ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú...
TRANSCRIPT
![Page 1: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/1.jpg)
Ȼ.ȼ.Ɋɨɦɚɧɨɜɫɤɢɣɏɢɦɢɱɟɫɤɢɣ
ɮɚɤɭɥɶɬɟɬ
ɆȽɍ
Ɍɟɥ: 939-20-54, ɮɚɤɫ: 939-35-70,e-mail: [email protected]
Ʌɟɤɰɢɹ
10 ɢɡ
ɰɢɤɥɚ
«Ɏɭɧɞɚɦɟɧɬɚɥɶɧɵɟɨɫɧɨɜɵ
ɧɚɧɨɬɟɯɧɨɥɨɝɢɣ»
(27-ɦɚɪ-09)
![Page 2: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/2.jpg)
• Catalysis is the central field of nanoscience
and nanotechnology
G. Somorjai,
Chem. Commun., 2003,
2257
•
…
Ƚ-ɧ ɀɭɪɞɟɧ (ɀ.-Ȼ.Ɇɨɥɶɟɪ, «Ɇɟɳɚɧɢɧ ɜɨ ɞɜɨɪɹɧɫɬɜɟ»)
ɇɚɧɨɤɚɬɚɥɢɡ: ɷɬɨ
ɧɨɜɨɟ
ɢɥɢɯɨɪɨɲɨ ɡɚɛɵɬɨɟ ɫɬɚɪɨɟ?
![Page 3: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/3.jpg)
ɇ.ɂ.Ʉɨɛɨɡɟɜ, 1939 ɝ.(!!)
0
0,3
0,6
0,9
1,2
1,5
0 1 2 3 4
Ɋɚɡɦɟɪ ɤɥɚɫɬɟɪɚ Pt, ɧɦL
og
(ȺɄȺ
), ɦɨɥ
/ɦɢɧ
*ɚɬ
. P
t
Ɉɤɢɫɥɟɧɢɟ
ɜɨɞɨɪɨɞɚ
ɧɚ
Pt/A2
O3
Ƚ.Ʉ.Ȼɨɪɟɫɤɨɜ
ɢ
ɞɪ., 1982 ɝ.
ɇɚɧɨɤɚɬɚɥɢɡ
-
ɯɨɪɨɲɨ
ɡɚɛɵɬɨɟ
ɫɬɚɪɨɟ!
![Page 4: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/4.jpg)
ȼȼȿȾȿɇɂȿ
![Page 5: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/5.jpg)
Ʉɚɬɚɥɢɡ
ɤɚɤ
ɫɚɦɨɫɬɨɹɬɟɥɶɧɵɣ
ɪɚɡɞɟɥɯɢɦɢɱɟɫɤɨɣ
ɧɚɭɤɢ
(1779-1848)
1835 ɝɨɞ
![Page 6: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/6.jpg)
ȼȼɉ ɏɢɦ. ɩɪɨɦ.
25% 80%
Ʉɚɬɚɥɢɡ: ɜɤɥɚɞ
ɜ
ȼȼɉ
ɢ
ɩɪɨɞɭɤɰɢɸ ɯɢɦɢɱɟɫɤɨɣ
ɩɪɨɦɵɲɥɟɧɧɨɫɬɢ
![Page 7: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/7.jpg)
ɑɬɨ
ɬɚɤɨɟ
«ɤɚɬɚɥɢɡ»?
«Ʉɚɬɚɥɢɡ
–
ɭɫɤɨɪɟɧɢɟ
ɢɥɢ ɢɧɢɰɢɢɪɨɜɚɧɢɟ
ɯɢɦɢɱɟɫɤɢɯ
ɪɟɚɤɰɢɣ
ɜ ɩɪɢɫɭɬɫɬɜɢɢ
ɜɟɳɟɫɬɜ (ɤɚɬɚɥɢɡɚɬɨɪɨɜ), ɦɧɨɝɨɤɪɚɬɧɨ ɜɫɬɭɩɚɸɳɢɯ
ɜ
ɩɪɨɦɟɠɭɬɨɱɧɨɟ ɯɢɦɢɱɟɫɤɨɟ
ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ
ɫ ɢɫɯɨɞɧɵɦɢ
ɪɟɚɝɟɧɬɚɦɢ
ɢ ɜɨɫɫɬɚɧɚɜɥɢɜɚɸɳɢɯ
ɫɜɨɣ ɩɟɪɜɨɧɚɱɚɥɶɧɵɣ
ɫɨɫɬɚɜ
ɩɨɫɥɟ
ɤɚɠɞɨɝɨ ɰɢɤɥɚ
ɬɚɤɨɝɨ
ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ»
![Page 8: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/8.jpg)
Ɏɢɡɢɤɨ-ɯɢɦɢɱɟɫɤɢɟ
ɨɫɧɨɜɵ
ɤɚɬɚɥɢɡɚ
•Ʉɚɬɚɥɢɡɚɬɨɪ
ɧɟ
ɫɦɟɳɚɟɬ
ɯɢɦɢɱɟɫɤɨɟ
ɪɚɜɧɨ-
ɜɟɫɢɟ, ɚ
ɬɨɥɶɤɨ
ɭɫɤɨɪɹɟɬ
ɟɝɨ
ɞɨɫɬɢɠɟɧɢɟ.
