исследование анодного окисления этанола в топливном

444
Структура и динамика молекулярных систем, 2007 г., Выпуск №1
ɍȾɄ 543.429.22:547.556.3:546.289
ɂɋɋɅȿȾɈȼȺɇɂȿ ȺɇɈȾɇɈȽɈ ɈɄɂɋɅȿɇɂə ɗɌȺɇɈɅȺ ȼ
ɌɈɉɅɂȼɇɈɆ ɗɅȿɆȿɇɌȿ ɆȿɌɈȾɈɆ ɗɉɊ
Ʉɚɞɢɪɨɜ Ɇ.Ʉ.
ɂɧɫɬɢɬɭɬ ɨɪɝɚɧɢɱɟɫɤɨɣ ɢ ɮɢɡɢɱɟɫɤɨɣ ɯɢɦɢɢ Ʉɇɐ ɊȺɇ
e-mail: [email protected]
ɗɬɚɧɨɥ ɹɜɥɹɟɬɫɹ ɩɪɢɜɥɟɤɚɬɟɥɶɧɵɦ ɬɨɩɥɢɜɨɦ ɞɥɹ ɷɥɟɤɬɪɢɱɟɫɤɢɯ
ɬɪɚɧɫɩɨɪɬɧɵɯ ɫɪɟɞɫɬɜ ɧɚ ɨɫɧɨɜɟ ɬɨɩɥɢɜɧɵɯ ɷɥɟɦɟɧɬɨɜ (Ɍɗ), ɬɚɤ ɤɚɤ ɨɧ
ɧɟ ɬɨɤɫɢɱɟɧ ɢ ɥɟɝɤɨ ɦɨɠɟɬ ɛɵɬɶ ɩɪɨɢɡɜɟɞɟɧ ɜ ɛɨɥɶɲɨɦ ɤɨɥɢɱɟɫɬɜɟ
ɩɭɬɟɦ ɮɟɪɦɟɧɬɚɰɢɢ ɫɚɯɚɪɫɨɞɟɪɠɚɳɢɯ ɫɵɪɶɟɜɵɯ ɦɚɬɟɪɢɚɥɨɜ. ɀɢɞɤɢɟ
ɬɨɩɥɢɜɚ, ɬɚɤɢɟ ɤɚɤ ɫɩɢɪɬɵ ɧɢɡɤɨɦɨɥɟɤɭɥɹɪɧɨɝɨ ɜɟɫɚ, ɢɦɟɸɬ
ɩɪɟɢɦɭɳɟɫɬɜɚ ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɱɢɫɬɵɦ ɜɨɞɨɪɨɞɨɦ, ɩɨɬɨɦɭ ɱɬɨ ɫ ɧɢɦɢ
ɥɟɝɤɨ ɨɛɪɚɳɚɬɶɫɹ, ɢɯ ɥɟɝɤɨ ɯɪɚɧɢɬɶ ɢ ɬɪɚɧɫɩɨɪɬɢɪɨɜɚɬɶ, ɢɫɩɨɥɶɡɭɹ
ɢɦɟɸɳɭɸɫɹ
ɬɨɩɥɢɜɧɭɸ
ɢɧɮɪɚɫɬɪɭɤɬɭɪɭ
ɫ
ɧɟɛɨɥɶɲɢɦɢ
ɦɨɞɢɮɢɤɚɰɢɹɦɢ. Ȼɨɥɟɟ ɬɨɝɨ, ɢɯ ɷɧɟɪɝɟɬɢɱɟɫɤɚɹ ɩɥɨɬɧɨɫɬɶ ɫɪɚɜɧɢɦɚ ɫ
ɷɧɟɪɝɟɬɢɱɟɫɤɨɣ ɩɥɨɬɧɨɫɬɶɸ ɩɪɢɜɵɱɧɨɝɨ ɠɢɞɤɨɝɨ ɬɨɩɥɢɜɚ, ɨɬ 6 ɤȼɬ ɤɝ-1
(5 ɤȼɬ ɥ-1) ɞɥɹ ɦɟɬɚɧɨɥɚ ɞɨ ɩɪɢɦɟɪɧɨ 10 ɤȼɬ ɤɝ-1 (8 ɤȼɬ ɥ-1) ɞɥɹ ɬɹɠɟɥɵɯ
