Atomically precise copper dopants in metal clusters boost up stability, fluorescence, and photocatalytic activity
Yifei Zhang, Jingjing Zhang, Zhiwen Li, Zhaoxian Qin, Sachil Sharma, Gao Li
Abstract
Abstract The structurally precise alloy nanoclusters have been emerged as a burgeoning nanomaterial for their unique physical/chemical features. We here report a rod-like nanocluster [Au 12 Cu 13 (PPh 3 ) 10 I 7 ](SbF 6 ) 2 (Au 12 Cu 13 ), which was generated through a transformation of a [Au 9 (PPh 3 ) 8 ] 3+ intermediate in the presence of CuI, unveiled by time-dependent UV-vis spectroscopy, electrospray ionization mass spectrometry as well as single crystal X-ray diffraction. Au 12 Cu 13 is comprised of two pentagonal bipyramids Au 6 Cu units and a pentagonal prism Cu 11 unit, where the copper and gold species are presented in +1 and 0 chemical states. The Cu-dopants significantly improved the stability and fluorescence (quantum yield: ~34%, 34-folds of homo-Au 25 (PPh 3 ) 10 Br 7 ). The high stability of Au 12 Cu 13 is attributed to the high binding energy of iodine ligands, Au-Cu synergistic effects and its 16-electon system as an 8-electron superatom dimer. Finally, the robust Au 12 Cu 13 exhibited high catalytic activity (~92% conversion and ~84% methyl formate-selectivity) and good durability in methanol photo-oxidation.