Architecting Hierarchically Porous Electrocatalyst for Direct Liquid Carbon Utilization

Abstract Carbon dioxide (CO 2 ) capture and utilization (CCU), driven by renewable electricity, are pivotal technologies to achieve the mitigation of CO 2 emissions and further valorization, respectively. Integrating CO 2 capture with upgrading represents an emerging cutting‐edge approach, given that each individual process step incurs significant energetic and economic costs. Herein, hierarchically porous N‐doped carbon‐supported Ni catalyst (Ni‐HP) is architected for KOH‐based reactive CO 2 capture. Benefiting from the hierarchical porous structures with enriched exposure of active sites as well as accelerated mass transfer, this catalyst achieves a high Faradaic efficiency (FE) for CO exceeding 90%. Moreover, this catalyst facilitates industrial syngas production over 60 h of cyclic operation at −100 mA cm −2 in alkaline solutions saturated with simulated flue gas containing 20 vol% CO 2 . This work not only provides in‐depth insight into the origin of the catalytic activity of porous carbon‐based catalysts but also offers electrochemical guidance for the rational integration of reactive CO 2 capture within the broader carbon management community.