Boosting the Direct Coupling of CH 4 to C 2 H 4 via Plasma Catalysis over CuO/ZrO 2 ‐Al 2 O 3 Catalyst

ABSTRACT Non‐thermal plasma is considered a promising technology for driving non‐oxidative methane coupling at ambient temperature, but it suffers from low ethylene (C 2 H 4 ) selectivity due to the lack of efficient catalysts. Herein, we combine earth‐abundant CuO with easily prepared ZrO 2 ‐Al 2 O 3 mixed oxides for efficient coupling of methane to C 2 products in non‐thermal plasma. The catalyst demonstrates 23% CH 4 conversion, with C 2 and C 2 H 4 fractions in the gas products reaching 80.5% and 45.9%, respectively. Notably, CuO undergoes in‐situ reconstruction in plasma into hybrid CuO‐Cu 2 O‐Cu species with strong interactions during the reaction, which contributes to the high C 2 H 4 production. DFT calculation and in‐situ plasma‐coupled FTIR spectroscopy reveal that the formed Cu‐CuO interfaces preferentially stabilize * CH 2 intermediates to promote C═C bond formation. The electron transfer between the phases creates an electron‐enriched CuO surface, which suppresses the over‐cracking of activated CH x radicals to carbon deposition, thereby enhancing C 2 selectivity. Furthermore, the surface‐modulated acidity of ZrO 2 ‐Al 2 O 3 support promotes the dispersion of Cu x O and generates abundant Cu/CuO interfaces, which promote CH 4 activation, thereby collectively enhancing the coupling efficiency. This work provides insights into the role of catalyst reconstruction under plasma conditions in determining the catalytic performance, offering a practical strategy for designing high‐performance catalysts for plasma‐driven processes.