•Ʉɚɬɚɥɢɡɚɬɨɪ
ɜɫɟɝɞɚ
ɨɛɪɚɡɭɟɬ
ɫ
ɢɫɯɨɞɧɵɦɢɪɟɚɝɟɧɬɚɦɢ
ɧɟɭɫɬɨɣɱɢɜɵɟ
ɩɪɨɦɟɠɭɬɨɱɧɵɟɫɨɟɞɢɧɟɧɢɹ.
•ȼ
ɤɚɬɚɥɢɬɢɱɟɫɤɢɯ
ɪɟɚɤɰɢɹɯ
ɩɨɬɟɧɰɢɚɥɶɧɵɣɛɚɪɶɟɪ
ɜɫɟɝɞɚ
ɧɢɠɟ, ɱɟɦ
ɜ
ɬɚɤɨɣ
ɠɟ, ɧɨ
ɧɟɤɚɬɚ-
ɥɢɬɢɱɟɫɤɨɣ
ɪɟɚɤɰɢɢ.
Ɍɪɢ
ɩɪɢɧɰɢɩɚ
ɤɚɬɚɥɢɡɚ
![Page 9: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/9.jpg)
Cɧɢɠɟɧɢɟ
ɷɧɟɪɝɢɢ
ɚɤɬɢɜɚɰɢɢ
Reaction acceleration ~ exp {(Ea(no
cat)
– Ea(with
cat)
)/RT}
When ǻEa
= 50 kJ/mol, then reaction acceleration ~ 105
at 500K
ǻEa
![Page 10: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/10.jpg)
Ʉɜɚɡɢɝɨɦɨɝɟɧɧɵɣɤɚɬɚɥɢɡ
(ɚ) ɋɬɚɛɢɥɢɡɢɪɨɜɚɧɧɵɟ
ɥɢɨɡɨɥɢɦɟɬɚɥɥɨɜ (Pt, Pd, Rh, Ni, ɢ ɬ.ɩ.)
(ɛ) Ⱥɬɦɨɫɮɟɪɧɵɟ
ɡɨɥɢ
(ɥɺɞ, ɫɚɠɚ,ɨɤɫɢɞɵ ɢ ɬ.ɩ.)
