RESUMEN

In the electrochemical CO2 reduction reaction (CO2RR), Cu alloy electrocatalysts can control the CO2RR selectivity by modulating the intermediate binding energy. Here, we report the thermodynamic-based Cu-Sn bimetallic phase control in heterogeneous catalysts for selective CO2 conversion. Starting from the thermodynamic understanding about Cu-Sn bimetallic compounds, we established the specific processing window for Cu-Sn bimetallic phase control. To modulate the Cu-Sn bimetallic phases, we controlled the oxygen partial pressure (pO2) during the calcination of electrospun Cu and Sn ions-incorporated nanofibers (NFs). This resulted in the formation of CuO-SnO2 NFs (full oxidation), Cu-SnO2 NFs (selective reduction), Cu3Sn/CNFs, Cu41Sn11/CNFs, and Cu6Sn5/CNFs (full reduction). In the CO2RR, CuO-SnO2 NFs exhibited formate (HCOO-) production and Cu-SnO2 NFs showed carbon monoxide (CO) production with the faradaic efficiency (FE) of 65.3% at -0.99 V (vs. RHE) and 59.1% at -0.89 V (vs. RHE) respectively. Cu-rich Cu41Sn11/CNFs and Cu3Sn/CNFs enhanced the methane (CH4) production with the FE of 39.1% at -1.36 V (vs. RHE) and 34.7% at -1.50 V (vs. RHE). However, Sn-rich Cu6Sn5/CNFs produced HCOO- with the FE of 58.6% at -2.31 V (vs. RHE). This study suggests the methodology for bimetallic catalyst design and steering the CO2RR pathway by controlling the active sites of Cu-Sn alloys.