ɫɩɢɪɬɨɜ. Ɉɞɧɚɤɨ ɨɫɬɚɟɬɫɹ ɧɟɫɤɨɥɶɤɨ ɧɟɪɟɲɟɧɧɵɯ ɩɪɨɛɥɟɦ, ɹɜɥɹɸɳɢɯɫɹ
ɫɟɪɶɟɡɧɵɦ ɩɪɟɩɹɬɫɬɜɢɟɦ ɧɚ ɩɭɬɢ ɩɪɚɤɬɢɱɟɫɤɨɝɨ ɩɪɢɦɟɧɟɧɢɹ ɩɪɹɦɵɯ
ɫɩɢɪɬɨɜɵɯ Ɍɗ (ɉɋɌɗ). ɗɬɨ, ɜɨ-ɩɟɪɜɵɯ, ɜɵɫɨɤɢɣ ɚɤɬɢɜɚɰɢɨɧɧɵɣ ɛɚɪɶɟɪ
ɪɟɚɤɰɢɢ ɩɪɹɦɨɝɨ ɷɥɟɤɬɪɨɯɢɦɢɱɟɫɤɨɝɨ ɨɤɢɫɥɟɧɢɹ ɫɩɢɪɬɚ (ɊɉɗɈɋ) ɧɚ
ɚɧɨɞɟ, ɜɨ-ɜɬɨɪɵɯ, ɡɚɝɪɹɡɧɟɧɢɟ ɩɥɚɬɢɧɨɜɨɝɨ (Pt-) ɤɚɬɚɥɢɡɚɬɨɪɚ
ɫɨɩɪɨɞɭɤɬɧɵɦ ɦɨɧɨɤɫɢɞɨɦ ɭɝɥɟɪɨɞɚ (ɋɈ), ɨɛɪɚɡɭɸɳɢɦɫɹ ɜ ɯɨɞɟ
ɊɉɗɈɋ, ɢ, ɜ-ɬɪɟɬɶɢɯ, ɩɟɪɟɫɟɱɟɧɢɟ (ɤɪɨɫɫɨɭɜɟɪ) ɦɨɥɟɤɭɥɨɣ ɫɩɢɪɬɚ
ɩɨɥɢɷɥɟɤɬɪɨɥɢɬɢɱɟɫɤɨɣ ɦɟɦɛɪɚɧɵ.
ɉɨɥɧɨɟ ɨɤɢɫɥɟɧɢɟ ɷɬɚɧɨɥɚ ɜɤɥɸɱɚɟɬ 12 ɷɥɟɤɬɪɨɧɨɜ:
ɋ2ɇ5Ɉɇ + 3ɇ2Ɉ ĺ 2CO2 + 12H+aq + 12e(1)
Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɜ ɪɟɚɤɰɢɸ ɨɤɚɡɵɜɚɸɬɫɹ ɜɨɜɥɟɱɟɧɧɵɦɢ ɦɧɨɝɨ
ɩɪɨɦɟɠɭɬɨɱɧɵɯ ɩɪɨɞɭɤɬɨɜ. ɉɨɷɬɨɦɭ ɩɨɢɫɤ ɩɨɞɯɨɞɨɜ ɞɥɹ ɩɨɫɬɚɞɢɣɧɨɝɨ
ɢɫɫɥɟɞɨɜɚɧɢɹ ɷɬɨɝɨ ɩɪɨɰɟɫɫɚ ɩɪɟɞɫɬɚɜɥɹɟɬɫɹ ɢɧɬɟɪɟɫɧɨɣ ɡɚɞɚɱɟɣ. ɗɬɨ
ɜɚɠɧɨ ɞɥɹ ɭɩɪɚɜɥɟɧɢɹ ɨɛɪɚɡɨɜɚɧɢɟɦ ɚɞɫɨɪɛɢɪɨɜɚɧɧɵɯ ɩɪɨɦɟɠɭɬɨɱɧɵɯ
ɩɪɨɞɭɤɬɨɜ ɢ, ɬɚɤɢɦ ɨɛɪɚɡɨɦ, ɢɫɤɥɸɱɟɧɢɹ ɨɛɪɚɡɨɜɚɧɢɹ ɡɚɝɪɹɡɧɹɸɳɢɯ
ɜɟɳɟɫɬɜ, ɤɨɬɨɪɵɟ ɩɪɢɡɧɚɧɵ ɜɪɟɞɧɵɦɢ ɞɥɹ ɪɚɛɨɬɵ ɬɨɩɥɢɜɧɨɝɨ ɷɥɟɦɟɧɬɚ.