Ƚɟɬɟɪɨɝɟɧɧɵɣɤɚɬɚɥɢɡ
(ɚ) ɇɚɧɨɫɬɪɭɤɬɭɪɢɪɨɜɚɧɧɵɟɧɚɧɟɫɟɧɧɵɟ
ɦɟɬɚɥɥɵVIII ɝɪɭɩɩɵ
(ɚ) ɇɚɧɨɫɬɪɭɤɬɭɪɢɪɨɜɚɧɧɵɟɧɚɧɟɫɟɧɧɵɟ
ɩɪɨɫɬɵɟ
ɢɫɦɟɲɚɧɧɵɟ
ɨɤɫɢɞɵ
Ɍɢɩɵ
ɧɚɧɨɤɚɬɚɥɢɬɢɱɟɫɤɢɯ
ɫɢɫɬɟɦ
![Page 11: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/11.jpg)
Ɉɫɧɨɜɧɵɟ
ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ
ɤɚɬɚɥɢɡɚɬɨɪɨɜ
Ʉɨɥɢɱɟɫɬɜɨ ɢɫɯɨɞɧɨɝɨ ɪɟɚɝɟɧɬɚ (ɦɨɥɶ, ɤɝ…), ɤɨɬɨɪɨɟ ɞɚɧɧɨɟɤɨɥɢɱɟɫɬɜɨ ɤɚɬɚɥɢɡɚɬɨɪɚ (ɦɨɥɶ, ɤɝ ... ), ɫɩɨɫɨɛɧɨ ɩɟɪɟɪɚɛɨɬɚɬɶɜ ɟɞ. ɜɪɟɦɟɧɢ (ɫɟɤ, ɦɢɧ…)
Ⱥɤɬɢɜɧɨɫɬɶ
Ⱦɨɥɹ
ɰɟɥɟɜɨɝɨ
ɩɪɨɞɭɤɬɚ
(ɦɚɫ.%, ɦɨɥ.% …) ɜ
ɨɛɳɟɦ
ɤɨɥɢɱɟɫɬɜɟ
ɜɫɟɯɩɨɥɭɱɟɧɧɵɯ
ɩɪɨɞɭɤɬɨɜ
ɋɟɥɟɤɬɢɜɧɨɫɬɶ
ȼɪɟɦɹ
ɷɤɫɩɥɭɚɬɚɰɢɢ
ɤɚɬɚɥɢɡɚɬɨɪɚ
(ɱɚɫ, ɫɭɬɤɢ
…), ɜ
ɬɟɱɟɧɢɟɤɨɬɨɪɨɝɨ
ɤɚɬɚɥɢɡɚɬɨɪ
ɧɟ
ɬɟɪɹɟɬ
ɫɜɨɢɯ
«ɯɨɪɨɲɢɯ»
ɫɜɨɣɫɬɜ
ɋɬɚɛɢɥɶɧɨɫɬɶ
![Page 12: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/12.jpg)
ɑȺɋɌɖ
I
![Page 13: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/13.jpg)
Ɉɛɴɟɦ
= 8 ɫɦ3
Ɉɛɴɟɦ
= 1×8= 8 ɫɦ3
ɉɨɜɟɪɯɧɨɫɬɶ = 24 ɫɦ2
ɉɨɜɟɪɯɧɨɫɬɶ = 6×8=48 ɫɦ2
2 ɫɦ 2 ɫɦ
1 ɫɦ
1 ɫɦ
1 ɫɦ
8 ×
Ⱦɢɫɩɟɪɫɧɨɫɬɶ
= ɩɨɜɟɪɯɧɨɫɬɶ/ɨɛɴɟɦ
![Page 14: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/14.jpg)
ɋɨɨɬɧɨɲɟɧɢɟ
ɚɬɨɦɨɜ
ɜ
ɨɛɴɟɦɟɢ ɧɚ ɩɨɜɟɪɯɧɨɫɬɢ
![Page 15: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/15.jpg)
ɋɨɨɬɧɨɲɟɧɢɟ
ɚɬɨɦɨɜ
ɜ
ɜɟɪɲɢɧɚɯ, ɧɚ ɪɟɛɪɚɯ
ɢ
ɧɚ
ɝɪɚɧɹɯ
ɤɭɛɚ
8 ×
8 : 48 : 96 64 : 96 : 48
ɉɨɤɚɡɚɧɚ
ɬɨɥɶɤɨɨɞɧɚ
ɝɪɚɧɶ
![Page 16: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/16.jpg)
Ɍɟɦɧɵɟ
ɤɪɭɠɤɢ
-
ɨɤɢɫɥɟɧɧɵɟ
ɚɬɨɦɵ
Co
Ɉɤɢɫɥɟɧɢɟ
ɧɚɧɨɱɚɫɬɢɰ
Co (ɦɨɞɟɥɶ)
![Page 17: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/17.jpg)
Ɉɤɢɫɥɟɧɢɟ
ɧɚɧɨɱɚɫɬɢɰ
Co
(ɌɗɆ)
ɗɮɮɟɤɬ
Ʉɢɪɤɟɧɞɚɥɥɚ
Ɇɢɤɪɨɮɨɬɨɝɪɚɮɢɹ
ɱɚɫɬɢɱɧɨɨɤɢɫɥɟɧɧɵɯ
ɧɚɧɨɱɚɫɬɢɰ
Co
Ɇɨɫɬɢɤɢ
![Page 18: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/18.jpg)
H2
/ Fe = 1,5
(ɬɟɨɪɟɬɢɱ.)
