Rapid Joule‐Heating‐Induced Non‐Equilibrium Exsolution in Perovskite Oxides for Enhanced Photothermal <scp> CO ₂ </scp> Methanation

Achieving selective CO 2 methanation under photothermal conditions requires catalysts capable of maintaining non‐equilibrium interfacial states that balance reduction and oxidation processes—an ability rarely attainable through conventional thermal synthesis. Here, we propose a rapid Joule‐heating strategy that injects energy in a kinetically non‐equilibrium, current‐induced manner, triggering rapid exsolution of nanoparticles and electronic reconstruction within seconds. This approach creates LaNiO 3 ‐La 2 NiO 4 heterostructures embedded with socketed alloying Ni—Fe nanoparticles, where the coupled oxygen migration and charge redistribution give rise to electronically modulated metal/oxide interfaces. The kinetically confined process produces finely dispersed, electronically asymmetric active sites while avoiding the structural degradation typical of slow thermal treatments. The optimized catalyst (LNF‐JH1100) achieves a CH 4 production rate of 166.5 mmol g −1 h −1 with &gt;97% selectivity at 350 °C, showing a remarkable activity, selectivity, and stability. Combined spectroscopic and theoretical analyses reveal that this non‐equilibrium interface modulates the local electron density and intermediate binding sequence, and is associated with a shift in the dominant reaction pathway from a single HCOOH‐mediated surface hydrogenation pathway prone to CO release to a cooperative HCOO/HCOOH cycle that promotes direct CH 4 formation. This work demonstrates the potential of rapid Joule heating as an effective route to couple structural exsolution with electronic reconfiguration, offering new opportunities for the rational design of adaptive, high‐performance photothermal catalysts.