Ȼ.ȼ.Ɋɨɦɚɧɨɜɫɤɢɣɏɢɦɢɱɟɫɤɢɣ

ɮɚɤɭɥɶɬɟɬ

ɆȽɍ

Ɍɟɥ: 939-20-54, ɮɚɤɫ: 939-35-70,e-mail: bvromanovsky@mail.ru

Ʌɟɤɰɢɹ

10 ɢɡ

ɰɢɤɥɚ

«Ɏɭɧɞɚɦɟɧɬɚɥɶɧɵɟɨɫɧɨɜɵ

ɧɚɧɨɬɟɯɧɨɥɨɝɢɣ»

(27-ɦɚɪ-09)

• 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?

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!

ȼȼȿȾȿɇɂȿ

Ʉɚɬɚɥɢɡ

ɤɚɤ

ɫɚɦɨɫɬɨɹɬɟɥɶɧɵɣ

ɪɚɡɞɟɥɯɢɦɢɱɟɫɤɨɣ

ɧɚɭɤɢ

(1779-1848)

1835 ɝɨɞ

ȼȼɉ ɏɢɦ. ɩɪɨɦ.

25% 80%

Ʉɚɬɚɥɢɡ: ɜɤɥɚɞ

ɜ

ȼȼɉ

ɢ

ɩɪɨɞɭɤɰɢɸ ɯɢɦɢɱɟɫɤɨɣ

ɩɪɨɦɵɲɥɟɧɧɨɫɬɢ

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»

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

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

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

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

ɑȺɋɌɖ

I

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

ɋɨɨɬɧɨɲɟɧɢɟ

ɚɬɨɦɨɜ

ɜ

ɨɛɴɟɦɟɢ ɧɚ ɩɨɜɟɪɯɧɨɫɬɢ

ɋɨɨɬɧɨɲɟɧɢɟ

ɚɬɨɦɨɜ

ɜ

ɜɟɪɲɢɧɚɯ, ɧɚ ɪɟɛɪɚɯ

ɢ

ɧɚ

ɝɪɚɧɹɯ

ɤɭɛɚ

8 ×

8 : 48 : 96 64 : 96 : 48

ɉɨɤɚɡɚɧɚ

ɬɨɥɶɤɨɨɞɧɚ

ɝɪɚɧɶ

Ɍɟɦɧɵɟ

ɤɪɭɠɤɢ

-

ɨɤɢɫɥɟɧɧɵɟ

ɚɬɨɦɵ

Co

Ɉɤɢɫɥɟɧɢɟ

ɧɚɧɨɱɚɫɬɢɰ

Co (ɦɨɞɟɥɶ)

Ɉɤɢɫɥɟɧɢɟ

ɧɚɧɨɱɚɫɬɢɰ

Co

(ɌɗɆ)

ɗɮɮɟɤɬ

Ʉɢɪɤɟɧɞɚɥɥɚ

Ɇɢɤɪɨɮɨɬɨɝɪɚɮɢɹ

ɱɚɫɬɢɱɧɨɨɤɢɫɥɟɧɧɵɯ

ɧɚɧɨɱɚɫɬɢɰ

Co

Ɇɨɫɬɢɤɢ

H2

/ Fe = 1,5

(ɬɟɨɪɟɬɢɱ.)

ɉɨɝɥɨɳɟɧɢɟ

ɇ2

ɧɚɧɨɤɥɚɫɬɟɪɚɦɢ

Fe(0)

?

0

1

2

3

4

H2/ Fe

0,10,8

19ɦɚɫ.% Fe

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)