ɉɨɝɥɨɳɟɧɢɟ
ɇ2
ɧɚɧɨɤɥɚɫɬɟɪɚɦɢ
Fe(0)
?
0
1
2
3
4
H2/ Fe
0,10,8
19ɦɚɫ.% Fe
![Page 19: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/19.jpg)
334
335
336
337
338
0 1 2 3 4 5 6
ɑɢɫɥɨ ɚɬɨɦɨɜ Pd ɜ ɤɥɚɫɬɟɪɟ
Eb, ɷȼ
Ɇɟɬɚɥɥɢɱɟɫɤɢɣ
Pd
ɋɢɥɶɧɨɟ
ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ«ɦɟɬɚɥɥ-ɧɨɫɢɬɟɥɶ» (SIMS)
ɗɧɟɪɝɢɹ
ɫɜɹɡɢ
Pd 3d5/2
(ɗɋɏȺ)
ɞɥɹ ɤɚɬɚɥɢɡɚɬɨɪɚ
Pd/SiO2
Pd(0)
Pd(II)
![Page 20: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/20.jpg)
Ƚɢɞɪɢɪɨɜɚɧɢɟ
ɩɢɪɪɨɥɚ
ɧɚ
ɧɚɧɨɤɥɚɫɬɟɪɚɯɩɚɥɥɚɞɢɹɊɚɡɦɟɪɧɵɣ
ɷɮɮɟɤɬ: ɚɤɬɢɜɧɨɫɬɶ
Ƚɢɞɪɢɪɨɜɚɧɢɟ
ɩɢɪɪɨɥɚ
ɧɚ
ɧɚɧɨɤɥɚɫɬɟɪɚɯ
Pd
![Page 21: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/21.jpg)
Ƚɢɞɪɢɪɨɜɚɧɢɟ
ɩɢɪɪɨɥɚ
ɧɚ
ɧɚɧɨɤɥɚɫɬɟɪɚɯɩɚɥɥɚɞɢɹɊɚɡɦɟɪɧɵɣ
ɷɮɮɟɤɬ: (+), (-) ɢ
(ɨ)
Ɉɤɢɫɥɟɧɢɟ ɋɈ ɧɚ ɦɟɬɚɥɥɚɯ VIII ɝɪɭɩɩɵ
Rh/Al2
O3
Pd/Al2
O3 Pt/Al2
O3
10
ɧɦ
<5
ɧɦ
8
ɧɦ
<3
ɧɦ
20
ɧɦ
<5
ɧɦ
![Page 22: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/22.jpg)
Ɋɚɡɦɟɪɧɵɣ
ɷɮɮɟɤɬ: ɚɤɬɢɜɧɨɫɬɶ
Ɉɤɢɫɥɟɧɢɟ
ɋɈ
ɧɚ
ɧɚɧɨɤɥɚɫɬɟɪɚɯ
Au/TiO2
![Page 23: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/23.jpg)
Ɋɚɡɦɟɪɧɵɣ
ɷɮɮɟɤɬ: ɚɤɬɢɜɧɨɫɬɶ
Ɉɤɢɫɥɟɧɢɟ
ɋɈ
ɧɚ
ɧɚɧɨɤɥɚɫɬɟɪɚɯ
Au/TiO2
·Mo2
O3
![Page 24: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/24.jpg)
ɉɟɪɟɯɨɞ
«ɦɟɬɚɥɥ
–
ɩɨɥɭɩɪɨɜɨɞɧɢɤ»
![Page 25: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/25.jpg)
Ɉɤɢɫɥɟɧɢɟ
ɋɈ
ɧɚ
Au/MgO ɩɪɢ
200Ʉ
![Page 26: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/26.jpg)
ɑȺɋɌɖ
II
![Page 27: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/27.jpg)
Ɋɚɡɦɟɪɧɵɣ
ɷɮɮɟɤɬ: ɫɟɥɟɤɬɢɜɧɨɫɬɶ
ɂɡɨɦɟɪɢɡɚɰɢɹ
ɚɥɥɢɥɛɟɧɡɨɥɚ
ɧɚ
ɧɚɧɨɤɥɚɫɬɟɪɚɯ
Au
0
0,1
0,2
0,3
0,4
0,5
0 0,4 0,8 1,2 1,6
Log(DAu)
ɐɢɫ
/ɬɪɚɧɫ
2,5 6,3 15,8
39,8
dAu
, ɧɦ
![Page 28: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/28.jpg)
Ⱥɞɫɨɪɛɰɢɹ
ɧɚ
ɪɚɡɧɵɯ
ɝɪɚɧɹɯ
Ƚɪɚɧɶ
[111]ɤ.ɱ. = 3
Ƚɪɚɧɶ
[110]ɤ.ɱ. = 4
Ⱥɞɫɨɪɛɢɪɨɜɚɧɧɵɟ
ɦɨɥɟɤɭɥɵ
![Page 29: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/29.jpg)
Ʉɚɬɚɥɢɡ
ɧɚ
ɪɚɡɧɵɯ
ɝɪɚɧɹɯ
ɇɚ
ɝɪɚɧɢ
[110]
ɚɤɬɢɜɧɨɫɬɶ
= 1 ɭ.ɟ.
