Co ⁰ /Co ²⁺ Engineered N/O‐Doped Porous Carbon Catalysts for High‐Performance CO ₂ Hydrogenation Under Mild Conditions

Developing efficient and tunable catalysts for low‐temperature CO 2 hydrogenation remains a central challenge for CO 2 valorization. Here, cobalt nanoparticles supported on benzimidazole‐derived N/O‐doped porous carbon (BIDC) are reported as an effective catalytic platform enabling high CO 2 conversion and controllable product selectivity. The high surface area and interconnected porosity of BIDC, together with N/O‐derived Lewis basic sites, promote CO 2 adsorption and activation while stabilizing well‐dispersed cobalt species. Systematic reduction studies demonstrate that the cobalt oxidation state governs catalytic behavior: Co 2+ sites facilitate CO 2 adsorption and activation, whereas metallic Co 0 sites enable H 2 dissociation. An optimal Co 0 /Co 2+ ratio, achieved by reduction at 450°C, balances these functionalities and delivers a CO 2 conversion of 98% at 250°C and 30 bar, exceeding typical values reported for Co‐based catalysts. Reaction conditions further tune the pathway: at 250°C and WHSV = 2.4 L g −1 h −1 , methane is formed almost exclusively (>96% selectivity), while under milder conditions (170°C, WHSV = 7.2 L g −1 h −1 ) alcohols become dominant (51.2% selectivity) with strong suppression of methanation. These results identify BIDC‐supported cobalt as a promising platform for CO 2 hydrogenation with tunable selectivity.