DFT calculations support these results, revealing reduced energy barriers for CO2 dissociation and modulated energetics of surface oxygen vacancies. In SOERs, the FNR@FeOx-enhanced SFMNR electrode achieves remarkable performance in concurrent CO₂ reduction and propylene production from separate CO2 and propane gas feeds, attaining C3H6 selectivity of 41% (80% selectivity for olefins) while maintaining stable operation over 150 h, highlighting system robustness. This study provides critical insights for the design of heterostructures with tailored electronic and catalytic properties, contributing to environmental sustainability and economic viability in the pursuit of a carbon-neutral future.