ɇɚ
ɝɪɚɧɢ
[111]
ɚɤɬɢɜɧɨɫɬɶ
= 418 ɭ.ɟ.
ɋɢɧɬɟɡ
ɚɦɦɢɚɤɚ
ɧɚ
ɦɨɧɨɤɪɢɫɬɚɥɥɟ
Fe
![Page 30: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/30.jpg)
ɋɟɥɟɤɬɢɜɧɨɫɬɶ
ɧɚ
ɪɚɡɧɵɯ
ɚɬɨɦɚɯ
ɉɪɟɜɪɚɳɟɧɢɟ
ɛɭɬɚɧɚ
ɋ4
ɇ10
ȽɢɞɪɨɝɟɧɨɥɢɡC4
H10
+ H2
= 2C2
H6
ȾɟɝɢɞɪɢɪɨɜɚɧɢɟC4
H10
= C4
H8 + H2
![Page 31: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/31.jpg)
ɑȺɋɌɖ
III
![Page 32: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/32.jpg)
Ɍɟɬɪɚɝɟɤɫɚɷɞɪɚɥɶɧɵɟ
ɧɚɧɨɱɚɫɬɢɰɵ
Pt
200 ɧɦ
![Page 33: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/33.jpg)
Ɇɨɪɮɨɥɨɝɢɱɟɫɤɢ
ɨɞɧɨɪɨɞɧɵɟ ɧɚɧɨɫɬɪɭɤɬɭɪɵ
«ɇɚɧɨɤɭɛɢɤɢ»MgO: ɬɨɥɶɤɨɝɪɚɧɢ (100)
«ɇɚɧɨɤɭɛɢɤɢ»Ag: ɬɨɥɶɤɨɝɪɚɧɢ (100)
ɇɚɧɨɱɚɫɬɢɰɵIr ɧɚ SiO2
![Page 34: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/34.jpg)
ΔGsurf.ΔGsurf.
Ɍɟɪɦɨɞɢɧɚɦɢɱɟɫɤɚɹ
ɧɟɭɫɬɨɣɱɢɜɨɫɬɶ ɧɚɧɨɱɚɫɬɢɰ
![Page 35: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/35.jpg)
Ɇɚɬɪɢɱɧɚɹ
ɫɬɚɛɢɥɢɡɚɰɢɹ
ɧɚɧɨɱɚɫɬɢɰ
?
![Page 36: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/36.jpg)
ɋɬɪɭɤɬɭɪɚ
ɦɨɥɟɤɭɥɹɪɧɨɝɨ
ɫɢɬɚ
3D-ɪɟɤɨɧɫɬɪɭɤɰɢɹ
ɞɚɧɧɵɯ
ɊɋȺ
![Page 37: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/37.jpg)
•Ɍɟɤɫɬɭɪɚ ɩɪɨɫɬɪɚɧɫɬɜɟɧɧɨ-ɭɩɨɪɹɞɨɱɟɧɧɚɹɫɢɫɬɟɦɚ ɤɚɧɚɥɨɜ ɢ ɩɨɥɨɫɬɟɣ
•Ⱦɢɚɦɟɬɪ
ɩɨɪ
ɨɬ
0,3
ɞɨ
30
ɧɦ
•ɍɞ.ɩɨɜɟɪɯɧ. ɞɨ
1200
ɦ2/ɝ
•ɏɢɦ.ɫɨɫɬɚɜ
Si, Al, Ti, P, B, Co ... ɢ ɟɳɟ 20 ɷɥɟɦ.!
