Bond-selective control of a heterogeneously catalyzed reaction

被引：184

作者：

Killelea, Daniel R. ^{[1
,2
]}

Campbell, Victoria L. ^{[1
,2
]}

Shuman, Nicholas S. ^{[1
,2
]}

Utz, Arthur L. ^{[1
,2
]}

机构：

[1] Tufts Univ, Dept Chem, Medford, MA 02155 USA

[2] Tufts Univ, WM Keck Fdn Lab Mat Chem, Medford, MA 02155 USA

来源：

SCIENCE | 2008年 / 319卷 / 5864期

关键词：

D O I：

10.1126/science.1152819

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Energy redistribution, including the many phonon- assisted and electronically assisted energy- exchange processes at a gas- metal interface, can hamper vibrationally mediated selectivity in chemical reactions. We establish that these limitations do not prevent bond- selective control of a heterogeneously catalyzed reaction. State- resolved gas- surface scattering measurements show that the nu(1) C-H stretch vibration in trideuteromethane ( CHD3) selectively activates C-H bond cleavage on a Ni( 111) surface. Isotope- resolved detection reveals a CD3: CHD2 product ratio > 30: 1, which contrasts with the 1: 3 ratio for an isoenergetic ensemble of CHD3 whose vibrations are statistically populated. Recent studies of vibrational energy redistribution in the gas and condensed phases suggest that other gas- surface reactions with similar vibrational energy flow dynamics might also be candidates for such bond- selective control.

引用

页码：790 / 793

页数：4

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