ɉɨɞɪɨɛɧɵɣ ɚɧɚɥɢɡ ɩɪɨɞɭɤɬɨɜ ɪɟɚɤɰɢɢ ɯɪɨɦɚɬɨɝɪɚɮɢɱɟɫɤɢɦɢ
ɦɟɬɨɞɚɦɢ [1] ɢɥɢ ɞɢɮɮɟɪɟɧɰɢɚɥɶɧɨɣ ɷɥɟɤɬɪɨɯɢɦɢɱɟɫɤɨɣ ɦɚɫɫ-ɫɩɟɤɬɪɨɦɟɬɪɢɟɣ (ȾɗɆɋ) [2-4] ɩɨɡɜɨɥɢɥ ɫɮɨɪɦɭɥɢɪɨɜɚɬɶ ɛɨɥɟɟ ɞɟɬɚɥɶɧɵɣ
ɦɟɯɚɧɢɡɦ ɪɟɚɤɰɢɢ ɨɤɢɫɥɟɧɢɹ ɷɬɚɧɨɥɚ ɧɚ Pt-ɷɥɟɤɬɪɨɞɚɯ ɜ ɤɢɫɥɨɣ ɫɪɟɞɟ,
Раздел 2
ɤɨɬɨɪɵɣ ɜɤɥɸɱɚɟɬ ɩɚɪɚɥɥɟɥɶɧɵɟ
ɨɤɢɫɥɟɧɢɹ, ɤɚɤ ɩɨɤɚɡɚɧɨ ɧɢɠɟ:
H2O
445
ɢ
ɩɨɫɥɟɞɨɜɚɬɟɥɶɧɵɟ
ɪɟɚɤɰɢɢ
CH3-COOH + 4H+ + 4e-
(2)
CH3-CHO + 2H+ + 2e-
(3)
CH3-CH2OH
Ɋɟɚɤɰɢɹ (2) ɢɦɟɟɬ ɦɟɫɬɨ, ɝɥɚɜɧɵɦ ɨɛɪɚɡɨɦ, ɩɪɢ ɜɵɫɨɤɢɯ
ɩɨɬɟɧɰɢɚɥɚɯ [ȿ > 0.8 ȼ ɩɨ ɜɨɞɨɪɨɞɧɨɦɭ ɷɥɟɤɬɪɨɞɭ ɫɪɚɜɧɟɧɢɹ (ȼɗɋ)],
ɩɪɢ ɤɨɬɨɪɵɯ ɦɨɥɟɤɭɥɵ ɜɨɞɵ ɚɤɬɢɜɢɪɭɸɬɫɹ ɞɨ ɨɛɪɚɡɨɜɚɧɢɹ ɨɤɢɫɥɟɧɧɵɯ
ɩɪɨɞɭɤɬɨɜ ɧɚ ɩɨɜɟɪɯɧɨɫɬɢ ɩɥɚɬɢɧɵ; ɪɟɚɤɰɢɹ (3) ɢɦɟɟɬ ɦɟɫɬɨ ɩɪɢ ɧɢɡɤɢɯ
ɩɨɬɟɧɰɢɚɥɚɯ (ȿ < 0.6 ȼ)[1]. ɉɪɢ ɩɪɨɦɟɠɭɬɨɱɧɵɯ ɩɨɬɟɧɰɢɚɥɚɯ (0.6 ȼ ” ȿ
” 0.8 ȼ) ɩɪɨɢɫɯɨɞɢɬ ɞɢɫɫɨɰɢɚɬɢɜɧɚɹ ɚɞɫɨɪɛɰɢɹ ɜɨɞɵ:
Pt + H2O ĺ Pt-OHads + H+ + e(4)
ɬɚɤ ɱɬɨ ɨɤɢɫɥɟɧɢɟ ɚɞɫɨɪɛɢɪɨɜɚɧɧɨɝɨ ɋɇ3-ɋɇɈ ɦɨɠɟɬ ɞɚɬɶ ɭɤɫɭɫɧɭɸ
ɤɢɫɥɨɬɭ, ɤɚɤ ɩɨɤɚɡɚɧɨ ɧɢɠɟ:
(ɋɇ3-ɋɈɈɇ)ads + Pt-OHads ĺ CH3-COH + H+ + e- + Pt
(5)