•Ɍɟɪɦ. ɫɬɚɛ. ɞɨ
900° ɋ
•ɋɬɨɢɦɨɫɬɶ
ɨɬ
$2
(ɩɪɨɦ.ɨɛɪɚɡɰɵ) ɞɨ$10000 (ɥɚɛ.ɨɛɪɚɡɰɵ) ɡɚ ɤɝ
•ɉɪɨɦ.ɩɪɨ-ɜɨ
ɛɨɥɟɟ
105
ɬɨɧɧ/ɝɨɞ
Ɇɨɥɟɤɭɥɹɪɧɵɟ
ɫɢɬɚ
ɤɚɤ
ɧɨɫɢɬɟɥɢ
![Page 38: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/38.jpg)
ȼɜɟɞɟɧɢɟ
ɩɪɟɤɭɪɫɨɪɚ
Ɉɤɢɫɥɟɧɢ
ɟ
ȼɨɫɫɬɚɧɨɜɥɟɧɢɟ
«Ship-in-bottle»
cɢɧɬɟɡ
ɧɚɧɨɱɚɫɬɢɰ
Ɇɚɬɪɢɰɚ
ɇɚɧɨɤɥɚɫɬɟɪ
ɦɟɬɚɥɥɚ
ɇɚɧɨɤɥɚɫɬɟɪ
ɨɤɫɢɞɚ
![Page 39: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/39.jpg)
Fe3
(CO)12
LaCo(cit)n
LaCo(gly)n
LaFe(CN)x
Zn3
(acac)6
Ni3
(acac)6
Ag2
(FAcO)2
Cu2
(FAcO)4
Ni2
(FAcO)4
[Ru2
(AcO)4
]Cl
ReMoO3
(MeO)7
Fe4
(CO)13
(Et4
N)2
Fe6
C(CO)16
(Et4
N)2
Cu4
Cl6
O(N,N-DENA)4
[Fe3
O(AcO)6
(H2
O)3
]AcO
[Ru3
O(AcO)6
(H2
O)3
]ClO4
Co2
Ni2
(acac)4
(MeO)4
(AcO)2
CuNi2(OH)(EtCOO)3(OCH(CH3)N(CH3)2)2
ɉɨɥɢɹɞɟɪɧɵɟ
ɩɪɟɤɭɪɫɨɪɵ
![Page 40: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/40.jpg)
Ɇɚɬɪɢɱɧɵɣ
ɫɢɧɬɟɡ
ɧɚɧɨɤɥɚɫɬɟɪɨɜ
Fe2
O3
«Ƚɨɫɬɶ» - ɦɨɥɟɤɭɥɚ
Fe3
(CO)12 «ɏɨɡɹɢɧ» - ɦɚɬɪɢɰɚ
NaY
Fe3
(CO)12
Fe2
O3
![Page 41: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/41.jpg)
0
200
400
600
ȐȄȕ.%Fe
ǤǮǤ
·103/c-1
Ɉɤɢɫɥɟɧɢɟ
ɦɟɬɚɧɨɥɚ
ɧɚ
ɧɚɧɨ-Fe2
O3
![Page 42: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/42.jpg)
0
1
2
3
4
5
0,12 Fe
0,40 Fe
9,0 Fe
ln(A
KA
)+7
Ɉɤɢɫɥɟɧɢɟ ɋɈ ɧɚ ɧɚɧɨ-Fe2
O3
![Page 43: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/43.jpg)
ɆɚɬɪɢɰɚMCM-41
Ɉɤɢɫɥɟɧɢɟ,
600°C
ɇɚɧɨɱɚɫɬɢɰɵLaCoO2,6
Ɇɚɬɪɢɱɧɵɣ
ɫɢɧɬɟɡ
ɧɚɧɨ-LaCoO3
ɉɪɨɩɢɬɤɚ
LaCoɩɪɟɤɭɪɫɨɪɨɦ
![Page 44: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/44.jpg)
0 2 4 6 8
r, Å
Co3
O4
/MCM-41
LaCoO3
/MCM-41
CoO
Co3
O4
LaCoO3
FT
(k2
. χ(k
))
ɋɬɪɭɤɬɭɪɧɚɹ
ɪɚɡɭɩɨɪɹɞɨɱɟɧɧɨɫɬɶ ɧɚɧɨɱɚɫɬɢɰ
(EXAFS)
![Page 45: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/45.jpg)
Ɇɚɫɫɢɜɧɵɣ
LaCoO2,98
LaCoO2,6
/MCM-41
0
50
100
150
200
250
300
100 150 200°ɋ
W, ɦɦɨɥɶ/ɝ·ɫ
Ɉɤɢɫɥɟɧɢɟ
ɦɟɬɚɧɨɥɚ
ɜ
ɮɨɪɦɚɥɶɞɟɝɢɞ
![Page 46: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/46.jpg)
-XXI:
ɁȺɄɅɘɑȿɇɂȿ
![Page 47: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/47.jpg)