Ƚɢɞɪɢɪɨɜɚɧɢɟ

ɩɢɪɪɨɥɚ

ɧɚ

ɧɚɧɨɤɥɚɫɬɟɪɚɯɩɚɥɥɚɞɢɹɊɚɡɦɟɪɧɵɣ

ɷɮɮɟɤɬ: ɚɤɬɢɜɧɨɫɬɶ

Ƚɢɞɪɢɪɨɜɚɧɢɟ

ɩɢɪɪɨɥɚ

ɧɚ

ɧɚɧɨɤɥɚɫɬɟɪɚɯ

Pd

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

Ɋɚɡɦɟɪɧɵɣ

ɷɮɮɟɤɬ: ɚɤɬɢɜɧɨɫɬɶ

Ɉɤɢɫɥɟɧɢɟ

ɋɈ

ɧɚ

ɧɚɧɨɤɥɚɫɬɟɪɚɯ

Au/TiO2

Ɋɚɡɦɟɪɧɵɣ

ɷɮɮɟɤɬ: ɚɤɬɢɜɧɨɫɬɶ

Ɉɤɢɫɥɟɧɢɟ

ɋɈ

ɧɚ

ɧɚɧɨɤɥɚɫɬɟɪɚɯ

Au/TiO2

·Mo2

O3

ɉɟɪɟɯɨɞ

«ɦɟɬɚɥɥ

–

ɩɨɥɭɩɪɨɜɨɞɧɢɤ»

Ɉɤɢɫɥɟɧɢɟ

ɋɈ

ɧɚ

Au/MgO ɩɪɢ

200Ʉ

ɑȺɋɌɖ

II

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

Ⱥɞɫɨɪɛɰɢɹ

ɧɚ

ɪɚɡɧɵɯ

ɝɪɚɧɹɯ

Ƚɪɚɧɶ

[111]ɤ.ɱ. = 3

Ƚɪɚɧɶ

[110]ɤ.ɱ. = 4

Ⱥɞɫɨɪɛɢɪɨɜɚɧɧɵɟ

ɦɨɥɟɤɭɥɵ

Ʉɚɬɚɥɢɡ

ɧɚ

ɪɚɡɧɵɯ

ɝɪɚɧɹɯ

ɇɚ

ɝɪɚɧɢ

[110]

ɚɤɬɢɜɧɨɫɬɶ

= 1 ɭ.ɟ.

ɇɚ

ɝɪɚɧɢ

[111]

ɚɤɬɢɜɧɨɫɬɶ

= 418 ɭ.ɟ.

ɋɢɧɬɟɡ

ɚɦɦɢɚɤɚ

ɧɚ

ɦɨɧɨɤɪɢɫɬɚɥɥɟ

Fe

ɋɟɥɟɤɬɢɜɧɨɫɬɶ

ɧɚ

ɪɚɡɧɵɯ

ɚɬɨɦɚɯ

ɉɪɟɜɪɚɳɟɧɢɟ

ɛɭɬɚɧɚ

ɋ4

ɇ10

ȽɢɞɪɨɝɟɧɨɥɢɡC4

H10

+ H2

= 2C2

H6

ȾɟɝɢɞɪɢɪɨɜɚɧɢɟC4

H10

= C4

H8 + H2

ɑȺɋɌɖ

III

Ɍɟɬɪɚɝɟɤɫɚɷɞɪɚɥɶɧɵɟ

ɧɚɧɨɱɚɫɬɢɰɵ

Pt

200 ɧɦ

Ɇɨɪɮɨɥɨɝɢɱɟɫɤɢ

ɨɞɧɨɪɨɞɧɵɟ ɧɚɧɨɫɬɪɭɤɬɭɪɵ

«ɇɚɧɨɤɭɛɢɤɢ»MgO: ɬɨɥɶɤɨɝɪɚɧɢ (100)

«ɇɚɧɨɤɭɛɢɤɢ»Ag: ɬɨɥɶɤɨɝɪɚɧɢ (100)

ɇɚɧɨɱɚɫɬɢɰɵIr ɧɚ SiO2

ΔGsurf.ΔGsurf.

Ɍɟɪɦɨɞɢɧɚɦɢɱɟɫɤɚɹ

ɧɟɭɫɬɨɣɱɢɜɨɫɬɶ ɧɚɧɨɱɚɫɬɢɰ

Ɇɚɬɪɢɱɧɚɹ

ɫɬɚɛɢɥɢɡɚɰɢɹ

ɧɚɧɨɱɚɫɬɢɰ

?

