24. 実測の再現から活性起源の解明へ:遷移状態解析
24
TS* I TS 2N
1883 cm-1
1846 cm-1
ΔG (350 °C) in eV
1844 cm-1
2N
N2 TS* I TS 2N
a f
g h
N2
N2
2161 cm-1
2066 cm-1
N2
c
TS
TS* I TS 2N
N2
N2 TS* I TS 2N
i
N2 TS* I TS 2N
1711 cm-1
1.94 0.90
0.98
1.09
0.64
0.65
https://arxiv.org/abs/2208.13385
25. 実測の再現から活性起源の解明へ:高活性構造の特定
25
≈ 2160 cm-1
i
iii
iv
v
ii
≈ 2090 cm-1
i
ii
iii
iv
v
≈ 2060 cm-1
i
ii
iii
iv
v
≈ 1965 cm-1
i
ii
iii
iv
v
≈ 1917 cm-1
i
ii
iii
iv
v
≈ 1883 cm-1
ii
iii
iv
v
≈ 1844 cm-1
ii
iii
iv
v
≈ 1771 cm-1
ii
iii
iv
v
i i i
低活性化障壁
の局所構造
⇒高活性の起源
https://arxiv.org/abs/2208.13385
26. 実測の再現から活性起源の解明へ:高活性構造の特定
26
States A C G H F I
ΔG(350 °C) (eV) 1.94 0.90 1.09 0.98 0.65 0.64
ഥ
𝑁𝑁2
(𝑇red
= 500 °C) 12.14 0.06 2.78 2.15
ഥ
𝑁𝑁2
𝑇red
= 650 °C 12.26 0.50 1.69 2.56
TS* I TS 2N
1883 cm-1
1846 cm-1
ΔG (350 °C) in eV
1844 cm-1
N2 TS* I TS 2N
a f
g h
N2
N2
2161 cm-1
2066 cm-1
N2
c
TS* I TS 2N
N2
N2 TS* I TS 2N
i
N2 TS* I TS 2N
1711 cm-1
2N
TS
https://arxiv.org/abs/2208.13385
27. サイバー触媒科学:実測の活性起源は?
27
States A C G H F I
ΔG(350 °C) (eV) 1.94 0.90 1.09 0.98 0.65 0.64
ഥ
𝑁𝑁2
(𝑇red
= 500 °C) 12.14 0.06 2.78 2.15
ഥ
𝑁𝑁2
𝑇red
= 650 °C 12.26 0.50 1.69 2.56
https://arxiv.org/abs/2208.13385
44. 理論触媒科学4.0~サイバー触媒科学
44
金属元素:60強(合金や酸化物・複合アニオンなどに活用可能)
H
Li Be
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
B C N O F Ne
He
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba Ln Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra An Rf Db Sg Bh Hs Mt Ds Rg Cn
Na Mg Al Si P S Cl Ar
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Nh Fl Mc Lv Ts Og
元素の組み合わせ(60元素の場合)
2元素:~2×103通り
3元素:~4×104通り
5元素:~8×106通り
10元素:~3×1011通り
×(元素の組成)×(合成条件)×(反応条件)=∞
合金の多元素化による膨大な探索空間
45. ナノ粒子化による熱力学の変化
45
https://www.jst.go.jp/pr/announce/20111024-3/index.html
Nature Materials volume 11, pages 49–52 (2012)
https://sites.google.com/site/catcalcphase/metal/au/au-pd
Bulk Phase Diagram(Au, Pd)
Crown Jewel Catalyst Data from: “Binary Alloy Phase Diagrams”, 2nd Ed., eds. T. B. Massalski, H. Okamoto, P.
R. Subramanian and L. Kacprzak, in 3 volumes, ASM International, Ohio, USA, 1990
Solid Solution @ High T
Segregation at Low T
Bulk Phase Diagram(Pd,Pt)
Pd/Pt
H2
Treatment
Solid Solution
Kobayashi et al., J. Am. Chem. Soc, 132, 5576 (2010).
Pd
Au
46. ナノ粒子の熱力学
46
−
+
=
−
= −
−
6
3
1 1
2
1
N
t
i
v
vib
T
i
v
T
i
v
e
e
T
RT
E
T: Temperature
R: Gas constant
: Vibrational Temperature
k: Boltzmann’s constant
w: Frequency
h: Planck’s constant
c: Velocity of Light
N: Freedom
W: Number of possible configurations
kT
c
h
T
i
i
v w
=
−
=
−
−
−
−
−
−
=
6
3
1
1
ln
1
N
t
i
v
vib
T
i
v
T
i
v
T
i
v
e
e
e
T
R
S
W
k
Sconfig ln
=
Vibrational Enthalpy
Vibrational Entropy
Configurational Entropy
From First-principles Calculations
Excess Energy
𝜀𝑒𝑥𝑐𝑒𝑠𝑠 =
1
𝑁
𝜀𝑀𝑀′ − 𝑥𝜀𝑀 − 1 − 𝑥 𝜀𝑀′ 𝜀𝑀:Derived from
First-principles Calculation
𝑥:Composition
arXiv:2007.06137
51. 多元素ナノ合金:吸着特性の網羅的計算
51
吸着サイト⇒649 サイト C O
Pt Ru Ir
CO
ontop bridge
3-fold 4-fold
40:40:121 40:121:40 41:80:80 67:67:67
80:41:80 80:80:41 121:40:40
組成 Pt:Ru:Ir
C-O distance / Å
E
ads
/
eV
C-O distance / Å
E
ads
/
eV
E
ads
/
eV
C-O distance / Å C-O distance / Å C-O distance / Å
Bridge
3-fold
fcc
3-fold
hcp
Ontop
PtRuIr
PtRuIr PtRuIr PtRuIr
Monometal
Ontop
ca. 5000 calc.
SCCJ2022秋 2O09
60. Team Members
KOYAMA, Michihisa, Professor
HISAMA, Kaoru, Assistant Professor
NGUYEN, Quang, Research Assistant Professor
TABOROSI, Attila, Research Assistant Professor
NANBA, Yusuke, Postdoctoral Fellow
VALADEZ HUERTA, Gerardo, Postdoctoral Fellow
TAMURA, Ayako, Research Fellow
ISHIZAWA, Masashi, Research Assistant
MORIYAMA, Masahiro, Research Assistant
KITAMURA, Nagahisa, Research Assistant
TAKAHASHI, Kayo, Research Assistant
NAKAJIMA, Kaoru, Secretarial Staff
Group Members
60