Abstract
Doped metal oxide catalysts have important applications in heterogeneous catalysis, whereas the fundamental effects of doping on the reactivity of catalysts are elusive. Herein, benefiting from the study of a series of atomic clusters MVO5- (M = V-Zn) in catalytic CO oxidation by molecular O2 under thermal collision conditions, the crucial effects of doping on the electronic structure and then the catalytic reactivity of MVO5- were successfully rationalized by using mass spectrometry and theoretical calculations. We defined the energy gap of active orbitals that are closely related to electron transfer in MVO5- during CO oxidation. It was discovered that such an energy gap can modulate reaction thermodynamics, whereas the orbital overlap of MVO5- with CO controls the kinetics. The doped clusters MVO5- (M = Cr-Zn) have reduced energy gaps than that in host V2O5-, and doping can modify the orbital overlap of MVO5- (M = Cr-Zn) with CO. Only the MnVO5- and ZnVO5- clusters that have rational energy gaps and proper orbital overlap with CO are catalytically reactive.
Original language | English |
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Pages (from-to) | 14180-14186 |
Number of pages | 7 |
Journal | Journal of Physical Chemistry C |
Volume | 123 |
Issue number | 23 |
DOIs | |
Publication status | Published - 13 Jun 2019 |
Externally published | Yes |