Ⱦɚɥɶɧɟɣɲɟɟ ɨɤɢɫɥɟɧɢɟ ɞɨ ɭɝɥɟɤɢɫɥɨɝɨ ɝɚɡɚ ɨɛɵɱɧɨ ɡɚɬɪɭɞɧɟɧɨ ɧɚ
ɱɢɫɬɵɯ Pt-ɷɥɟɤɬɪɨɞɚɯ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ. Ɉɞɧɚɤɨ, ɦɨɧɨɤɫɢɞ
ɭɝɥɟɪɨɞɚ, ɞɟɣɫɬɜɭɸɳɢɣ ɤɚɤ ɨɬɪɚɜɥɹɸɳɢɣ ɚɝɟɧɬ, ɢ ɋɈ2 ɛɵɥɢ ɱɟɬɤɨ
ɧɚɛɥɸɞɟɧɵ ɢɧɮɪɚɤɪɚɫɧɨɣ ɨɬɪɚɠɚɬɟɥɶɧɨɣ ɫɩɟɤɬɪɨɫɤɨɩɢɟɣ [5], ȾɗɆɋ [2]
ɢ ɝɚɡɨɜɨɣ ɯɪɨɦɚɬɨɝɪɚɮɢɟɣ [1], ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ, ɫɨɜɦɟɫɬɧɨ ɫ ɧɟɤɨɬɨɪɵɦɢ
ɫɥɟɞɚɦɢ ɦɟɬɚɧɚ ɩɪɢ ɧɢɡɤɢɯ ɩɨɬɟɧɰɢɚɥɚɯ (ȿ < 0.4 ȼ ɩɨ ȼɗɋ) [2]. ɗɬɨ
ɦɨɠɧɨ ɨɛɴɹɫɧɢɬɶ ɫɥɟɞɭɸɳɢɦɢ ɦɟɯɚɧɢɡɦɚɦɢ:
Pt + ɋɇ3-ɋHO ĺ Pt-(CO-CH3)ads + H+ + e(6)
Pt + Pt-(CO-CH3)ads ĺ Pt-(CO)ads + Pt-(CH3)ads
(7)
Pt + H2O ĺ Pt-Hads + Pt-OHads
(8)
Pt-(CH3)ads + Pt-Hadsĺ CH4
(9)
Pt-(CO)ads + Pt-OHads ĺ CO2 + H+ + e(10)
ɂɫɫɥɟɞɨɜɚɧɢɹ ɩɪɨɜɨɞɢɥɢɫɶ ɫ ɩɨɦɨɳɶɸ Ɍɗ, ɫɩɟɰɢɚɥɶɧɨ
ɫɤɨɧɫɬɪɭɢɪɨɜɚɧɧɨɝɨ ɧɚɦɢ ɞɥɹ ɢɫɫɥɟɞɨɜɚɧɢɹ ɜ ɪɟɡɨɧɚɬɨɪɟ ɫɩɟɤɬɪɨɦɟɬɪɚ
ɗɉɊ. ɋɤɨɪɨɫɬɢ ɩɨɬɨɤɚ ɤɢɫɥɨɪɨɞɚ ɢ ɜɨɞɨɪɨɞɚ ɩɨɞɞɟɪɠɢɜɚɥɢɫɶ ɧɚ ɭɪɨɜɧɟ
10 ɢ 20 ɦɥ ɦɢɧ-1. ɉɥɨɬɧɨɫɬɶ ɩɥɚɬɢɧɨɜɨɝɨ ɤɚɬɚɥɢɡɚɬɨɪɚ, ɧɚɧɟɫɟɧɧɨɝɨ ɧɚ
ɇɚɮɢɨɧ 115, ɛɵɥɚ ɩɪɢɦɟɪɧɨ 1.8 ɦɝ ɫɦ-2. 10 ɦɤɥ 1 Ɇ ɫɩɢɪɬɨɜɨɝɨ
