Ni 3 (HITP) 2 @PTFE Molecular Fence Enables Selective C 2 Coupling in Methane Contact‐Electro‐Catalysis

Contact‐Electro‐Catalysis (CEC) enables methane activation under ambient conditions; however, the poorly understood interfacial active sites and uncontrolled evolution of reactive radical intermediates cause methane conversion to remain dominated by C 1 oxygenation rather than selective C─C coupling. Herein, we assemble the established Ni 3 (HITP) 2 framework (HITP = 2,3,6,7,10,11‐hexaiminotriphenylene) on PTFE (polytetrafluoroethylene) to construct a molecular fence interface integrating Ni–N 4 sites with spatial confinement for selective C 2 coupling. During CEC, contact electrification at the PTFE–water interface supports radical generation for methane conversion, while the coupled Ni–N 4 sites further facilitate O 2 activation and modulate reactive species utilization. Simultaneously, the porous Ni 3 (HITP) 2 outer layer shows enhanced CH 4 uptake near the charged interface and is proposed to favor C─C coupling by promoting local methane enrichment and retention of methane‐derived intermediates. As a result, methane conversion is redirected from C 1 oxygenation toward selective C 2 coupling under ambient conditions, delivering a C 2 yield of 0.58 mmol g −1 h −1 with 82.4% selectivity. In situ spectroscopy and density functional theory calculations support a mechanistic model in which interfacial Ni–N 4 sites and the porous framework jointly influence reactive‐species utilization and methane‐derived intermediate reactions, favoring pathway‐selective methane CEC.