Ru‐Co Interface Unlocks Efficient Solar‐Driven CO₂ Conversion into Value‐Added Hydrocarbons under Mild Conditions

Abstract Co‐based catalysts exhibit high activity for C–C coupling in the Fischer‐Tropsch synthesis unit, however, they tend to produce primarily C₁ hydrocarbons (CO or CH₄) during CO₂ hydrogenation. Here, a novel 0.04RuCo/MnO‐500 catalyst for photothermocatalytic CO₂ hydrogenation, exhibiting a CO₂ conversion of 65.6% and a value‐added hydrocarbons (C₂₊) selectivity of 63.2% (excluding CO) under mild conditions is reported. The time‐yield of C₂₊ hydrocarbons over 0.04RuCo/MnO‐500 catalyst reaches 8.2 mmol_CH2 g_cat⁻¹ h⁻¹, which is 3.0‐fold and 3.3‐fold higher than that of Co/MnO‐500 (2.7 mmol_CH2 g_cat⁻¹ h⁻¹) and 0.04Ru/MnO‐500 (2.5 mmol_CH2 g_cat⁻¹ h⁻¹), respectively. Further investigations disentangle the exceptional performance that should be attributed to the interface sites between Co and Ru within the catalyst. The presence of interfacial sites enhances the ability of the catalyst to adsorb and activate intermediate (*CO) produced during CO₂ hydrogenation, achieving low CO selectivity and promoting the production of value‐added hydrocarbons with high CO₂ conversion. This work presents a novel approach to developing the Ru/Co catalyst for directly converting CO₂ into value‐added hydrocarbons through photothermocatalytic hydrogenation, realizing the demand for sustainable energy sources.