Highly selective photocatalytic reduction of CO₂ to CH₄ on electron‐rich Fe species cocatalyst under visible light irradiation

Abstract Efficient photocatalytic reduction of CO₂ to high‐calorific‐value CH₄, an ideal target product, is a blueprint for C₁ industry relevance and carbon neutrality, but it also faces great challenges. Herein, we demonstrate unprecedented hybrid SiC photocatalysts modified by Fe‐based cocatalyst, which are prepared via a facile impregnation‐reduction method, featuring an optimized local electronic structure. It exhibits a superior photocatalytic carbon‐based products yield of 30.0 µmol g⁻¹ h⁻¹ and achieves a record CH₄ selectivity of up to 94.3%, which highlights the effectiveness of electron‐rich Fe cocatalyst for boosting photocatalytic performance and selectivity. Specifically, the synergistic effects of directional migration of photogenerated electrons and strong π‐back bonding on low‐valence Fe effectively strengthen the adsorption and activation of reactants and intermediates in the CO₂ → CH₄ pathway. This study inspires an effective strategy for enhancing the multielectron reduction capacity of semiconductor photocatalysts with low‐cost Fe instead of noble metals as cocatalysts.