Spontaneous Nano‐ZrO2 Exsolution from Ni‐Zr‐O Mixed Oxides Enables Facile Fabrication of ZrO2/Ni Inverse Catalysts for Efficient COx Methanation

Ni‐based inverse catalysts with nano‐oxide dispersed on metallic substrates have emerged as promising candidates for low‐temperature CO2 methanation, but it remains challenging in facile synthesis of well‐dispersed oxide‐metal interactions. Herein, a spontaneous oxide exsolution strategy for the fabrication of Ni‐based inverse catalyst via monodispersed Zr species of Ni‐Zr‐O mixed oxide is demonstrated, where precisely tailored calcination and reduction of the mixed oxide enable in situ nano‐ZrO2 segregation on the metallic Ni matrix. The formation evolution of inverse configuration is elucidated through comprehensive ex/in situ characterizations. X‐ray photoelectron spectroscopy reveals the electron transfer between the exsolved ZrO2 and the Ni matrix, indicating the presence of metal‐oxide interactions. The prepared ZrO2/Ni inverse catalyst achieves ~90% CO2 conversion and >99% CH4 selectivity at low‐temperature of 200 °C, and also demonstrates excellent catalytic performance and dynamic operational stability in complex COx hydrogenation reactions, validating its industrial applicability under realistic syngas‐equivalent feedstock conditions.