Surface-Enhanced Raman Spectroscopy for Boosting Electrochemical CO₂ Reduction on Amorphous-Surfaced Tin Oxide...

Amorphous materials disrupt the intrinsic linear scalar dependence seen in their crystalline counterparts, typically exhibiting enhanced catalytic characteristics. Nevertheless, substantial obstacles remain in terms of boosting their stability, enhancing their conductivity, and elucidating distinct catalytic mechanisms. Herein, a core-shell catalyst, comprising a crystalline SnO₂ core and an amorphous SnO shell supported on MXene (denoted as SnO₂@SnO/MXene), was prepared utilizing hydrothermal and solution reduction methods. The SnO₂@SnO/MXene catalyst excels in the electrocatalytic conversion of CO₂ to formate, yielding a Faradaic efficiency (FE) as high as 93% for formate production at -1.17 V vs RHE and demonstrating exceptional durability. Both density functional theory (DFT) calculations and experimental results indicate that the SnO shell bolsters formate formation by fine-tuning the adsorption energy of the *OCHO intermediate. In SnO₂@SnO/MXene, MXene plays a vital role in enhancing the conductivity and stability of the amorphous shell and especially amplifying Raman signals of catalyst components. The ex/in situ surface-enhanced Raman scattering (SERS) application further confirms the formation of amorphous SnO and further enables the direct detection of the formation of the intermediate species. This work provides the basis for the application of amorphous materials in practical electrocatalytic reduction of CO₂ reduction.