Industry‐Level Electrocatalytic CO2 to CO Enabled by 2D Mesoporous Ni Single Atom Catalysts

Electrocatalytic CO2 reduction reaction (eCO2RR) has captivated widespread attentions, yet achieving the requisite efficiency, selectivity and stability for industrial applications poses a persistent challenge. Here, we report the synthesis of 2D mesoporous Ni single atom catalysts in N‐doped carbon framework via a bottom‐up interfacial assembly strategy. The 2D mesoporous Ni−N−C catalyst showcases an ultrathin thickness (~6.7 nm) with well‐distributed 5 to 40 nm‐width mesopores in plane and a high surface area. As a result, the Ni single atom sites with a high density (~6.0 wt %) are almost completely exposed and can be accessible, and the mass transfer can be greatly promoted even at high current densities. Thus, a high current density of 446 mA cm−2 with >95 % CO selectivity in a flow cell can be obtained. Concurrently, the catalyst demonstrates an impressive stability, maintaining a 50‐hours continuous electrolysis in the membrane electrode assembly test and achieving an energy efficiency of 42 %. Finite element analysis reveals that the 2D mesoporous design enhances CO2 diffusion, ensuring efficient adsorption and swift CO desorption at high current densities. Our study paves a way for the fabrication of 2D mesoporous single atom catalysts with nearly 100 % accessibility and expedited mass transport. 2D mesoporous Ni single atom catalysts in the N‐doped carbon framework with a high density (~6.0 wt %) and ~100 % accessibility are synthesized via a bottom‐up interfacial assembly strategy, which deliver a high current density of 446 mA cm−2 with >95 % CO selectivity in the electrochemical CO2 reduction.