ɪɚɫɬɜɨɪɚ ȾɆɉɈ ɧɚɧɨɫɢɥɫɹ ɧɚ ɨɞɧɭ ɢɡ ɫɬɨɪɨɧ ɩɨɤɪɵɬɨɣ ɤɚɬɚɥɢɡɚɬɨɪɨɦ
446
Структура и динамика молекулярных систем, 2007 г., Выпуск №1
ɦɟɦɛɪɚɧɵ (ɉɄɆ). Ɍɚ ɫɬɨɪɨɧɚ ɉɄɆ, ɤɭɞɚ ɩɨɞɚɜɚɥɫɹ ɤɢɫɥɨɪɨɞ, ɫɥɭɠɢɥɚ
ɤɚɬɨɞɨɦ, ɞɪɭɝɚɹ ɫɬɨɪɨɧɚ, ɤɭɞɚ ɩɨɞɚɜɚɥɫɹ ɜɨɞɨɪɨɞ, - ɚɧɨɞɨɦ. Ⱦɥɹ
ɪɟɝɢɫɬɪɚɰɢɢ ɪɚɞɢɤɚɥɶɧɵɯ ɢɧɬɟɪɦɟɞɢɚɬɨɜ ɩɪɢɦɟɧɹɥɚɫɶ ɫɩɢɧɨɜɚɹ
ɥɨɜɭɲɤɚ – ɰɢɤɥɢɱɟɫɤɢɣ ɧɢɬɪɨɧ, 5,5-ɞɢɦɟɬɢɥɩɢɪɪɨɥɢɧ-N-ɨɤɫɢɥ
(ȾɆɉɈ). ȾɆɉɈ ɩɪɨɹɜɥɹɟɬ ɪɟɚɤɰɢɸ ɩɪɢɫɨɟɞɢɧɟɧɢɹ ɤɨɪɨɬɤɨɠɢɜɭɳɟɝɨ
ɪɚɞɢɤɚɥɚ ɏ ɢ ɨɛɪɚɡɭɟɬ ɫɬɚɛɢɥɶɧɵɣ ɪɚɞɢɤɚɥ, ɫɩɢɧ-ɚɞɞɭɤɬ ȾɆɉɈ*/ɏ.
Me
H
Me
N
+
X
.
Me
H
Me
X
N
O
O
ȾɆɉɈ
ȾɆɉɈ/X
(11)
.
ɂɧɮɨɪɦɚɰɢɹ ɨ ɪɚɞɢɤɚɥɟ ɏ ɢɡɜɥɟɤɚɟɬɫɹ ɢɡ ɜɟɥɢɱɢɧ ɤɨɧɫɬɚɧɬ
ɫɜɟɪɯɬɨɧɤɨɝɨ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ ɚɬɨɦɚ ɚɡɨɬɚ ɚN ɧɢɬɪɨɤɫɢɥɶɧɨɝɨ ɪɚɞɢɤɚɥɚ ɢ
ȕ-ɩɪɨɬɨɧɚ ɚɇ ɩɨ ɥɢɬɟɪɚɬɭɪɧɵɦ ɞɚɧɧɵɦ. ȼ ɯɨɞɟ ɪɚɛɨɬɵ Ɍɗ ɧɚ ɚɧɨɞɧɨɣ
ɫɬɨɪɨɧɟ ɛɵɥɢ ɨɛɧɚɪɭɠɟɧɵ ɫɩɢɧ-ɚɞɞɭɤɬɵ ȾɆɉɈ*·ɋɇ(Ɉɇ)ɋɇ3 [6] (aN =
15.7 Ƚɫ, aH = 23.0 Ƚɫ) ɢ ȾɆɉɈ*·ɋɈɋɇ3 [7] (aN = 14.5 Ƚɫ, aH = 18.6 Ƚɫ)
(ɪɢɫ.1), ɫɜɢɞɟɬɟɥɶɫɬɜɭɸɳɢɟ ɨ ɩɪɨɬɟɤɚɧɢɢ ɪɟɚɤɰɢɣ (12)-(13):
