Spontaneous Nano‐ZrO 2 Exsolution from Ni‐Zr‐O Mixed Oxides Enables Facile Fabrication of ZrO 2 /Ni Inverse Catalysts for Efficient CO x Methanation

Abstract Ni‐based inverse catalysts with nano‐oxide dispersed on metallic substrates have emerged as promising candidates for low‐temperature CO 2 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‐ZrO 2 segregation on the metallic Ni matrix. The formation evolution of inverse configuration is elucidated through comprehensive ex situ/in situ characterizations. X‐ray photoelectron spectroscopy reveals the electron transfer between the exsolved ZrO 2 and the Ni matrix, indicating the presence of metal‐oxide interactions. The prepared ZrO 2 /Ni inverse catalyst achieves ∼90% CO 2 conversion and >99% CH 4 selectivity at low‐temperature of 200 °C, and also demonstrates excellent catalytic performance and dynamic operational stability in complex CO x hydrogenation reactions, validating its industrial applicability under realistic syngas‐equivalent feedstock conditions.