Catalytic NO Reduction by Noble-Metal-Free Vanadium-Aluminum Oxide Cluster Anions

By using state-of-the-art mass spectrometry and guided by the newly discovered single-electron mechanism (SEM; e.g., Ti³⁺ + 2NO → Ti⁴⁺-O^•- + N₂O), we determined experimentally that the vanadium-aluminum oxide clusters V_4-xAl_xO_10-x^- (x = 1-3) can catalyze the reduction of NO by CO and substantiated theoretically that the SEM still prevails in driving the catalysis. This finding marks an important step in cluster science in which a noble metal had been demonstrated to be indispensable in NO activation mediated by heteronuclear metal clusters. The results provide new insights into the SEM in which active V-Al cooperative communication favors the transfer of an unpaired electron from the V atom to NO attached to the Al atom on which the reduction reaction actually takes place. This study provides a clear picture for improving our understanding of related heterogeneous catalysis, and the electron hopping behavior induced by NO adsorption could be a fundamental chemistry for driving NO reduction.