Microfluidic Printing‐Induced Dynamic Splitting of Conductive MOF to Expose High‐Density Active Sites for Boosted CO 2 Electroreduction

ABSTRACT Electrocatalytic CO 2 reduction (CO 2 RR) is vital for carbon recycling, yet scalable production of well‐defined catalysts remains challenging. Herein, we develop a rapid and scalable microfluidic printing strategy that enables dynamic splitting and directional construction of conductive metal‐organic framework (cMOF). Within the confined microfluidic channel, the shear forces induced by laminar flow play a dominant role in effectively suppressing interlayer interactions along the vertical direction, while simultaneously promoting 2D in‐plane crystallization. Consequently, cMOF with preferentially exposed (001) planes are formed within only several minutes. Compared with the conventional perpendicular rod‐like ST‐cMOF, microfluidic‐processed MF‐cMOF Qx/ty series exhibit ripple‐like ultrathin lamellar with the substantially reduced thickness of 11–2 nm. Such ultra‐thin features dramatically increase the density of accessible active sites, enhancing reactivity toward CO 2 RR. Besides, benefiting from the continuous flow and high throughput, the optimized MF‐cMOF Q1.28/t5 achieves a remarkable yield of 0.29 g h −1 and an ultrahigh space‐time yield of 502 kg m −3 day −1 , representing 282‐fold enhancement over conventional synthesis. Moreover, MF‐cMOF Q1.28/t5 delivers CH 4 FE of 79.6 % at −1.2 V vs. RHE, outperforming a 1.8‐fold improvement of ST‐cMOF. This work establishes microfluidic printing as an effective strategy for structurally defined MOF and highlights the potential for sustainable and industrially scalable CO 2 electroreduction.