Asymmetric gradient orbital interaction of hetero-diatomic active sites for promoting C - C coupling

Abstract

Diatomic-site catalysts (DACs) garner tremendous attention for selective CO2 photoreduction, especially in the thermodynamical and kinetical mechanism of CO2 to C2+ products. Herein, we first engineer a novel Zn-porphyrin/RuCu-pincer complex DAC (ZnPor-RuCuDAC). The heteronuclear ZnPor-RuCuDAC exhibits the best acetate selectivity (95.1%), while the homoatomic counterparts (ZnPor-Ru(2)DAC and ZnPor-Cu(2)DAC) present the best CO selectivity. In-situ spectroscopic measurements reveal that the heteronuclear Ru-Cu sites easily appear C-1 intermediate coupling. The in-depth analyses confirm that due to the strong gradient orbital coupling of Ru4d-Cu3d resonance, two formed *CO intermediates of Ru-Cu heteroatom show a significantly weaker electrostatic repulsion for an asymmetric charge distribution, which result from a side-to-side absorption and narrow dihedral angle distortion. Moreover, the strongly overlapped Ru/Cu-d and CO molecular orbitals split into bonding and antibonding orbitals easily, resulting in decreasing energy splitting levels of C-1 intermediates. These results collectively augment the collision probability of the two *CO intermediates on heteronuclear DACs. This work first provides a crucial perspective on the symmetry-forbidden coupling mechanism of C-1 intermediates on diatomic sites. Molecular insights into the selectivity mechanism of dual-atom sites are required to engineer efficient solar-fuel catalysts. Here, the authors reveal symmetry-forbidden coupling mechanism of C1 intermediates on diatomic sites by manipulating metal gradient orbital interaction over diatomic COFs.