Pt +ɋ2ɇ5Ɉɇ ĺ Pt-[ɋɇ(Ɉɇ)CH3]ads + H+ + e(12)
ɋ2ɇ5Ɉɇ ĺ ɋɇ3-ɋHO + 2H+ + 2e(13)
ɢ ɪɟɚɤɰɢɢ (6), ɚ ɬɚɤɠɟ ɫɩɢɧ-ɚɞɞɭɤɬ ȾɆɉɈ*·Ɉɇ [8] (aN = 14.5 Ƚɫ, aH =
14.7 Ƚɫ), ɩɨɞɬɜɟɪɠɞɚɸɳɢɣ ɩɪɨɬɟɤɚɧɢɟ ɪɟɚɤɰɢɢ (8). ɂɬɚɤ, ɫ ɩɨɦɨɳɶɸ Ɍɗ
ɞɥɹ ɗɉɊ ɩɨɞɬɜɟɪɠɞɚɟɬɫɹ, ɱɬɨ ɩɪɢ ɧɢɡɤɢɯ ɩɨɬɟɧɰɢɚɥɚɯ ɨɤɢɫɥɟɧɢɟ
ɷɬɚɧɨɥɚ ɧɚ ɚɧɨɞɟ ɢɞɟɬ ɩɨ ɪɟɚɤɰɢɨɧɧɨɣ ɫɯɟɦɟ (3). ȼ ɨɬɥɢɱɢɟ ɨɬ ɞɪɭɝɢɯ
ɦɟɬɨɞɨɜ, ɗɉɊ ɩɨɡɜɨɥɹɟɬ ɪɟɝɢɫɬɪɢɪɨɜɚɬɶ ɢ ɪɚɧɧɢɣ ɩɪɨɞɭɤɬ ɪɚɡɥɨɠɟɧɢɹ
ɫɩɢɪɬɚ - ɪɚɞɢɤɚɥ ·ɋɇ(Ɉɇ)ɋɇ3, ɱɬɨ ɧɚɛɥɸɞɚɥɨɫɶ ɢ ɪɚɧɟɟ [9] ɫ
ɩɪɢɦɟɧɟɧɢɟɦ ɜ ɤɚɱɟɫɬɜɟ ɫɩɢɧɨɜɨɣ ɥɨɜɭɲɤɢ ɚɥɶɮɚ-(4-ɩɢɪɢɞɢɥ-1-ɨɤɫɢɞ)N-ɬɪɟɬ-ɛɭɬɢɥɧɢɬɪɨɧɚ. Ⱦɪɭɝɢɟ ɩɪɨɞɭɤɬɵ ɩɪɹɦɨɝɨ ɚɧɨɞɧɨɝɨ ɪɚɡɥɨɠɟɧɢɹ
ɷɬɚɧɨɥɚ – ɪɚɞɢɤɚɥɵ ·ɋɈɋɇ3 ɢ ·Ɉɇ ɦɟɬɨɞɨɦ ɗɉɊ ɨɛɧɚɪɭɠɟɧɵ ɜɩɟɪɜɵɟ.
Ɋɚɛɨɬɚ Ɍɗ ɤɨɧɬɪɨɥɢɪɨɜɚɥɚɫɶ ɩɭɬɟɦ ɫɧɹɬɢɹ ɞɢɚɝɧɨɫɬɢɱɟɫɤɢɯ
ɯɚɪɚɤɬɟɪɢɫɬɢɤ – E-i ɢ p-i, ɝɞɟ E – ɧɚɩɪɹɠɟɧɢɟ, p ɢ i – ɩɥɨɬɧɨɫɬɢ
ɦɨɳɧɨɫɬɢ ɢ ɬɨɤɚ, ɫɨɨɬɜɟɬɫɬɜɟɧɧɨ. ɉɨɤɚɡɚɧɨ, ɱɬɨ ɚɧɨɞɧɨɟ ɨɤɢɫɥɟɧɢɟ
ɷɬɚɧɨɥɚ ɩɪɢɜɨɞɢɬ ɤ ɡɧɚɱɢɬɟɥɶɧɨɦɭ ɭɯɭɞɲɟɧɢɸ ɯɚɪɚɤɬɟɪɢɫɬɢɤ ɜɨɞɨɪɨɞɤɢɫɥɨɪɨɞɧɨɝɨ Ɍɗ ɫ Pt-ɤɚɬɚɥɢɡɚɬɨɪɨɦ, ɱɬɨ ɱɟɬɤɨ ɜɢɞɧɨ ɩɨ ɪɢɫ. 2.