Nanocatalysis
is
one
of
the
most
exciting
subfields
to
have
emerged
from
nanoscience. Its
central
aim
is
the
control
of
chemical
reactions
by
changing
the
size, dimensionality,
chemical
composition
and
morphology
of
the
reaction
center
and
by
changing
the
kinetics
using
nanopatterning
of
the
reaction
centers. This
approach
opens
up
new
avenues
for
atom-by-atom
design
of
nanocatalysts
with
distinct
and
tunable
chemical
activity,
specificity, and
selectivity. By
Ulrich
Heiz, Uzi
Landman, 2nd
Ed.Published
by
Springer, 2007, 503 pp.
ɉɨɯɜɚɥɶɧɨɟ
ɫɥɨɜɨ
ɧɚɧɨɤɚɬɚɥɢɡɭ!
![Page 48: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/48.jpg)
!
![Page 49: ず ¡îó 10 îó¡¿í ÜïÖÜç ÖíÖÜö êÖÜ¿ÜÇóú (27-½íë-09)nano.msu.ru/files/basics/lecture10_Lunin.pdf · •Catalysis is the central field of nanoscience and](https://reader031.vdocuments.net/reader031/viewer/2022012922/601607def6b98c5cd11968c3/html5/thumbnails/49.jpg)
ɗɧɟɪɝɢɹ
ɫɜɹɡɢ
Au 4f7/2
(ɗɋɏȺ)
Ɋɚɡɦɟɪ
ɤɥɚɫɬɟɪɚ
Au, ɧɦ
Eb, ɷȼ
ɗɧɟɪɝɢɹɫɜɹɡɢ,
ɷȼ
ɋɢɥɶɧɨɟ
ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ«ɦɟɬɚɥɥ-ɧɨɫɢɬɟɥɶ»
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20ɨɋ 900ɨɋ 1400ɨɋ
(tɩɥ.
=
1554ɨɋ
–
ɞɥɹ
ɦɚɫɫɢɜɧɨɝɨ
Pd)
ɉɥɚɜɥɟɧɢɟ
ɧɚɧɨɧɢɬɟɣ
Pd
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ɑɟɪɟɡ
10 ɫɟɤ ɑɟɪɟɡ
50 ɫɟɤ
ɑɟɪɟɡ
100 ɫɟɤ ɑɟɪɟɡ
200 ɫɟɤ
Ɇɨɪɮɨɥɨɝɢɹ
ɨɤɢɫɥɟɧɧɵɯ
ɧɚɧɨɱɚɫɬɢɰ
Co
Ƚɪɚɧɶ
(111)
Ƚɪɚɧɶ
(100)
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Ɉɤɢɫɥɟɧɢɟ
ɧɚɧɨɱɚɫɬɢɰ
Co
Ɇɢɤɪɨɮɨɬɨɝɪɚɮɢɹ
ɩɨɥɧɨɫɬɶɸ
ɨɤɢɫɥɟɧɧɵɯ
ɧɚɧɨɱɚɫɬɢɰ
Co
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Re Mo
O
MeO
O
MeO
MeO
MeO MeO
MeO
MeO
Ɉɤɫɨɦɟɬɨɤɫɢɞɧɵɣ
Re-Mo ɩɪɟɤɭɪɫɨɪ
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Ni(CO)4
Ni(CO)4
o-C6
H4
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COo-C6
H4
(CN)2
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H4
(CN)2
o-C6
H4
(CN)2CO
CO
CO
Ɇɚɬɪɢɱɧɵɣ
«ship-in-bottle»
cɢɧɬɟɡ
ɮɬɚɥɨɰɢɚɧɢɧ
Ni