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Linear alkane C-C bond chemistry mediated by metal surfaces.

Chemphyschem : a European journal of chemical physics and physical chemistry (2015-03-11)
Zeying Cai, Meizhuang Liu, Limin She, Xiaoli Li, Jason Lee, Dao-Xin Yao, Haiming Zhang, Lifeng Chi, Harald Fuchs, Dingyong Zhong
ANOTACE

Linear alkanes undergo different C-C bond chemistry (coupling or dissociation) thermally activated on anisotropic metal surfaces depending on the choice of the substrate material. Owing to the one-dimensional geometrical constraint, selective dehydrogenation and C-C coupling (polymerization) of linear alkanes take place on Au(110) surfaces with missing-row reconstruction. However, the case is dramatically different on Pt(110) surfaces, which exhibit similar reconstruction as Au(110). Instead of dehydrogenative polymerization, alkanes tend to dehydrogenative pyrolysis, resulting in hydrocarbon fragments. Density functional theory calculations reveal that dehydrogenation of alkanes on Au(110) surfaces is an endothermic process, but further C-C coupling between alkyl intermediates is exothermic. On the contrary, due to the much stronger C-Pt bonds, dehydrogenation on Pt(110) surfaces is energetically favorable, resulting in multiple hydrogen loss followed by C-C bond dissociation.

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