ɇɚɩɪɹɠɟɧɢɟ, ɜɵɪɚɛɚɬɵɜɚɟɦɨɟ Ɍɗ, ɩɚɞɚɟɬ ɞɨ ɡɧɚɱɟɧɢɣ 0.2-0.4 ȼ, ɚ
ɩɥɨɬɧɨɫɬɶ ɦɨɳɧɨɫɬɢ ɭɦɟɧɶɲɚɟɬɫɹ ɛɨɥɟɟ ɱɟɦ ɧɚ ɩɨɪɹɞɨɤ. ɗɬɨ, ɝɥɚɜɧɵɦ
Раздел 2
447
ɨɛɪɚɡɨɦ, ɹɜɥɹɟɬɫɹ ɪɟɡɭɥɶɬɚɬɨɦ ɡɚɝɪɹɡɧɟɧɢɹ ɚɧɨɞɚ ɫɨɩɪɨɞɭɤɬɧɵɦ ɋɈ,
ɨɛɪɚɡɭɸɳɢɦɫɹ ɜ ɯɨɞɟ ɪɟɚɤɰɢɢ (7).
ɗɤɫɩɟɪ. ɫɩɟɤɬɪ
ɋɢɦɭɥ. ɫɩɟɤɬɪ
.
50%
ȾɆɉɈ/ ɋɇ(Ɉɇ)ɋɇ3
25%
ȾɆɉɈ/ ɋɈɋɇ3
25%
ȾɆɉɈ/ Ɉɇ
.
.
20 Ƚɫ
ɇ
Ɋɢɫɭɧɨɤ 1. ɋɩɟɤɬɪ ɗɉɊ (ɜɜɟɪɯɭ), ɩɨɥɭɱɟɧɧɵɣ ɫ 10 ɦɤɥ 1Ɇ ȾɆɉɈ/ɋ2ɇ5Ɉɇ
ɪɚɫɬɜɨɪɨɦ, ɧɚɧɟɫɟɧɧɵɦ ɧɚ ɚɧɨɞɧɭɸ ɫɬɨɪɨɧɭ ɇ2/Ɉ2 Ɍɗ ɞɥɹ ɗɉɊ, ɨɛɨɪɭɞɨɜɚɧɧɨɝɨ
ɫ 1.8 ɦɝ/ɫɦ2 Pt/ɇɚɮɢɨɧ ɉɄɆ; ɨɛɳɢɣ ɫɢɦɭɥɢɪɨɜɚɧɧɵɣ ɫɩɟɤɬɪ (2-ɣ ɫɜɟɪɯɭ) ɢ
ɫɢɦɭɥɢɪɨɜɚɧɧɵɟ ɫɩɟɤɬɪɵ (3-5-ɟ ɫɜɟɪɯɭ) ɫɩɢɧ-ɚɞɞɭɤɬɨɜ ȾɆɉɈ, ɜɧɨɫɹɳɢɟ ɜɤɥɚɞ
ɜ ɨɛɳɢɣ ɫɢɦɭɥɢɪɨɜɚɧɧɵɣ ɫɩɟɤɬɪ.
ɂɬɚɤ, Ɍɗ ɞɥɹ ɗɉɊ ɩɨɡɜɨɥɹɟɬ ɪɟɝɢɫɬɪɢɪɨɜɚɬɶ ɪɚɞɢɤɚɥɶɧɵɟ
ɩɪɨɞɭɤɬɵ ɧɚ ɷɥɟɤɬɪɨɞɚɯ ɢ ɫɧɢɦɚɬɶ ɞɢɚɝɧɨɫɬɢɱɟɫɤɢɟ ɯɚɪɚɤɬɟɪɢɫɬɢɤɢ.
