Inside‐Out Joule Heating Enables Coke‐Resistant Dry Reforming of Methane to Near‐Stoichiometric Syngas Over LDH‐Derived NiCo Catalysts

ABSTRACT Electrifying endothermic reactions offers a promising route toward sustainable chemical manufacturing, yet its practical implementation is constrained by inefficient outside‐in heat delivery. Herein, we report a Joule‐heating catalyst, NiCo/(Ni,Co)O‐AlO x /Ti, derived from layered double hydroxides (LDHs) rooted onto a Ti scaffold. This monolithic architecture establishes intimate electrical‐thermal coupling and creates an inside‑out thermal field that generates heat directly at the catalytic interface, shortening the heat‐transfer pathway and mitigating reaction‐induced catalyst‐surface cooling. Experimentally validated multiphysics simulations resolve the resulting inverted temperature field and reduced source‐to‐surface temperature drop compared with outside‐in furnace heating. Guided by this thermal design principle, the optimized Ni:Co = 2:1 catalyst achieves a high rate of 6.65 mmol·g Ni(Co) −1 ·s −1 with a near‐unity H 2 /CO ratio, together with stable operation over 200 h and markedly suppressed carbon accumulation. Co‐incorporation enriches vacancy‐associated defect sites in the oxide lattice, promoting CO 2 activation through carbonate intermediates and reducing the energy barrier for carbonate‐mediated carbon removal. These findings demonstrate how interfacial heat‐delivery engineering can be coupled with defect‐modulated catalyst design to advance electrified endothermic catalysis.