Engineering Steam Induced Surface Oxygen Vacancy onto Ni-Fe Bimetallic Nanocomposite for CO2 Electroreduction

Abstract

Surface oxygen vacancies (V_o ) regulation is an effective strategy to improve the electrochemical CO₂ reduction reaction (CO₂ RR) performance by lowering the activation energy barrier of CO₂ ; however, the lack of precise control over the local atomic structures severely hinders the large-scale application of V_o -activated electrocatalyst for CO₂ RR. Herein, an efficient strategy to facilitate CO₂ activation is developed by introducing V_o into transition metal nanoparticles (NPs) with a steam-assisted chemical vapor deposition method. With the steam process, abundant surface V_o are introduced into the assembled Ni-Fe bimetallic NPs composite (H-NiFe/NG), which adjust surface Ni/Fe atoms to low-valent coordinatively unsaturated Ni (+1)/Fe (+2) sites, serving as electron-rich centers to adsorb and activate inert CO₂ molecules. The as-prepared H-NiFe/NG composite exhibits excellent catalytic performance with a maximum Faradaic efficiency of 94% at -0.80 V (vs RHE) for CO production with remarkable stability. The density function theory calculations corroborate that the Ni atoms around surface V_o significantly lower the energy barrier for COOH* intermediate formation, which gives a low overpotential for reducing CO₂ to CO, exhibiting superior CO₂ RR performance. This general synthetic strategy provides a new insight to introduce surface V_o on transition metal for efficient CO₂ reduction.

Keywords: CO 2 reduction reaction; bimetallic nanocomposites; chemical vapor deposition; oxygen vacancies; steam treatment.