Transient pulsed laser synthesis: boosting CO2-ethanol conversion and Li-CO2 batteries performance by p-d orbital hybridization and electron delocalization

Cu-based electrocatalysts are promising for the electrocatalytic CO 2 reduction reaction (eCO 2 RR) to realize valuable chemicals production. Here, a Mg-doped Cu based electrocatalysts via transient CO 2 pulsed laser (L 4 -Mg/Cu x O) was synthesized for highly selective eCO 2 RR to ethanol (C 2 H 5 OH). The synergistic effect of Mg-doping and transient CO 2 pulsed laser irradiation enables excellent eCO 2 RR performance, realizing Faradaic efficiencies (FE) of 52.2% and 74.1% for C 2 H 5 OH and C 2 products under a high current density of 298.9 mA cm −2 , respectively. Operando Raman spectroscopy and DFT simulations results confirm that Mg-doping strategy suppresses the hydrogen evolution reaction (HER), enhances CO adsorption, elevates local pH and accelerates H 2 O dissociation, which could be beneficial for promoting OC–CO coupling and proton supply in eCO 2 RR. Furthermore, Mg incorporation induces electron delocalization in which electron accumulation on the C atom of *CHCOH intermediate and its enhanced p-d orbital coupling with Cu interface, which stabilizes the C–O bond from breakage and selectively favours the C 2 H 5 OH pathway, thus decoupling the selectivity between C 2 H 5 OH and ethylene. When employed in Li-CO 2 batteries, L 4 -Mg/Cu x O delivers 20480 mAh g −1 discharge capacity and cycling stability over 187 cycles. This work presents a universal strategy for regulating eCO 2 RR selectivity through precise laser energy delivery, demonstrating significant potential for renewable energy conversion and storage.