Interface engineering of a GaN/In2O3 heterostructure for highly efficient electrocatalytic CO2 reduction to formate

Electrocatalytic CO2 reduction reaction (eCO2RR) to obtain formate is a promising method to con-sume CO2 and alleviate the energy crisis. Indium-based electrocatalysts have demonstrated consid-erable potential to produce formate. However, their unsatisfactory long-term stability and selectiv-ity restrict their widespread application. In this study, a heterostructure of GaN-and In2O3-encapsulated porous carbon nanofibers was constructed via electrospinning and the phase transition of eutectic gallium-indium during calcination. The GaN and In2O3 nanoparti-cle-encapsulated porous carbon nanofibers, when used as electrocatalysts for eCO2RR, displayed high formate selectivity with a faradaic efficiency of 87% and maximum partial current density of 29.7 mA cm-2 in a 0.5 mol L-1 KHCO3 aqueous solution. The existence of the interface can cause a positive shift in the In 3d binding energy, leading to electronic redistribution. Moreover, the GaN component induced a higher proportion of O-vacancy sites in the In2O3 phase, resulting in improved selectivity for CO2-to-formate. In-situ Raman experiments and density functional theory calculations revealed that the interface between GaN and In2O3 could lower the adsorption energy of the key intermediates for formate production, thus providing superior eCO2RR performance. In addition, the framework of the porous carbon nanofibers exhibited a large electrochemically active surface area, which enabled the full exposure of the active sites. This study highlights the cooperation be-tween GaN and In2O3 components and provides new insights into the rational design of catalysts with high CO2-to-formate conversion efficiencies.& COPY; 2023, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.