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.

Keywords

artificial synthesis of CH ₄ / electronic structure optimization / Fe species cocatalyst / photocatalytic CO ₂ reduction / SiC

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