Circumventing Scaling Relations in Photocatalytic Non‐Oxidative Coupling of Methane via Breaking Temporal Uniformity by Localized Surface Plasmon Resonance

ABSTRACT Catalytic activity generally encounters limitations imposed by scaling relations where the adsorption strengths of different adsorbates are highly correlated. Here, we present a time‐breaking uniformity strategy to circumvent this constraint: independently modulating the adsorbate‐catalyst bonding strength in separate time frames via a transient alternating electric field. Employing the non‐oxidative coupling of methane as a model reaction, we develop the Au@TiO 2 core–shell catalyst composed of an Au core providing visible‐triggered alternating electric fields through localized surface plasmon resonance (LSPR) and a TiO 2 shell for photocatalysis in the ultraviolet region. This catalyst achieves CH 4 ‐to‐C 2 H 6 activity of 1.66 mmol g −1 h −1 and a high quantum efficiency of 5.2% at room temperature under ambient pressure. Mechanistic studies reveal that the reaction followed the gas‐phase ·CH 3 coupling pathway. The alternating electric field generated by LSPR leads to a net enhancement in both CH 4 adsorption and ·CH 3 desorption, thereby circumventing the scaling relations.