RESUMO
To investigate synergistic effect between geometric and electronic structures on directing CO2 RR selectivity, water phase synthetic protocol and surface architecture engineering strategy are developed to construct monodispersed Bi-doped Cu-based nanocatalysts. The strongly correlated catalytic directionality and Bi3+ dopant can be rationalized by the regulation of [*COOH]/[*CO] adsorption capacities through the appropriate doping of Bi3+ electronic modulator, resulting in volcano relationship between FECO /TOFCO and surface EVBM values. Spectroscopic study reveals that the dual-site binding mode ([CuâµâC(âO)OâBi3+ ]) enabled by Cu1 Bi3+ 2 motif in single-phase Cu150 Bi1 nanocatalyst drives CO2-to-CO conversion. In contrast, the study of dynamic Bi speciation and phase transformation in dual-phase Cu50 Bi1 nanocatalyst unveils that the Bi0 -Bi0 contribution emerges at the expense of BOC phase, suggesting metallic Bi0 phase acting as [H]Ë formation center switches CO2 RR selectivity toward CO2-to-HCOO- conversion via [*OCHO] and [*OCHOK] intermediates. This work provides significant insight into how geometric architecture cooperates with electronic effect and catalytic motif/phase to guide the selectivity of electrocatalytic CO2 reduction through the distinct surface-bound intermediates and presents molecular-level understanding of catalytic mechanism for CO/HCOO- formation.