ɋɬɪɭɤɬɭɪɚ

ɦɨɥɟɤɭɥɹɪɧɨɝɨ

ɫɢɬɚ

3D-ɪɟɤɨɧɫɬɪɭɤɰɢɹ

ɞɚɧɧɵɯ

ɊɋȺ

•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

ȼɜɟɞɟɧɢɟ

ɩɪɟɤɭɪɫɨɪɚ

Ɉɤɢɫɥɟɧɢ

ɟ

ȼɨɫɫɬɚɧɨɜɥɟɧɢɟ

«Ship-in-bottle»

cɢɧɬɟɡ

ɧɚɧɨɱɚɫɬɢɰ

Ɇɚɬɪɢɰɚ

ɇɚɧɨɤɥɚɫɬɟɪ

ɦɟɬɚɥɥɚ

ɇɚɧɨɤɥɚɫɬɟɪ

ɨɤɫɢɞɚ

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

Ɇɚɬɪɢɱɧɵɣ

ɫɢɧɬɟɡ

ɧɚɧɨɤɥɚɫɬɟɪɨɜ

Fe2

O3

«Ƚɨɫɬɶ» - ɦɨɥɟɤɭɥɚ

Fe3

(CO)12 «ɏɨɡɹɢɧ» - ɦɚɬɪɢɰɚ

NaY

Fe3

(CO)12

Fe2

O3

0

200

400

600

ȐȄȕ.%Fe

ǤǮǤ

·103/c-1

Ɉɤɢɫɥɟɧɢɟ

ɦɟɬɚɧɨɥɚ

ɧɚ

ɧɚɧɨ-Fe2

O3

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

ɆɚɬɪɢɰɚMCM-41

Ɉɤɢɫɥɟɧɢɟ,

600°C

ɇɚɧɨɱɚɫɬɢɰɵLaCoO2,6

Ɇɚɬɪɢɱɧɵɣ

ɫɢɧɬɟɡ

ɧɚɧɨ-LaCoO3

ɉɪɨɩɢɬɤɚ

LaCoɩɪɟɤɭɪɫɨɪɨɦ

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)

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

-XXI:

ɁȺɄɅɘɑȿɇɂȿ

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!

!

ɗɧɟɪɝɢɹ

ɫɜɹɡɢ

Au 4f7/2

(ɗɋɏȺ)

Ɋɚɡɦɟɪ

ɤɥɚɫɬɟɪɚ

Au, ɧɦ

Eb, ɷȼ

ɗɧɟɪɝɢɹɫɜɹɡɢ,

ɷȼ

ɋɢɥɶɧɨɟ

ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ«ɦɟɬɚɥɥ-ɧɨɫɢɬɟɥɶ»

20ɨɋ 900ɨɋ 1400ɨɋ

(tɩɥ.

=

1554ɨɋ

–

ɞɥɹ

ɦɚɫɫɢɜɧɨɝɨ

Pd)

ɉɥɚɜɥɟɧɢɟ

ɧɚɧɨɧɢɬɟɣ

Pd

ɑɟɪɟɡ

10 ɫɟɤ ɑɟɪɟɡ

50 ɫɟɤ

ɑɟɪɟɡ

100 ɫɟɤ ɑɟɪɟɡ

200 ɫɟɤ

Ɇɨɪɮɨɥɨɝɢɹ

ɨɤɢɫɥɟɧɧɵɯ

ɧɚɧɨɱɚɫɬɢɰ

Co

Ƚɪɚɧɶ

(111)

Ƚɪɚɧɶ

(100)

Ɉɤɢɫɥɟɧɢɟ

ɧɚɧɨɱɚɫɬɢɰ

Co

Ɇɢɤɪɨɮɨɬɨɝɪɚɮɢɹ

ɩɨɥɧɨɫɬɶɸ

ɨɤɢɫɥɟɧɧɵɯ

ɧɚɧɨɱɚɫɬɢɰ

Co

Re Mo

O

MeO

O

MeO

MeO

MeO MeO

MeO

MeO

Ɉɤɫɨɦɟɬɨɤɫɢɞɧɵɣ

Re-Mo ɩɪɟɤɭɪɫɨɪ

Ni(CO)4

Ni(CO)4

o-C6

H4

(CN)2

COo-C6

H4

(CN)2

o-C6

H4

(CN)2

o-C6

H4

(CN)2CO

CO

CO

Ɇɚɬɪɢɱɧɵɣ

«ship-in-bottle»

cɢɧɬɟɡ

ɮɬɚɥɨɰɢɚɧɢɧ

Ni