or less of Ba.

8. The ternary composite oxide according to claim 1 , wherein the ternary composite oxide is selected from Ba 0.1 La 0.45 Ce 0.45 O x , Ba 0.3 Pr 0.35 Ce 0.35 O x , Ba 0.3 Ce 0.35 Pr 0.35 O x , Ba 0.3 La 0.35 Ce 0.35 O x , Ba 0.1 La 0.3 Ce 0.6 O x , Ba 0.1 La 0.6 Ce 0.3 O x , Ba 0.1 La 0.8 Ce 0.1 O x , Ba 0.05 La 0.475 Ce 0.475 O x , Ba 0.15 La 0.425 Ce 0.425 O x , Ba 0.1 Pr 0.45 Ce 0.45 O x , and Ba 0.3 La 0.35 Pr 0.35 O x .

9. A metal-supported material in which one or more kinds of transition metal selected from the group consisting of Ru, Fe, Co, Ni, Rh, Pd, Os, Ir, and Pt is supported by the ternary composite oxide according to claim 1 .

10. The metal-supported material according to claim 9 , wherein a ratio of a D ads value of a Ru dispersion degree obtained by an H 2 pulse chemical adsorption method to a D TEM value of a Ru dispersion degree expected from an average particle diameter of Ru particles obtained from a TEM image satisfies 0<D ads /D TEM <1.

11. The metal-supported material according to claim 9 , wherein when nitrogen is adsorbed on the supported transition metal, N≡stretching vibration ν1 of nitrogen molecules that mutually act in a major-axis direction is observed in 2300 to 2000 cm −1 by an infrared absorption spectroscopy, and/or weakened N≡stretching vibration ν2 of the nitrogen molecules that mutually act in the major-axis direction for the transition metal is observed in 1900 to 1500 cm −1 .

12. The metal-supported material according to claim 9 , wherein an average particle diameter of the transition metal supported on the ternary composite oxide is 100 nm or less.

13. An ammonia synthesis catalyst comprising the metal-supported material according to claim 9 .

14. A manufacturing method for the ternary composite oxide according to claim 1 , the manufacturing method comprising:

mixing an A precursor including A, an X precursor including X, and an M precursor including M to obtain a mixture; and

calcinating the mixture at 600° C. or more.

15. A manufacturing method for the metal-supported material according to claim 9 , the manufacturing method comprising:

mixing an A precursor including A, an X precursor including X, and an M precursor including M to obtain a mixture;

calcinating the mixture at 600° C. or more to obtain a carrier including the ternary composite oxide;

supporting a compound including the transition metal by the ternary composite oxide to prepare a before-reducing process supporting material; and

performing a reducing process on the before-reducing process supporting material at 400° C. or more.

16. A manufacturing method for ammonia comprising bringing hydrogen, nitrogen, and a catalyst in contact with each other, the catalyst being the ammonia synthesis catalyst according to claim 13 .

17. A ternary composite oxide consisting of a metal element expressed by a composition of General Formula (1-2):

A n X y M m   (1-2)

wherein,

A represents a lanthanoid selected from the group consisting of Ce, Pr, Tb and La, wherein a ratio (A 3+ /A total , of) a number of moles of the element in a trivalent state (A 3+ ) to a total number of moles of the (A 3+ /(A total ) satisfies 0.1≤A 3+ ±/A total ≤1.0,

X represents an element that is a Group-2 element in the periodic table selected from the group consisting of Ca, Sr, and Ba, or a lanthanoid that is different from A,

M represents an element that is a Group-1 element in the periodic table, a Group-2 element selected from the group consisting of Ca, Sr, and Ba, or a lanthanoid that is different from A and X,

n satisfies 0<n<1,

y satisfies 0<y<1,

m satisfies 0<m<1, and

n+y+m= 1, and

the ternary composite oxide is in a mixed state in which:

(1) a solid solution of A and an oxide of one of X and M; and

(2) an oxide of the other of X and M

are mixed.