In this work, a rational catalyst design based on interfacial architecture engineering is proposed for low-temperature dry methane reforming (DMR) at 550 °C. Ni-based catalysts containing 10 wt% Ni were developed on a γ-Al₂O₃ support modified with 9 wt% MgO–1 wt% ZrO₂. Zirconia promoters were introduced either by dry impregnation or via an ammonia vapor-assisted route to construct a Ni–NiO–ZrO₂ interfacial network. The effects of ZrO₂ content (0, 1, and 3 wt%) and synthesis route on metal–support interactions, oxygen mobility, and coke resistance were systematically investigated. ZrO₂ promotion increased the fraction of reducible Ni species and preferentially enhanced CO₂ activation, thereby promoting the reverse water–gas shift (RWGS) reaction and lowering the H₂/CO ratio. In contrast, ammonia vapor-assisted preparation induced the formation of an LDH-derived Ni–NiO–ZrO₂ surface network, which increased the concentration of surface-accessible Ni species, suppressed excessive zirconia coverage, and significantly improved apparent oxygen mobility. These synergistic structural features are consistent with enhanced oxygen-assisted carbon removal and improved coke management through regulation of the nature of carbon species, leading to more balanced activation of CH₄ and CO₂. Overall, this study provides insights into interfacial structure–performance relationships for designing efficient Ni-based catalysts for CO₂ utilization.

This study investigates the development of Ni-based catalysts for low-temperature dry methane reforming (DMR) at 550 °C. The catalysts were prepared by dispersing Ni on γ-Al₂O₃ modified with 9 wt% MgO and 1 wt% ZrO₂, while 10 wt% Ni–x wt% ZrO₂ promoters (0, 1, and 3 wt%) were introduced using the incipient wetness impregnation method. A Ni–NiO–ZrO₂ surface network was generated on the 10 wt% Ni–3 wt% ZrO₂ catalyst via an ammonia vapor–assisted impregnation route. The ZrO₂ promoter strengthened the metal–support interaction, which increased the total amount of reducible Ni while shifting the reduction to higher temperatures. This modification also promoted CO₂ activation relative to CH₄, thereby enhancing the RWGS pathway and lowering the H₂/CO ratio. In contrast, the Ni–NiO–ZrO₂ network formed through the ammonia-assisted method increased the concentration of surface-accessible Ni, reduced excessive coverage by ZrO₂, and significantly improved oxygen mobility. These features facilitated continuous oxygen transfer, enhanced coke oxidation, and ensured a more balanced activation of both reactants. Overall, the combined structural and functional synergies achieved through promoter optimization and the ammonia vapor–assisted preparation method resulted in superior catalytic activity and selectivity for DMR at 550 °C.