Thermal Methane Conversion to Syngas Mediated by Rh1-Doped Aluminum Oxide Cluster Cations RhAl3O4<sup/>.
Laser ablation generated RhAl3O4+heteronuclear metal oxide cluster cations have been mass-selected using a quadrupole mass filter and reacted with CH4or CD4in a linear ion trap reactor under thermal collision conditions. The reactions have been characterized by state-of-the-art mass spectrometry and quantum chemistry calculations. The RhAl3O4+cluster can activate four C-H bonds of a methane molecule and convert methane to syngas, an important intermediate product in methane conversion to value-added chemicals. The Rh atom is the active site for activation of the C-H bonds of methane. The high electron-withdrawing capability of Rh atom is the driving force to promote the conversion of methane to syngas. The polarity of Rh oxidation state is changed from positive to negative after the reaction. This study has provided the first example of methane conversion to syngas by heteronuclear metal oxide clusters under thermal collision conditions. Furthermore, the molecular level origin has been revealed for the condensed-phase experimental observation that trace amounts of Rh can promote the participation of lattice oxygen of chemically very inert support (Al2O3) to oxidize methane to carbon monoxide.
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, P. R. China.|University of Chinese Academy of Sciences , Beijing 100049, P. R. China.
Ya-Ke
YK
Li
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, P. R. China.|University of Chinese Academy of Sciences , Beijing 100049, P. R. China.
Zhen
Z
Yuan
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, P. R. China.
Yan-Xia
YX
Zhao
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, P. R. China.|University of Chinese Academy of Sciences , Beijing 100049, P. R. China.
Chongyang
C
Zhao
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, P. R. China.|University of Chinese Academy of Sciences , Beijing 100049, P. R. China.
Qing-Yu
QY
Liu
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, P. R. China.
Hui
H
Chen
Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, P. R. China.
Sheng-Gui
SG
He