Hierarchically Ordered Pore Engineering of Carbon Supports with High‐Density Edge‐Type Single‐Atom Sites to Boost Electrochemical CO₂ Reduction

Abstract Metal sites at the edge of the carbon matrix possess unique geometric and electronic structures, exhibiting higher intrinsic activity than in‐plane sites. However, creating single‐atom catalysts with high‐density edge sites remains challenging. Herein, the hierarchically ordered pore engineering of metal–organic framework‐based materials to construct high‐density edge‐type single‐atomic Ni sites for electrochemical CO₂ reduction reaction (CO₂RR) is reported. The created ordered macroporous structure can expose enriched edges, further increased by hollowing the pore walls, which overcomes the low edge percentage in the traditional microporous substrates. The prepared single‐atomic Ni sites on the ordered macroporous carbon with ultra‐thin hollow walls (Ni/H‐OMC) exhibit Faraday efficiencies of CO above 90% in an ultra‐wide potential window of 600 mV and a turnover frequency of 3.4 × 10⁴ h⁻¹, much superior than that of the microporous material with dominant plane‐type sites. Theory calculations reveal that NiN₄ sites at the edges have a significantly disrupted charge distribution, forming electron‐rich Ni centers with enhanced adsorption ability with ^*COOH, thereby boosting CO₂RR efficiency. Furthermore, a Zn–CO₂ battery using the Ni/H‐OMC cathode shows an unprecedentedly high power density of 15.9 mW cm⁻² and maintains an exceptionally stable charge–discharge performance over 100 h.