Ⱦɚɧɧɵɟ ɦɟɬɨɞɚ ɗɉɊ ɞɨɩɨɥɧɹɸɬ ɢ ɭɬɨɱɧɹɸɬ ɪɟɡɭɥɶɬɚɬɵ, ɩɨɥɭɱɟɧɧɵɟ
ɞɪɭɝɢɦɢ ɦɟɬɨɞɚɦɢ. Ɉɛɳɟɢɡɜɟɫɬɧɨ, ɱɬɨ ɤɚɬɚɥɢɬɢɱɟɫɤɢɟ ɫɜɨɣɫɬɜɚ
ɦɚɬɟɪɢɚɥɚ ɷɥɟɤɬɪɨɞɚ ɹɜɥɹɸɬɫɹ ɤɥɸɱɨɦ ɭɩɪɚɜɥɟɧɢɹ ɨɛɪɚɡɨɜɚɧɢɟɦ
ɚɞɫɨɪɛɢɪɨɜɚɧɧɵɯ ɩɪɨɦɟɠɭɬɨɱɧɵɯ ɩɪɨɞɭɤɬɨɜ ɢ, ɬɚɤɢɦ ɨɛɪɚɡɨɦ,
ɢɫɤɥɸɱɟɧɢɹ ɨɛɪɚɡɨɜɚɧɢɹ ɡɚɝɪɹɡɧɹɸɳɢɯ ɤɚɬɚɥɢɡɚɬɨɪ ɜɟɳɟɫɬɜ.
Ɇɭɥɶɬɢɦɟɬɚɥɥɢɱɟɫɤɢɟ ɤɚɬɚɥɢɡɚɬɨɪɵ ɧɟɨɛɯɨɞɢɦɵ ɞɥɹ ɬɨɝɨ, ɱɬɨɛɵ
ɫɟɥɟɤɬɢɜɧɨ ɨɪɢɟɧɬɢɪɨɜɚɬɶ ɪɟɚɤɰɢɸ ɨɤɢɫɥɟɧɢɹ ɫɩɢɪɬɨɜ ɜ ɧɚɩɪɚɜɥɟɧɢɢ
ɩɨɥɧɨɝɨ ɫɝɨɪɚɧɢɹ ɞɨ ɭɝɥɟɤɢɫɥɨɝɨ ɝɚɡɚ. Ɍɗ ɞɥɹ ɗɉɊ, ɨɫɧɚɳɟɧɧɵɣ
ɦɨɞɢɮɢɰɢɪɨɜɚɧɧɵɦ
ɤɚɬɚɥɢɡɚɬɨɪɨɦ,
ɛɭɞɟɬ
ɹɜɥɹɬɶɫɹ
ɦɨɳɧɵɦ
ɢɧɫɬɪɭɦɟɧɬɨɦ ɢɫɫɥɟɞɨɜɚɧɢɹ ɫɜɨɣɫɬɜ ɧɨɜɵɯ ɦɟɦɛɪɚɧɧɨ-ɷɥɟɤɬɪɨɞɧɵɯ
ɛɥɨɤɨɜ ɞɥɹ Ɍɗ.
448
Структура и динамика молекулярных систем, 2007 г., Выпуск №1
E-H 2
E-H 2 /EtO H
1.0
0.8
E/B
0.6
0.4
0.2
0.0
0
20
40
60
80
100
120
140
2
i/(ɦ Ⱥ/ɫɦ )
ɚ
p -H 2
p -H 2 /E tO H
35
30
20
2
p/(ɦȼɬ/ɫɦ )
25
15
10
5
0
-5
0
20
40
60
80
100
120
140
2
i/(ɦ Ⱥ /ɫ ɦ )
ɛ
Ɋɢɫɭɧɨɤ 2. Ⱦɢɚɝɧɨɫɬɢɱɟɫɤɢɟ ɤɪɢɜɵɟ (ɱɟɪɧɵɟ ɤɪɭɠɤɢ) ɇ2/Ɉ2 Ɍɗ ɞɥɹ ɗɉɊ,
ɨɛɨɪɭɞɨɜɚɧɧɨɝɨ ɫ 1.8 ɦɝ/ɫɦ2 Pt/ɇɚɮɢɨɧ ɉɄɆ; ɞɢɚɝɧɨɫɬɢɱɟɫɤɢɟ ɤɪɢɜɵɟ (ɫɜɟɬɥɵɟ
ɤɪɭɠɤɢ) ɞɥɹ ɬɨɝɨ ɠɟ Ɍɗ, ɧɚ ɚɧɨɞɧɭɸ ɫɬɨɪɨɧɭ ɤɨɬɨɪɨɝɨ ɧɚɧɟɫɟɧ 10 ɦɤɥ 1 Ɇ
ȾɆɉɈ/ɋ2ɇ5Ɉɇ ɪɚɫɬɜɨɪ.
Раздел 2
449
Ʌɢɬɟɪɚɬɭɪɚ
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