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Linear Alkane CC Bond Chemistry Mediated by Metal Surfaces
Author(s) -
Cai Zeying,
Liu Meizhuang,
She Limin,
Li Xiaoli,
Lee Jason,
Yao DaoXin,
Zhang Haiming,
Chi Lifeng,
Fuchs Harald,
Zhong Dingyong
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500097
Subject(s) - dehydrogenation , chemistry , endothermic process , exothermic reaction , alkane , dissociation (chemistry) , alkyl , hydrocarbon , photochemistry , exothermic process , computational chemistry , adsorption , organic chemistry , catalysis
Linear alkanes undergo different CC 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 CC 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 CC coupling between alkyl intermediates is exothermic. On the contrary, due to the much stronger CPt bonds, dehydrogenation on Pt(110) surfaces is energetically favorable, resulting in multiple hydrogen loss followed by CC bond dissociation.